Rare earth mixed transparent oxyfluoride glass ceramic and preparation process thereof

Abstract

A transparent glass ceramics of RE-doped oxyfluoride is proportionally prepared from SiO2, Al2O3, EnF2, MF2 and ReF3, where M is 2-valence alkali-earth metal ion chosen from Mg, Ca, Sr, and Ba and Re is 3-valence RE ion chosen from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, through high fusing and heat treating. It can be extensive used in laser, luminous and optical communication field.

Description

technical field

[0001] The invention relates to rare earth-doped transparent oxyfluoride glass ceramics and a preparation method thereof. Background technique

[0002] Rare earth ion-doped oxyfluoride glass-ceramics have attracted widespread attention for their potential applications in laser fibers, fiber amplifiers, and upconversion luminescence. By heat treatment of rare earth ion doped oxyfluoride glass, oxyfluoride glass ceramics uniformly distributed with fluoride nanocrystal phases can be obtained, and rare earth ions can be enriched in these fluoride nanocrystals as nucleating agents. Therefore, this kind of material can not only provide a low phonon energy environment of fluoride that is favorable for the luminescence of rare earth ions, but also contain a large amount of oxides in the matrix, and also have mechanical properties and chemical stability comparable to oxide glasses.

[0003] As early as the early 1990s, Y.Wang and J.0hwaki (“New Transparent Vitroceram...

Examples

Embodiment 1

[0021] By composition 47.6SiO 2 -19Al 2 o 3 -28.6CaF 2 -4.8ErF 3 Weigh high-purity rare earth fluoride ErF 3 , SiO 2 , Al 2 o 3 and CaF 2 , and mix the above raw materials evenly, put them into a high-purity corundum crucible or platinum crucible, put them into a furnace that has been heated to 1400°C to melt the raw materials into a liquid state, and make the melt uniform, and keep the melt temperature constant for 1 hour Finally, the crucible is quickly taken out from the high-temperature furnace, and the melt in the crucible is quickly poured on the mold to form a glass sample. The glass can be obtained after the nucleation heat treatment at 600°C for 0.5 hours and the crystallization heat treatment at 660°C for 2 hours. 2 Nanocrystalline glass ceramics. Under 980nm LD laser pumping, a strong and wide emission band can be produced near 1537nm. The half-maximum width of this strong and wide emission band is about 75nm (about 80nm for erbium-doped ZBLAN glass). The...

Embodiment 2

[0023] By composition 47.4SiO 2 -19Al 2 o 3 -28.4CaF 2 -4.7YbF 3 -0.5ErF 3 Weigh high-purity rare earth fluoride ErF 3 , YbF 3 , SiO 2 , Al 2 o 3 and CaF 2 , and mix the above raw materials evenly, put them into a high-purity corundum crucible or platinum crucible, put them into a furnace that has been heated to 1400°C to melt the raw materials into a liquid state, and make the melt uniform, and keep the melt temperature constant for 1 hour Finally, the crucible is quickly taken out from the high-temperature furnace, and the melt in the crucible is quickly poured on the mold to form a glass sample. The glass can be obtained after the nucleation heat treatment at 600°C for 0.5 hours and the crystallization heat treatment at 660°C for 2 hours. 2 Nanocrystalline glass ceramics. The present invention Er 3+ / Yb 3+ Co-doped glass ceramics, due to the co-doped Yb 3+ As a sensitizer, it can more effectively convert invisible near-infrared light into visible green and re...

Embodiment 3

[0025] By composition 47.6SiO 2 -9.5Al 2 o 3 -19ZnF 2 -19.1SrF 2 -4.8ErF 3 Weigh high-purity rare earth fluoride ErF 3 , SiO 2 , Al 2 o 3 , ZnF 2 and SrF 2, and mix the above raw materials evenly, put them into a high-purity corundum crucible or platinum crucible, put them into a furnace that has been heated to 1400°C to melt the raw materials into a liquid state, and make the melt uniform, and keep the melt temperature constant for 1 hour Finally, the crucible is quickly taken out from the high-temperature furnace, and the melt in the crucible is quickly poured on the mold to form a glass sample. The glass can be obtained after the nucleation heat treatment at 600°C for 0.5 hours and the crystallization heat treatment at 630°C for 1 hour. 2 Nanocrystalline glass ceramics. Under the pumping of 980nmLD laser, the glass ceramic can effectively convert infrared light into visible green light and red light, and the effective half maximum width of the infrared emission ...

technical field

[0001] The invention relates to rare earth-doped transparent oxyfluoride glass ceramics and a preparation method thereof. Background technique

[0002] Rare earth ion-doped oxyfluoride glass-ceramics have attracted widespread attention for their potential applications in laser fibers, fiber amplifiers, and upconversion luminescence. By heat treatment of rare earth ion doped oxyfluoride glass, oxyfluoride glass ceramics uniformly distributed with fluoride nanocrystal phases can be obtained, and rare earth ions can be enriched in these fluoride nanocrystals as nucleating agents. Therefore, this kind of material can not only provide a low phonon energy environment of fluoride that is favorable for the luminescence of rare earth ions, but also contain a large amount of oxides in the matrix, and also have mechanical properties and chemical stability comparable to oxide glasses.

[0003] As early as the early 1990s, Y.Wang and J.0hwaki (“New Transparent Vitroceram...

Examples

Embodiment 1

[0021] By composition 47.6SiO 2 -19Al 2 o 3 -28.6CaF 2 -4.8ErF 3 Weigh high-purity rare earth fluoride ErF 3 , SiO 2 , Al 2 o 3 and CaF 2 , and mix the above raw materials evenly, put them into a high-purity corundum crucible or platinum crucible, put them into a furnace that has been heated to 1400°C to melt the raw materials into a liquid state, and make the melt uniform, and keep the melt temperature constant for 1 hour Finally, the crucible is quickly taken out from the high-temperature furnace, and the melt in the crucible is quickly poured on the mold to form a glass sample. The glass can be obtained after the nucleation heat treatment at 600°C for 0.5 hours and the crystallization heat treatment at 660°C for 2 hours. 2 Nanocrystalline glass ceramics. Under 980nm LD laser pumping, a strong and wide emission band can be produced near 1537nm. The half-maximum width of this strong and wide emission band is about 75nm (about 80nm for erbium-doped ZBLAN glass). The...

Embodiment 2

[0023] By composition 47.4SiO 2 -19Al 2 o 3 -28.4CaF 2 -4.7YbF 3 -0.5ErF 3 Weigh high-purity rare earth fluoride ErF 3 , YbF 3 , SiO 2 , Al 2 o 3 and CaF 2 , and mix the above raw materials evenly, put them into a high-purity corundum crucible or platinum crucible, put them into a furnace that has been heated to 1400°C to melt the raw materials into a liquid state, and make the melt uniform, and keep the melt temperature constant for 1 hour Finally, the crucible is quickly taken out from the high-temperature furnace, and the melt in the crucible is quickly poured on the mold to form a glass sample. The glass can be obtained after the nucleation heat treatment at 600°C for 0.5 hours and the crystallization heat treatment at 660°C for 2 hours. 2 Nanocrystalline glass ceramics. The present invention Er 3+ / Yb 3+ Co-doped glass ceramics, due to the co-doped Yb 3+ As a sensitizer, it can more effectively convert invisible near-infrared light into visible green and re...

Embodiment 3

[0025] By composition 47.6SiO 2 -9.5Al 2 o 3 -19ZnF 2 -19.1SrF 2 -4.8ErF 3 Weigh high-purity rare earth fluoride ErF 3 , SiO 2 , Al 2 o 3 , ZnF 2 and SrF 2, and mix the above raw materials evenly, put them into a high-purity corundum crucible or platinum crucible, put them into a furnace that has been heated to 1400°C to melt the raw materials into a liquid state, and make the melt uniform, and keep the melt temperature constant for 1 hour Finally, the crucible is quickly taken out from the high-temperature furnace, and the melt in the crucible is quickly poured on the mold to form a glass sample. The glass can be obtained after the nucleation heat treatment at 600°C for 0.5 hours and the crystallization heat treatment at 630°C for 1 hour. 2 Nanocrystalline glass ceramics. Under the pumping of 980nmLD laser, the glass ceramic can effectively convert infrared light into visible green light and red light, and the effective half maximum width of the infrared emission ...