CN106007365B - Prepare rare earth ion Tm3+Method of alumina silicate glass being co-doped with ZnO nano crystalline substance and products thereof and application - Google Patents

Abstract

Rare earth ion Tm is prepared the invention discloses a kind of³⁺The method for the alumina silicate glass being co-doped with ZnO nano crystalline substance first mixes silica, aluminium oxide, potassium carbonate, zinc oxide and thulium oxide, after heating melting, is poured on copper coin or graphite cake and is cooled to room temperature to obtain toughened glass；Silica, aluminium oxide, potassium carbonate, zinc oxide and thulium oxide molar ratio be 44:11:10:35:0.005~0.05；After toughened glass is warm, annealed glass is obtained, then thermally treated obtains rare earth ion Tm³⁺The alumina silicate glass being co-doped with ZnO nano crystalline substance.The present invention provides a kind of rare earth ion Tm³⁺The preparation method for the alumina silicate glass being co-doped with ZnO nano crystalline substance, simple process are of low cost.The total transmitting of white light may be implemented in the product being prepared.

Description

Method for preparing aluminosilicate glass co-doped with rare earth ion Tm3+ and ZnO nanocrystals and its products and applications

technical field

The invention relates to the field of preparation of aluminosilicate glass, in particular to a method for preparing aluminosilicate glass co-doped with rare earth ions Tm3 ⁺ and ZnO nanocrystals, as well as its product and application.

Background technique

Compared with traditional lighting materials, white LEDs have the characteristics of high luminous efficiency, low energy consumption, fast response, and long life. At present, the preparation of commercial white LEDs mainly utilizes GaN chips with blue light emission and YAG:Ce phosphors with yellow light emission through resin encapsulation. This type of white LED has the disadvantages of low color rendering index, poor color temperature stability, short service life caused by packaging resin, and complicated manufacturing process.

Due to the characteristics of stable physical and chemical properties, simple preparation process and easy preparation into various shapes, white light-emitting glass can improve the performance of white light LEDs to a certain extent. White light-emitting glass is generally realized by doping rare earth ions in the glass. Rare earth ions have narrow and strong emission bands in the visible band and are widely used in the preparation of fluorescent lamps and white LEDs. However, white light glasses with narrow emission bands have low color rendering index, so it is very important to introduce broad emission bands into glasses doped with rare earth ions. The introduction of broad emission bands can be achieved by growing crystals with luminescent properties in glass species.

ZnO crystals have broad-band emission in the visible band and are therefore an important candidate crystal. If the co-emission of rare earth ions and ZnO crystals can be realized in the glass to achieve white light emission, then this white light emitting glass co-doped with rare earth ions and nano-ZnO crystals can be used as a candidate material for improving white LEDs.

The Chinese patent document with the publication number CN102225845A discloses a method for preparing zinc aluminosilicate glass co-doped with zinc oxide nanocrystals and rare earth ions. The steps are as follows: firstly, zinc oxide powder, silicon dioxide , aluminum oxide, potassium oxide and rare earth oxides are uniformly mixed, then melted at high temperature, cooled to room temperature, and then heat-treated at 600-700°C to obtain the product. The rare earth oxide used in this patent document is at least one of europium oxide, dysprosium oxide and erbium oxide. The analysis of the test results shows that the products prepared by using the above rare earth oxides have stronger emission intensity at around 400nm, but they have not achieved white light co-emission, which shows that not all rare earth ions and ZnO crystal co-doping can achieve white light co-emission. emission.

Contents of the invention

The invention provides a method for preparing aluminosilicate glass co-doped with rare earth ions Tm3 ⁺ and ZnO nanocrystals, with simple and convenient process and low cost. The prepared product can realize co-emission of white light.

The invention discloses a method for preparing aluminosilicate glass co-doped with rare earth ions Tm3 ⁺ and ZnO nanocrystals, comprising the following steps:

1) Mix silicon oxide, aluminum oxide, potassium carbonate, zinc oxide and thulium oxide, heat and melt, pour it on a copper plate or graphite plate and cool to room temperature to obtain tempered glass;

The molar ratio of silicon oxide, aluminum oxide, potassium carbonate, zinc oxide and thulium oxide is 44:11:10:35:0.005～0.05;

2) The tempered glass obtained in step 1) is kept warm to obtain annealed glass, and then heat-treated to obtain the aluminosilicate glass co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals.

Preferably, in step 1), the heating and melting temperature is 1500°C, the heating rate is 7-10°C/min, and the heat preservation is 1-3h.

Preferably, in step 1), the temperature of the copper plate or graphite plate is 300-500°C.

Preferably, in step 2), the tempered glass is kept at 600° C. for 1-3 hours, and the heating rate is 3-5° C./min.

Preferably, in step 2), the temperature of the heat treatment is 730-750° C., and the time is 1-10 min.

The invention also discloses the aluminosilicate glass co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals prepared according to the above method and its application in white light emission.

Compared with prior art, the present invention has following advantage:

The preparation method of the present invention is simple, the raw material cost is low, the whole preparation process is carried out in the air atmosphere, no special device is needed, and the required equipment is simple.

In the present invention, rare earth ions Tm ³⁺ and ZnO nanocrystals are co-doped in the aluminosilicate glass matrix for the first time, and the ZnO nanocrystals are evenly distributed in the aluminosilicate glass, with a diameter of about 10nm. The ZnO nanocrystals emit in the orange-red band, and The blue emission of rare-earth ions Tm ³⁺ interacts to produce white emission, which can be used to prepare white LEDs.

Description of drawings

Fig. 1 is the X-ray diffraction pattern of the aluminosilicate glass that the rare earth ion Tm of embodiment 1 and embodiment ⁴ prepares respectively and ZnO nanocrystal co-doped, and provides the X-ray of the sample without heat treatment in embodiment 1 Ray diffraction pattern as a comparison;

2 is the emission spectrum of the aluminosilicate glass co-doped with rare earth ions Tm3 ⁺ and ZnO nanocrystals prepared respectively in Examples 1 to 4, and provides the emission spectrum of the sample without heat treatment in Example 1 as a comparison;

Fig. 3 is the CIE chromaticity diagram of the emission spectrum of the aluminosilicate glass co-doped with the rare earth ion Tm3 ⁺ and ZnO nanocrystals prepared respectively in Examples 1 to 4;

4 is a CIE chromaticity diagram of aluminosilicate glasses co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals prepared in Examples 1 to 3 and products prepared in Comparative Examples.

Detailed ways

The present invention will be further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

Example 1

1) Put silicon oxide, aluminum oxide, potassium carbonate, zinc oxide, and thulium oxide powder into an agate mortar, mix well and pour into a 30ml crucible, the moles of silicon dioxide, aluminum oxide, potassium carbonate, zinc oxide, and thulium oxide The ratio is 44:11:10:35:0.05;

2) Put the crucible in step 1) into a high-temperature furnace, heat up to 1500°C at a heating rate of 7°C/min, keep warm for 2 hours to melt, pour the molten glass on a copper plate or graphite plate at 300°C and cool to room temperature to obtain quenching Glass;

3) Then put the tempered glass into a muffle furnace, raise the temperature to 600°C at a heating rate of 3°C/min, and then keep it at 600°C for 2 hours to obtain annealed glass;

4) The annealed glass was heat-treated at 750° C. for 5 min to obtain an aluminosilicate glass co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals.

Curve a among Fig. 1 is the X-ray diffraction pattern of the annealed glass without the heat treatment of step 4), is the ^Tm doped aluminosilicate glass when not generating nanocrystal; Curve b is the rare earth prepared by the present embodiment The X-ray diffraction pattern of the aluminosilicate glass co-doped with ion Tm ³⁺ and ZnO nanocrystals is the Tm ³⁺ doped aluminosilicate glass when nanocrystals are formed. Comparing the two curves, it can be seen that aluminosilicate glass doped with ZnO nanocrystals was obtained after heat treatment at 750°C for 5 minutes. Calculated by the Scherrer equation, the average diameter of ZnO crystals in the glass is 10 nm.

Curve a in Fig. 2 is Tm when not generating nanocrystal in the present embodiment ³⁺ doped aluminosilicate glass (the annealed glass without the heat treatment of step 4), curve b is when having nanocrystal to generate Tm ³⁺ doped aluminosilicate glass. Comparing curve a and curve b in the figure, it can be seen that in this example, except for the emission of Tm ³⁺ at 453nm, the aluminosilicate glass after heat treatment at 750°C for 5 minutes is one more than the aluminosilicate glass without heat treatment by 475 ~700nm broadband emission. It can be seen that there is co-emission of Tm ³⁺ and ZnO nanocrystals in the aluminosilicate glass co-doped with Tm ³⁺ and ZnO nanocrystals.

Point a in Figure 3 is the CIE chromaticity diagram of the aluminosilicate glass co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals prepared in this example at an excitation wavelength of 365 nm. The coordinates of point a in the CIE chromaticity diagram are (x=0.33, y=0.32), indicating that the aluminosilicate glass co-doped with Tm ³⁺ and ZnO nanocrystals prepared in this example has the property of white light emission.

Example 2

1) Put silicon oxide, aluminum oxide, potassium carbonate, zinc oxide, and thulium oxide powder into an agate mortar, mix well and pour into a 30ml crucible, the moles of silicon dioxide, aluminum oxide, potassium carbonate, zinc oxide, and thulium oxide The ratio is 44:11:10:35:0.01;

2) Put the crucible in step 1) into a high-temperature furnace, heat up to 1500°C at a heating rate of 8°C/min, keep warm for 2 hours to melt, pour the molten glass on a copper plate or graphite plate at 400°C and cool to room temperature to obtain quenching Glass;

3) Then put the tempered glass into a muffle furnace, raise the temperature to 600°C at a heating rate of 4°C/min and then keep it at 600°C for 2 hours to obtain annealed glass;

4) The annealed glass was heat-treated at 750° C. for 5 min to obtain an aluminosilicate glass co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals.

Curve c in FIG. 2 is the emission spectrum of the aluminosilicate glass co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals prepared in this example at an excitation wavelength of 365 nm. It can be seen from the figure that the aluminosilicate glass co-doped with Tm ³⁺ and ZnO nanocrystals prepared in this example has Tm ³⁺ emission at 453 nm and ZnO crystallite emission at 475-700 nm in a wide band at an excitation wavelength of 365 nm , illustrating the co-emission of Tm ³⁺ and ZnO nanocrystals in Tm ³⁺ and ZnO nanocrystals co-doped aluminosilicate glasses.

Point b in Figure 3 is the CIE chromaticity diagram of the aluminosilicate glass co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals prepared in this example at an excitation wavelength of 365 nm. The coordinates of point b in the CIE chromaticity diagram are (x=0.37, y=0.37), indicating that the aluminosilicate glass co-doped with Tm ³⁺ and ZnO nanocrystals prepared in this example has the property of white light emission.

Example 3

1) Put silicon oxide, aluminum oxide, potassium carbonate, zinc oxide, and thulium oxide powder into an agate mortar, mix well and pour into a 30ml crucible, the moles of silicon dioxide, aluminum oxide, potassium carbonate, zinc oxide, and thulium oxide The ratio is 44:11:10:35:0.005;

2) Put the crucible in step 1) into a high-temperature furnace, heat up to 1500°C at a heating rate of 9°C/min, keep warm for 2 hours to melt, pour the molten glass on a copper plate or graphite plate at 500°C and cool to room temperature to obtain quenching Glass;

3) Then put the tempered glass into a muffle furnace, raise the temperature to 600°C at a heating rate of 5°C/min and then keep it at 600°C for 2 hours to obtain annealed glass;

4) The annealed glass was heat-treated at 750° C. for 5 min to obtain an aluminosilicate glass co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals.

Curve d in FIG. 2 is the emission spectrum of the aluminosilicate glass co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals prepared in this example at an excitation wavelength of 365 nm. It can be seen from the figure that the aluminosilicate glass co-doped with Tm ³⁺ and ZnO nanocrystals prepared in this example has Tm ³⁺ emission at 453 nm and ZnO crystallite emission at 475-700 nm in a wide band at an excitation wavelength of 365 nm , illustrating the co-emission of Tm ³⁺ and ZnO nanocrystals in Tm ³⁺ and ZnO nanocrystals co-doped aluminosilicate glasses.

Point c in Figure 3 is the CIE chromaticity diagram of the aluminosilicate glass co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals prepared in this example at an excitation wavelength of 365 nm. The coordinates of point c in the CIE chromaticity diagram are (x=0.32, y=0.36), indicating that the aluminosilicate glass co-doped with Tm ³⁺ and ZnO nanocrystals prepared in this example has the property of white light emission.

Example 4

1) Put silicon oxide, aluminum oxide, potassium carbonate, zinc oxide, and thulium oxide powder into an agate mortar, mix well and pour into a 30ml crucible, the moles of silicon dioxide, aluminum oxide, potassium carbonate, zinc oxide, and thulium oxide The ratio is 44:11:10:35:0.05;

2) Put the crucible in step 1) into a high-temperature furnace, heat up to 1500°C at a heating rate of 10°C/min, keep warm for 2 hours to melt, pour the molten glass on a copper plate or graphite plate at 500°C and cool to room temperature to obtain quenching Glass;

3) Then put the tempered glass into a muffle furnace, raise the temperature to 600°C at a heating rate of 5°C/min and then keep it at 600°C for 2 hours to obtain annealed glass;

4) The annealed glass was heat-treated at 730° C. for 5 min to obtain an aluminosilicate glass co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals.

Curve c in Figure 1 is the X-ray diffraction spectrum of the aluminosilicate glass co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals prepared in this example. It can be seen from the figure that ZnO nanocrystals are formed in the glass. Calculated by the Scherrer equation (Scherrer equation), the average crystal diameter is 7 nm.

Curve e in FIG. 2 is the emission spectrum of the aluminosilicate glass co-doped with rare earth ions Tm ³⁺ and ZnO nanocrystals prepared in this example at an excitation wavelength of 365 nm. It can be seen from the figure that the aluminosilicate glass co-doped with Tm ³⁺ and ZnO nanocrystals prepared in this example has Tm ³⁺ emission at 453 nm and ZnO crystallite emission at 475-700 nm in a wide band at an excitation wavelength of 365 nm , illustrating the co-emission of Tm ³⁺ and ZnO nanocrystals in Tm ³⁺ and ZnO nanocrystals co-doped aluminosilicate glasses.

Point d in Figure 3 is the CIE chromaticity diagram of the aluminosilicate glass prepared in this example at an excitation wavelength of 365 nm. The coordinates of point d in the CIE chromaticity diagram are (x=0.37, y=0.38), indicating that the aluminosilicate glass co-doped with Tm ³⁺ and ZnO nanocrystals prepared in this example has the property of white light emission.

comparative example

The preparation process is the same as that in Example 1, except that in step 1), the molar ratio of silicon dioxide, aluminum oxide, potassium carbonate, zinc oxide, and thulium oxide is 44:11:10:35:0.1.

Figure 4 shows the CIE chromaticity diagrams of the products prepared in Examples 1 to 4 and this comparative example respectively. The comparison shows that as the doping concentration of Tm ³⁺ increases gradually, the emission of ZAS:x Tm ³⁺ glass-ceramic The color gradually moves from yellow through the white light region to the blue light region. Among them, when the doping concentration of Tm ³⁺ is 0.05mol%, the emission color of ZAS:x Tm ³⁺ glass ceramics is in the white light range, and when the doping concentration of Tm ³⁺ is 0.1mol%, the emission color of glass ceramics is The emission color is in the blue light range.

Claims (7)

1. a kind of preparing rare earth ion Tm³⁺The method for the alumina silicate glass being co-doped with ZnO nano crystalline substance, which is characterized in that including Following steps：

1) silica, aluminium oxide, potassium carbonate, zinc oxide and thulium oxide are mixed, after heating melting, is poured on copper coin or graphite cake It is cooled to room temperature to obtain toughened glass；

The silica, aluminium oxide, potassium carbonate, zinc oxide and thulium oxide molar ratio be 44:11:10:35:0.005~0.05；

2) after step 1) obtains toughened glass is warm, annealed glass is obtained, then thermally treated obtains the rare earth ion Tm³⁺The alumina silicate glass being co-doped with ZnO nano crystalline substance.

2. according to claim 1 prepare rare earth ion Tm³⁺The method for the alumina silicate glass being co-doped with ZnO nano crystalline substance, It is characterized in that, in step 1), the temperature of the heating melting is 1500 DEG C, and heating rate is 7~10 DEG C/min, heat preservation 1~ 3h。

3. according to claim 1 prepare rare earth ion Tm³⁺The method for the alumina silicate glass being co-doped with ZnO nano crystalline substance, It is characterized in that, in step 1), the temperature of the copper coin or graphite cake is 300~500 DEG C.

4. according to claim 1 prepare rare earth ion Tm³⁺The method for the alumina silicate glass being co-doped with ZnO nano crystalline substance, It is characterized in that, in step 2), the toughened glass keeps the temperature 1~3h at 600 DEG C, and heating rate is 3~5 DEG C/min.

5. according to claim 1 prepare rare earth ion Tm³⁺The method for the alumina silicate glass being co-doped with ZnO nano crystalline substance, It is characterized in that, in step 2), the temperature of the heat treatment is 730~750 DEG C, and the time is 1~10min.

6. rare earth ion Tm prepared by a kind of method according to Claims 1 to 5 any claim³⁺With ZnO nano crystalline substance The alumina silicate glass being co-doped with.

7. a kind of rare earth ion Tm according to claim 6³⁺The alumina silicate glass being co-doped with ZnO nano crystalline substance is sent out in white light The application hit.