Long fluorescence lifetime fluorophosphate laser glass, its preparation method and application

Abstract

This invention belongs to the field of laser glass and discloses a long fluorescence lifetime fluorophosphate laser glass, its preparation method, and its applications. The molar percentage composition of this glass is: Zn(PO3)2: 10-50%, Ba(PO3)2: 1-35%, KF: 30-70%, AlF3: 0-20%, with 2-10 mol% YbF3 externally doped from the aforementioned Zn(PO3)2, Ba(PO3)2, KF, and AlF3 raw materials. This laser glass is prepared by a melt-cooling method and has a wide range of adjustable composition, high rare earth solubility, and low nonlinear refractive index. Under 980nm laser diode pumping, it can achieve 1.0μm emission and a fluorescence lifetime of 2.67ms, which is higher than that of existing ytterbium-doped fluorophosphate laser glasses. It is suitable for the preparation and application of 1.0μm rare earth-doped laser glasses, glass fibers, and fiber lasers.

Description

Technical Field

[0001] This invention belongs to the field of laser glass, specifically relating to a long fluorescence lifetime fluorophosphate laser glass, its preparation method, and its application. Background Technology

[0002] In recent years, Yb-doped ions with emission wavelengths in the 1.0 μm band have been... 3+ Fiber lasers have attracted considerable attention, Yb 3+ With its simple energy level structure and high quantum efficiency, fiber laser is suitable for high-power laser output. It has broad application prospects in fields such as biomedicine, materials processing, lidar, advanced remote sensing, and national defense. Laser devices are the core of laser science and technology. Solid-state lasers using rare-earth-doped laser glass or optical fibers as gain media have attracted widespread attention due to their advantages such as compact structure, long lifespan, ease of maintenance, high power, and low cost.

[0003] Compared to commercial quartz glass, phosphate glass has higher rare-earth solubility. This higher solubility leads to higher fiber gain, which is beneficial for the miniaturization and compactness of fiber laser devices. Fluorophosphate glass, obtained by introducing fluorides into phosphate glass, combines the advantages of both: high rare-earth solubility, good machinability, low refractive index, and nonlinear refractive index. Fluorophosphate glass has broad application prospects in ultrashort pulse high-energy laser glass, ultraviolet transmitting materials and achromatic optical glass, as well as fiber lasers and fiber amplifiers. 3+ Yb-doped fluorinated phosphate (YB) lasers exhibit low pump thresholds, large emission cross-sections and effective linewidths, and flat gain curves within a fluorinated phosphate (YPB) glass matrix, making them ideal for ultrashort pulse laser output. Existing commercially available YB-doped fluorinated phosphate laser glasses, such as the FCD-10 reported by Hoya (Japan) and Schott (Germany), have fluorescence lifetimes ranging from 1.50 to 2.12 ms. Fluorescence lifetime affects the number of inverted particles, thus reflecting the unity gain; a longer fluorescence lifetime can improve laser gain and lower the pump threshold. Therefore, YB-doped fluorinated phosphate lasers with high doping concentrations and long fluorescence lifetimes are highly suitable for ultrashort pulse laser output. 3+ Fluorophosphorus glass shows promise as a novel matrix material for ultrashort pulse lasers. Summary of the Invention

[0004] In order to overcome the shortcomings and deficiencies of the prior art, the primary objective of this invention is to provide a long fluorescence lifetime fluorophosphate laser glass, which has a wide range of adjustable composition, high rare earth solubility, and low nonlinear refractive index, and achieves long lifetime 1.0 μm luminescence under 980 nm laser diode pumping.

[0005] Another object of the present invention is to provide a method for preparing long fluorescence lifetime fluorophosphate laser glass, which is prepared by melt cooling method.

[0006] Another object of the present invention is to provide the application of the above-mentioned long fluorescence lifetime fluorophosphate laser glass.

[0007] The technical solution of the present invention is as follows:

[0008] A long fluorescence lifetime fluorophosphate laser glass, with the following molar percentage composition:

[0009]

[0010] RF3 is composed of 2-10 mol% of the aforementioned Zn(PO3)2, Ba(PO3)2, KF, and AlF3 raw materials, wherein R is one of the rare earth elements Yb, Er, Tm, and Ho.

[0011] Preferably, the molar percentage composition of the laser glass is as follows:

[0012]

[0013] YbF3 is composed of 5-10 mol% of the aforementioned Zn(PO3)2, Ba(PO3)2, KF, and AlF3 raw materials.

[0014] A method for preparing a long fluorescence lifetime fluorophosphate laser glass includes the following steps:

[0015] (1) Weighing: Calculate the corresponding raw material weights according to the molar percentage of the above raw material formula, accurately weigh all raw materials and grind and mix them to obtain a mixture;

[0016] (2) Melting: The mixture is placed in a platinum crucible and heated in a silicon carbide rod electric furnace at 1150-1200℃ to melt. After clarification and homogenization, glass melt is obtained.

[0017] (3) Pouring: Pour the molten glass into a preheated graphite mold;

[0018] (4) Annealing: Keep warm in a muffle furnace, cool to room temperature, and obtain laser glass after complete cooling.

[0019] Preferably, the melting time in step (2) is 20-30 min.

[0020] Preferably, the preheating of the graphite mold in step (3) is achieved by placing the graphite mold in a muffle furnace and preheating it to 400-500°C with the furnace temperature rise.

[0021] Preferably, the heat preservation time in step (4) is 2-4 hours.

[0022] Preferably, the cooling rate in step (4) is 5-7°C / h.

[0023] The above-mentioned application of a long fluorescence lifetime fluorophosphate laser glass in fiber lasers.

[0024] The above-mentioned long fluorescence lifetime fluorophosphate laser glass is used in fiber amplifiers.

[0025] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0026] This invention utilizes Yb 3+ The doping process yields a long-lifetime 1.0μm emission under 980nm laser diode pumping, with a fluorescence lifetime of 2.67ms, which is higher than that of existing commercially available ytterbium-doped fluorine phosphate laser glass. It is suitable for applications such as 1.0μm rare-earth-doped laser glass, fiber lasers, and fiber amplifiers. Attached Figure Description

[0027] Figure 1 The fluorescence spectra of the 1.0 μm luminescent rare-earth-doped fluorophosphate laser glasses in Examples 1, 2, 3, 4, and 5 of this invention are shown. 1# to 5# represent Examples 1 to 5.

[0028] Figure 2 The fluorescence decay curves of the 1.0 μm luminescent rare-earth-doped fluorophosphate laser glass in Examples 1, 2, 3, 4, and 5 of this invention are shown.

[0029] Figure 3 This is the glass-forming region of the Zn(PO3)2-AlF3-KF system of the present invention. Detailed Implementation

[0030] The present invention will be further described in detail below with reference to specific embodiments, but the implementation of the present invention is not limited thereto. For process parameters not specifically noted, conventional techniques can be referred to.

[0031] Examples 1-5

[0032] The glass composition and molar ratio of five specific embodiments of the long fluorescence lifetime fluorophosphate laser glass of the present invention are shown in Table 1:

[0033] Table 1

[0034]

[0035] The preparation methods of Examples 1 to 5 are as follows:

[0036] ① Calculate the mass of the five compounds according to the molar percentage of glass components in Examples 1 to 5 in Table 1. Accurately weigh 20g of raw materials, including Zn(PO3)2, Ba(PO3)2, AlF3, and KF. Then weigh 10mol% of the above raw materials YbF3. Weigh 3.53g, 3.43g, 3.34g, 3.26g, and 3.23g of YbF3 in Examples 1 to 5, respectively. Put all raw materials into an agate mortar and mix them evenly.

[0037] ② Melting: The mixed material is placed in a platinum crucible and heated in a silicon carbide rod electric furnace at 1150-1200℃ for melting. The melting temperature in Example 1 is 1200℃, in Example 2 it is 1190℃, in Example 3 it is 1180℃, in Example 4 it is 1160℃, and in Example 5 it is 1150℃. The melting process takes 20-30 minutes. After that, the mixture is clarified and homogenized to obtain molten glass.

[0038] ③ Pouring: Place the clean graphite mold in a muffle furnace and preheat it to 400°C. Pour the molten glass into the preheated graphite mold in the furnace.

[0039] ④ Annealing: Hold the glass sample in a muffle furnace for 2 hours, then cool the muffle furnace to room temperature at a cooling rate of 5-7℃ / h. After complete cooling, remove the glass sample. Table 2 shows the molar percentage of each component in the obtained glass sample.

[0040] The annealed glass sample was cut into 10×10×2mm thin slices, and both surfaces were polished. The fluorescence spectrum of the glass was measured using a spectrometer under 980nm laser diode pumping. The decay curve was measured using an oscilloscope and waveform generator, and the fluorescence lifetime was obtained by fitting the curve. Experimental results show that doping the fluorine-phosphorus glass composition of this invention with ytterbium ions can achieve a fluorescence output of 1.0μm (e.g., ...). Figure 1 As shown), Example 2 has a longer fluorescence lifetime, reaching 2.67 ms (as shown). Figure 2 As shown), it is suitable for use in new solid-state lasers and fiber lasers in the 1.0μm band.

[0041] Table 2

[0042]

[0043] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A long fluorescence lifetime fluorophosphate laser glass, characterized in that, The molar percentage composition of the laser glass is as follows: Zn(PO3)2: 10-50%, Ba(PO3)2: 5-35%, KF: 30-70%, AlF3: 0-20%; YbF3 is composed of 2-10 mol% of the aforementioned Zn(PO3)2, Ba(PO3)2, KF, and AlF3 raw materials.

2. The long fluorescence lifetime fluorophosphate laser glass according to claim 1, characterized in that, The molar percentage composition of the laser glass is as follows: Zn(PO3)2: 15-35%, Ba(PO3)2: 5-25%, KF: 50-60%, AlF3: 0-10%; YbF3 is composed of 5-10 mol% of the aforementioned Zn(PO3)2, Ba(PO3)2, KF, and AlF3 raw materials.

3. A method for preparing a long fluorescence lifetime fluorophosphate laser glass according to claim 1 or 2, characterized in that, Includes the following steps: (1) Weighing: Calculate the corresponding raw material weight according to the molar percentage of the above raw material formula, accurately weigh all raw materials and grind and mix them to obtain the mixture; (2) Melting: The mixture is placed in a platinum crucible and heated in a silicon carbide rod electric furnace at 1150-1200 ℃ to melt, and then clarified and homogenized to obtain glass melt; (3) Pouring: Pour the molten glass into a preheated graphite mold; (4) Annealing: keep warm, cool to room temperature, and obtain laser glass after complete cooling.

4. The method for preparing a long fluorescence lifetime fluorophosphate laser glass according to claim 3, characterized in that, The melting time in step (2) is 20-30 min.

5. The method for preparing a long fluorescence lifetime fluorophosphate laser glass according to claim 3, characterized in that, The preheating temperature of the graphite mold in step (3) is 400~500℃.

6. The method for preparing a long fluorescence lifetime fluorophosphate laser glass according to claim 3, characterized in that, The heat preservation time in step (4) is 2-4 hours.

7. The method for preparing a long fluorescence lifetime fluorophosphate laser glass according to claim 3, characterized in that, The cooling rate in step (4) is 5-7℃ / h.

8. The application of the long fluorescence lifetime fluorophosphate laser glass as described in claim 1 or 2 in fiber lasers.

9. The application of the long fluorescence lifetime fluorophosphate laser glass according to claim 1 or 2 in fiber amplifiers.

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