A fluoride glass-ceramics containing ErF 3 crystalline phase and its preparation method

Abstract

The present invention discloses a novel fluoride glass-ceramics containing ErF3 crystal phase with extremely high red light emission intensity and a preparation method thereof. Its composition is ZrF4-BaF2-AlF3-NaF-ErF3, and the molar percentage of its ErF3 component is 15-27 mol.%. This material is a glass-ceramics formed by a large number of ErF3 microcrystals uniformly distributed in a fluoride glass matrix. Different from low-concentration Er-doped fluoride glasses that emit green light, this material has extremely strong red fluorescence emission intensity and is expected to be applied in fields such as laser display, visual imaging, and visual detection of lasers.

Description

Technical Field

[0001] The present invention relates to the field of material preparation, and particularly to a fluoride microcrystalline glass-ceramics containing ErF 3 crystalline phase and a preparation method thereof. Background Art

[0002] Fluoride microcrystalline glass-ceramics are mid-infrared materials formed from pure fluoride materials and containing a crystalline phase and a glass phase. It has been found that in rare-earth ion-doped fluoride microcrystalline glass-ceramics, due to the different crystal environments of rare-earth ions having different energy-level transition probabilities, it is expected to regulate the transition energy levels of rare-earth ions by controlling the composition and structure of the microcrystals in the fluoride microcrystalline glass-ceramics, so as to enhance the emission intensity in the target wavelength band.

[0003] In Er-ion-doped fluoride glass materials, Er ions have the characteristics of both green fluorescence emission and red fluorescence emission, and the green light emission intensity is slightly stronger than the red light emission intensity. Due to the sensitivity of the human eye to green light, the material usually exhibits green fluorescence under 980 nm pumping. Currently, there is no report on Er-ion-doped fluoride microcrystalline glass-ceramics having high-intensity red fluorescence emission. Summary of the Invention

[0004] The purpose of the present invention is to provide a fluoride microcrystalline glass-ceramics containing ErF 3 crystalline phase and a preparation method thereof. This glass-ceramics is different from the green fluorescence emission of traditional Er-doped fluoride glasses: it has extremely strong red light emission intensity.

[0005] The technical solution of the present invention is as follows:

[0006] The present invention first provides a fluoride microcrystalline glass-ceramics containing ErF 3 crystalline phase, and its component molar percentages are:

[0007] ZrF 4 : 55-65 mol.%;

[0008] BaF 2 -AlF 3 -NaF: 18-25 mol.%;

[0009] ErF 3 : 15-27 mol.%.

[0010] Preferably, the molar percentage of the said ErF 3 is: 17-24 mol.%.

[0011] Preferably, the said BaF 2 , AlF 3The molar percentages of each component of BaF and NaF are BaF 2 : AlF 3 : NaF = (12 - 19):(1 - 3):(1 - 3) mol%.

[0012] More preferably, for the fluoride microcrystalline glass-ceramics containing ErF 3 crystalline phase, the molar percentages of its components are as follows:

[0013] ZrF 4 : 62 mol%;

[0014] BaF 2 : 15 mol%;

[0015] AlF 3 : 2 mol%;

[0016] NaF: 2 mol%;

[0017] ErF 3 : 19 mol%.

[0018] The present invention also provides a method for preparing the aforementioned fluoride microcrystalline glass-ceramics containing ErF 3 crystalline phase, which includes the following steps:

[0019] S1. Raw material preparation: In an environment filled with inert gas, weigh the raw materials according to the molar percentages of the components of the fluoride microcrystalline glass-ceramics containing ErF 3 crystalline phase, fully grind them and then pass through a 100-mesh sieve. After the particle size meets the standard, fully mix the raw material components;

[0020] S2. Melting: In the same environment as in S1, transfer the uniformly mixed raw materials to a platinum crucible, place the crucible in a high-temperature heating furnace with a furnace temperature of 900 - 1000 °C, cover it with a lid with a ventilation pipe, and continuously pass 100 ml / min of oxygen through the ventilation pipe. After 15 minutes, stop passing oxygen, and melt for 50 - 70 minutes to obtain a glass melt;

[0021] S3. Casting: Use platinum tongs to hold the platinum crucible and cast the glass melt into a brass mold preheated to 200 - 220 °C to obtain a formed glass-ceramic.

[0022] Preferably, in step S1, the environment filled with inert gas is an environment filled with N 2 or Ar and with a water content less than 20 ppm.

[0023] Preferably, in step S2, the furnace temperature of the high-temperature heating furnace is 900 °C and the melting time is 50 minutes.

[0024] Preferably, in step S3, the temperature of the brass mold is 220 °C.

[0025] Compared with the prior art, the technical effects of the present invention are as follows:

[0026] As is known from the current prior art, in the ZrF 4 -BaF 2 -AlF 3 -NaF-ErF 3 system glass, Er has the fluorescence characteristics of green light and red light, and the emission intensity of green light is slightly stronger than that of red light. Due to the sensitivity of the human eye to green light, the material usually exhibits green fluorescence under 980 nm pumping. In the prior art research reported currently, both glass and microcrystalline ceramics have strong green fluorescence and show obvious green light emission to the naked eye, and there is no report of red fluorescence. The present invention creatively proposes to use high-concentration Er ion doping by designing the components of the fluoride system and regulating the molar ratio of ErF 3 . As the concentration of ErF 3 increases, the concentration of Er ions in the microcrystals and ceramics increases, the distance between Er ions in the glass-ceramics decreases, and the crystal environment changes, resulting in a certain degree of Er ion concentration quenching effect, thereby reducing the green light intensity and then realizing high-intensity red fluorescence emission different from low-concentration doping, achieving unexpected technical effects. The present invention discloses for the first time the result of high-intensity red fluorescence emission in Er ion-doped fluoride glass-ceramics. This material is expected to be applied in the fields of laser display, visual imaging, and visual detection of lasers. Description of the Drawings

[0027] Figure 1 XRD diffraction schematic diagram of the fluoride glass-ceramics containing ErF 3 crystalline phase in Example 1.

[0028] Figure 2 Up-conversion fluorescence spectrum of the fluoride glass-ceramics containing ErF 3 crystalline phase in Example 1.

[0029] Figure 3 Up-conversion fluorescence spectrum of the fluoride glass-ceramics containing ErF 3 crystalline phase in Comparative Example 1. Detailed Embodiments

[0030] The following specific embodiments illustrate the present invention by way of examples and help to further understand the present invention. However, the specific details of the embodiments are only for the purpose of illustrating the present invention and do not represent all the technical solutions under the concept of the present invention. Therefore, it should not be construed as a limitation to the overall technical solution of the present invention. Some non-substantive additions and modifications that do not deviate from the concept of the present invention in the view of those skilled in the art, such as simple replacement or substitution of technical features with the same or similar technical effects, all fall within the protection scope of the present invention.

[0031] Example 1

[0032] In an environment filled with N 2 gas and with a water content of less than 20 ppm, according to the molar percentage, 65ZrF 4 -15BaF 2 -2AlF 3 -3NaF-15ErF 3 Weigh 30 g of raw materials, grind them and pass through a 100-mesh sieve, then mix them evenly, transfer them to a platinum crucible, place the crucible in a high-temperature furnace with a furnace temperature of 900 °C, continuously introduce oxygen with a flow rate of 100 ml / min for 15 minutes, and melt for a total of 50 minutes to obtain a glass melt. Pour the glass melt into a brass mold preheated to 220 °C to obtain a formed glass-ceramic.

[0033] The test results of the obtained glass-ceramic are as follows:

[0034] (1) The XRD diffraction schematic diagram of the obtained glass-ceramic is as Figure 1 shown. Obvious ErF 3 crystalline phase characteristic peaks can be seen in the figure, indicating that the crystalline phase in the glass-ceramic is ErF 3 ;

[0035] (2) The 980 nm pump laser test spectrum of it is as Figure 2 shown, and it has extremely strong red fluorescence intensity.

[0036] Example 2

[0037] In an environment filled with N 2 gas and with a water content of less than 20 ppm, according to the molar percentage, 60ZrF 4 -16BaF 2 -2AlF 3 -2NaF-20ErF 3 Weigh 50 g of raw materials, grind them and pass through a 100-mesh sieve, then mix them evenly, transfer them to a platinum crucible, place the crucible in a high-temperature furnace with a furnace temperature of 950 °C, continuously introduce oxygen with a flow rate of 100 ml / min for 15 minutes, and melt for a total of 60 minutes to obtain a glass melt. Pour the glass melt into a brass mold preheated to 220 °C to obtain a formed glass-ceramic.

[0038] Examples 3 - 9

[0039] The experimental procedures of Examples 3 - 9 are the same as those of Examples 1 and 2, except for the parameter values. The specific parameters are shown in Table 1.

[0040] Table 1. Parameter values of each example

[0041]

[0042] In the XRD diffraction schematic diagrams of the glass ceramics obtained in Examples 1 - 9, obvious characteristic peaks of the ErF3 crystal phase can be seen. At the same time, the 980 - nm pump laser test spectra of them all show extremely strong red fluorescence intensity.

[0043] Comparative Example 1:

[0044] In an environment filled with N 2 gas and with a water content of less than 20 ppm, 30 g of raw materials were weighed, ground, passed through a 100 - mesh sieve, and then evenly mixed. The mixture was transferred to a platinum crucible, and the crucible was placed in a high - temperature furnace with a furnace temperature of 900 °C. Oxygen with a flow rate of 100 ml / min was continuously introduced for 15 minutes. After melting for 50 minutes, a glass melt was obtained. The glass melt was cast into a brass mold preheated to 220 °C to obtain a formed glass ceramic. 4 -17BaF 2 -3AlF 3 -20NaF - 7ErF 3 The test results of the obtained glass ceramic are as follows:

[0045] The 980 - nm pump laser test spectrum of it is as

[0046] shown, with green and red fluorescence emissions of similar intensity, showing obvious green fluorescence under naked - eye observation. Figure 3 As shown in

[0047] In summary, from the test results of Example 1 and Comparative Example 1, it can be seen that by adopting the technical solution provided by the present invention, with high - concentration Er ion doping, as the concentration of ErF 3 increases, the concentration of Er ions in the microcrystals and ceramics increases, the distance between Er ions in the glass - ceramics decreases, the crystal environment changes, and it has a certain degree of Er ion concentration quenching effect, thus reducing the green light intensity (as shown in Figure 2 and Figure 3 ), thereby achieving high - intensity red fluorescence emission different from that of low - concentration doping and obtaining unexpected technical effects.

[0048] The foregoing is only a preferred embodiment of the present invention and is not intended to limit it; although the present patent has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention are all included within the protection scope of the present invention.

Claims

1. A fluoride glass-ceramic containing an ErF 3 crystalline phase It is characterized in that The molar percentage of its components is: ZrF 4 : 55 to 65 mol.%; BaF 2 -AlF 3 -NaF: 18 - 25 mol.% ErF 3 : 15 to 27 mol%.

2. The fluoride glass-ceramics containing ErF 3 crystalline phase It is characterized in that The described ErF 3 has a molar percentage of: 17 to 24 mol.%.

3. The fluoride glass-ceramics containing ErF 3 crystalline phase It is characterized in that The described BaF 2 , AlF 3 and the molar percentages of each component of NaF are BaF 2 : AlF 3 : NaF = (12 - 19):(1 - 3):(1 - 3) mol%.

4. The fluoride glass-ceramics containing ErF 3 crystalline phase, It is characterized in that The molar percentage of its components is: ZrF 4 : 62 mol%; BaF 2 : 15 mol%; AlF 3 : 2 mol%; NaF: 2 mol.%; ErF 3 : 19 mol%.

5. A method for preparing a fluoride glass-ceramics containing an ErF 3 crystalline phase as claimed in claim 1 It is characterized in that It includes the following steps: S1. Raw material preparation: In an environment filled with inert gas, weigh the raw materials according to the molar percentage of the components of the fluoride glass-ceramics containing ErF 3 crystalline phase, grind them thoroughly, pass through a 100-mesh sieve, and fully mix the raw material components after the particle size meets the standard; S2. Melting: In the same environmental atmosphere as S1, transfer the uniformly mixed raw materials to a platinum crucible, place the crucible in a high-temperature heating furnace with a furnace temperature of 900 - 1000 °C, cover it with a lid with a ventilation pipe, and continuously introduce oxygen at 100 ml / min through the ventilation pipe. After 15 minutes, close the introduction of oxygen, and after melting for 50 - 70 minutes, obtain the glass melt; S3. Casting: Use platinum tongs to hold the platinum crucible, and cast the glass melt into a brass mold preheated to 200 - 220 °C to obtain the formed glass-ceramics.

6. The preparation method of the fluoride glass-ceramics containing ErF 3 crystalline phase, It is characterized in that In step S1, the inert gas-filled ambient atmosphere is an ambient atmosphere filled with N 2 or Ar and having a water content of less than 20 ppm.

7. The preparation method of fluoride glass-ceramics containing ErF 3 crystalline phase, It is characterized in that In step S2, the furnace temperature of the high-temperature heating furnace is 900 °C, and the melting time is 50 minutes.

8. The preparation method of fluoride glass-ceramics containing ErF 3 crystalline phase, It is characterized in that In step S3, the temperature of the brass mold is 220 °C.

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