A highly doped, long-life, wide-bandwidth ion hybrid laser glass and its preparation method and application

Abstract

The present invention belongs to the field of laser glass and discloses a highly doped, long-life, wide-bandwidth ion hybrid laser glass, its preparation method, and its application. The ion hybrid laser glass is composed of 40-100 mol% alkaline earth metal metaphosphate, 0-40 mol% alkali metal sulfate, 0-40 mol% fluoride, and 0-10 mol% rare earth ion oxide. Based on these components, ion hybrid laser glass with high doping (up to 3.5 mol%), long life (up to 12 ms), and wide bandwidth (greater than 100 nm) can be obtained simply by drying in a protective atmosphere and then melting at high temperature. No dehydration using a reactive atmosphere such as carbon tetrachloride is required, thus avoiding adverse effects on the glass composition, structure, and properties. The glass can be used to prepare high-gain, wide-bandwidth laser glass, widely tunable fiber lasers, wide-bandwidth fiber amplifiers, and high-repetition-rate pulsed fiber lasers.

Description

Technical Field

[0001] The present invention belongs to the field of laser glass, and specifically relates to a highly doped, long-life, wide-bandwidth ion hybrid laser glass, and a preparation method and application thereof. Technical Background

[0002] Laser glass is the core gain material of fiber lasers and fiber amplifiers, and its luminescence performance is mainly determined by the glass matrix and its activator - rare earth luminescent ions. The low solubility of rare earth ions in the traditional quartz glass matrix results in a narrow output range of Er-doped quartz laser glass, and a short fluorescence lifetime (<5ms) at higher rare earth doping levels, which limits the output band range of the laser and the laser gain, requiring a higher laser threshold pump. Kesavulu obtained a spectral output range of Er~1.5μm with a half-peak width of 63nm by adjusting the doping concentration of Er ions in silicate (Kesavulu CR, Sreedhar V B, Jayasankar CK, et al. Structural, thermal and spectroscopic properties of highly Er 3+ -doped novel oxyfluoride glasses for photonic application[J].Materials Research Bulletin,2014,51:336-344.). Pisarski modified silicate glass with heavy metals and obtained Er-doped ~ 1.5μm laser output with a half-peak width of 70.5nm and a lifetime of 3.5ms (Pisarski WA,Pisarska J,Lisiecki R,et al.Erbium-doped lead silicate glass for near-infrared emission and temperature-dependent up-conversion applications[J].Opto-electronics review,2017,25(3):238-241.). Compared with traditional quartz glass matrix, ion hybrid laser glass is composed of a variety of cation and anion groups and has a complex local microstructure. It can effectively regulate the luminescence properties of the activator rare earth ions and is expected to achieve low pumping threshold, high gain, and broadband laser output. However, there are few reports on the research of highly doped, long-life, and wide-bandwidth ion hybrid laser glasses at home and abroad. Summary of the Invention

[0003] In order to address the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide an ion-hybridized fluoride-sulfur-phosphate laser glass with high doping, long life and wide bandwidth.

[0004] Another object of the present invention is to provide a method for preparing the above-mentioned glass.

[0005] Another object of the present invention is to provide an application of the above-mentioned glass. The laser glass has the function of making high-gain laser glass optical fibers with low laser threshold and adjustable broadband, and can be used for laser materials, fiber lasers and fiber amplifiers.

[0006] The purpose of the present invention is achieved through the following technical solutions.

[0007] A highly doped, long-life, wide-bandwidth ion hybrid laser glass is composed of:

[0008]

[0009] Preferably, the composition of the highly doped, long-life, wide-bandwidth ion hybrid laser glass is:

[0010]

[0011] Preferably, the alkaline earth metal metaphosphate is one of Ba(PO3)2, Sr(PO3)2, Ca(PO3)2, and Mg(PO3)2;

[0012] The alkali metal sulfate is one of K2SO4, Na2SO4, and Li2SO4;

[0013] The rare earth ion oxides are Er2O3 and Yb2O3;

[0014] The fluoride is one of AlF3, LiF, NaF, KF, MgF2, CaF2, and SrF2.

[0015] Preferably, the ion hybrid laser glass further comprises alkaline earth metal metaphosphate, alkali metal sulfate, fluoride, and rare earth ion oxide, with a total mass of 5 to 10 wt% of BaF2.

[0016] Preferably, the molar percentage of Er2O3 is 2 to 5 mol%, and the molar percentage of Yb2O3 is 1.5 to 5 mol%;

[0017] More preferably, the composition of the ion hybrid laser glass is:

[0018]

[0019] The molar percentage of the above components Ba(PO3)2, K2SO4, AlF3, Er2O3, and Yb2O3 is 100%;

[0020] The invention also includes BaF2 in an amount of 5 wt% of the total weight of the above components.

[0021] A method for preparing highly doped, long-life, wide-bandwidth ion hybrid laser glass comprises the following steps:

[0022] (1) Weigh the raw materials according to the proportion, mix them evenly, move them into a tube furnace, and introduce a mixture of reducing gas and nitrogen or inert gas for drying;

[0023] (2) High-temperature melting: placing the dried raw material obtained in step (1) into a high-temperature electric furnace for melting;

[0024] (3) Molding: Cooling the glass liquid obtained in step (2) and pouring it into a mold for molding;

[0025] (4) Annealing: Annealing and heat preservation, cooling to room temperature to obtain ion hybrid laser glass.

[0026] Preferably, the volume ratio of the nitrogen or inert gas to the reducing gas is 70-80:20-30;

[0027] The reducing gas is hydrogen.

[0028] Preferably, the drying temperature in step (1) is 150-300° C., and the drying time is 8-14 hours.

[0029] Preferably, the high-temperature melting temperature in step (2) is 1000-1250° C., and the melting time is 20 min-2 h.

[0030] Preferably, the cooling in step (3) is to reduce the temperature of the glass liquid to 400-550°C;

[0031] The annealing temperature in step (4) is 350-500° C., the holding time is 2 h-6 h, and the cooling rate is 4-8° C. / h.

[0032] The application of the above-mentioned highly doped, long-life, wide-bandwidth ion hybrid laser glass in laser components.

[0033] The above-mentioned highly doped, long-life, wide-bandwidth ion hybrid laser glass is used in fiber lasers and fiber amplifiers.

[0034] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0035] (1) Based on the complex localized glass network structure of multiple ion cross-linking of ion hybrid glass, a wider effective linewidth is obtained;

[0036] (2) A higher fluorescence lifetime is further obtained under the combination of inert protection and reducing atmosphere drying conditions. Different from the traditional method of removing hydroxyl groups in glass using a dehydrating agent, the method of the present invention is simple, convenient, and more environmentally friendly.

[0037] (3) Based on external doping of fluorides (such as BaF2, etc.), the glass composition can be adjusted more conveniently based on the original components to obtain better high doping, long life and wide bandwidth.

[0038] The long-life, wide-bandwidth fluorine-sulfur-phosphate laser glass of the present invention has a high rare earth ion doping content (~3.5 mol%), a long fluorescence lifetime (~12 ms), and a wide effective linewidth (>100 nm). Different from the laser output performance of activated ions in other laser glasses, it can maintain relatively excellent spectral properties at a high rare earth ion doping content. This ion hybrid glass can be used to prepare high-gain, wide-bandwidth laser glass, widely tunable fiber lasers and fiber amplifiers, and high-repetition-rate pulsed fiber lasers. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is the lifetime decay curve of the highly doped, long-life, wide-bandwidth ion hybrid laser glass prepared by the present invention.

[0040] Figure 2 This is the emission spectrum of the highly doped, long-life, wide-bandwidth ion hybrid laser glass prepared by the present invention.

[0041] Figure 3 Schematic diagram of the microstructure of the highly doped, long-life, wide-bandwidth ion hybrid laser glass prepared by the present invention. DETAILED DESCRIPTION

[0042] The following is a further description of the embodiments of the present invention in conjunction with specific examples, but the embodiments of the present invention are only part of the embodiments of the present invention and are not limited to this. Based on the embodiments in the present invention, other embodiments used by ordinary technicians in this field without making creative work are all within the scope of protection of the present invention. Without departing from the concept of the present invention, several variations and improvements can also be made, which all fall within the scope of protection of the present invention. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided by the present invention are all within the scope of protection of the claims attached to the present invention. Therefore, the scope of protection of the patent of the present invention shall be based on the content of the attached claims, and the description can be used to interpret the content of the claims. For process parameters not specifically noted, conventional techniques can be used.

[0043] Table 1 lists the molar percentage compositions of the fluorine, sulfur, and phosphate ion hybrid laser glasses in the specific embodiments of the present invention and two comparative examples:

[0044] Table 1

[0045]

[0046] Example 1

[0047] The preparation method of long-life, wide-bandwidth fluorine-sulfur-phosphate laser glass using a tube furnace with low-temperature protective atmosphere drying combined with high-temperature melting is as follows:

[0048] (1) According to the proportions of Example 1 in Table 1, 10 g of high-purity (purity ≥ 99.999%) raw materials were weighed, wherein the molar percentages of Ba(PO3)2, K2SO4, AlF3, Er2O3, and Yb2O3 were 56.5, 25, 15, 2, and 1.5, respectively.

[0049] (2) Low-temperature drying: Grind the high-purity powdered raw materials evenly and pour them into a corundum crucible. Then transfer them into a crucible boat and heat them in a tube furnace. After introducing a protective atmosphere of nitrogen and hydrogen mixed gas (80:20 v / v), heat them at 250°C for 12 h to dry them.

[0050] (3) High-temperature smelting: transfer the low-temperature dried raw materials and crucible boat to a high-temperature electric furnace and melt them at 1200°C for 30 minutes;

[0051] (4) Molding: pour the glass liquid into the preheated mold, cool it to 450°C, and then move it to a tube furnace for direct annealing;

[0052] (5) Annealing: After annealing at 450°C in a tube furnace for 2 hours, the glass was cooled to room temperature at a rate of 5°C / h to obtain a highly doped, long-life, wide-bandwidth fluorine-sulfur-phosphate ion hybrid laser glass.

[0053] Example 2

[0054] According to the ratio in Table 1, high-purity raw materials Ba(PO3)2, K2SO4, AlF3, Er2O3, and Yb2O3 were weighed, with a total mass of 10 g. Then, 0.5 g of BaF2, which is 5 wt% of the mass of the above high-purity raw materials, was weighed. The annealing temperature in step (5) was 450°C, and the other operating steps were the same as in Example 1.

[0055] Example 3

[0056] According to the ratio in Table 1, high-purity raw materials Ba(PO3)2, K2SO4, AlF3, Er2O3, and Yb2O3 were weighed, with a total mass of 10 g. The annealing temperature in step (5) was 470°C, and the other operating steps were the same as in Example 1.

[0057] Example 4

[0058] According to the ratio in Table 1, high-purity raw materials Ba(PO3)2, K2SO4, AlF3, Er2O3, and Yb2O3 were weighed, with a total mass of 10 g. 0.5 g of BaF2, which is 5 wt% of the mass of the above high-purity raw materials, was then weighed. The annealing temperature in step (5) was 490°C, and the other operating steps were the same as in Example 1.

[0059] The compositions of the laser glasses finally prepared in Examples 1 to 4 are as follows (in mole percentage):

[0060] Table 2

[0061]

[0062] Highly doped, long-life, and wide-bandwidth ion hybrid laser glass was prepared by drying in a protective atmosphere and melting at high temperature. The fluorescence lifetime and effective line width of the laser glass were measured. Figure 1 and Figure 2 It can be seen that the fluorescence lifetime of the laser glass of Example 2 can reach 12.3ms, and the effective linewidth is 103.6nm, which is better than that of Example 1. The fluorescence lifetime of the laser glass of Example 4 can reach 7.62ms, and the effective linewidth is 104.7nm, which is better than that of Example 3. Experimental data show that the above Examples 1, 2, 3, and 4 can all achieve high fluorescence lifetime and laser emission bandwidth, and are expected to achieve low pump threshold, high gain, and broadband fiber laser output. This ion hybrid glass can be used to prepare high-gain, wide-bandwidth laser glass, widely tunable fiber lasers and fiber amplifiers, and high repetition rate pulsed fiber laser devices.

[0063] Table 3

[0064]

[0065] Comparative Example 1

[0066] Different from Example 2, when 10 wt% of BaF21g of high-purity raw materials was added and the annealing temperature in step (5) was 460°C, the performance of the prepared laser glass began to decline, with a fluorescence lifetime of 6.05 ms and an effective line width of 100.9 nm, and the fluorescence lifetime began to decrease significantly.

[0067] Comparative Example 2

[0068] Different from Example 2, no low-temperature protective atmosphere drying in a tube furnace was performed. After high-temperature melting, forming, and annealing at an annealing temperature of 480°C, the performance of the prepared laser glass began to decline further, with a fluorescence lifetime of 4.17ms and an effective line width of 100.2nm.

[0069] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A highly doped, long-life, wide-bandwidth ion hybrid laser glass, characterized in that: The composition of the ion hybrid laser glass is: Alkaline earth metal metaphosphate 40~60 mol% Alkali metal sulfate 10~40 mol% Fluoride 20~40 mol% Rare earth ion oxides 3.5~10 mol%; The sum of the contents of each component in the glass is 100%; The alkali metal sulfate is one of K2SO4, Na2SO4, and Li2SO4; The fluoride is one of AlF3, LiF, NaF, KF, MgF2, CaF2, and SrF2; The rare earth ion oxides are Er2O3 and Yb2O3; the molar percentage of Er2O3 is 2-5 mol%, and the molar percentage of Yb2O3 is 1.5-5 mol%.

2. The highly doped, long-life, wide-bandwidth ion hybrid laser glass according to claim 1, characterized in that: The alkaline earth metal metaphosphate is one of Ba(PO3)2, Sr(PO3)2, Ca(PO3)2, and Mg(PO3)2.

3. The highly doped, long-life, wide-bandwidth ion hybrid laser glass according to claim 1, characterized in that: The ion hybrid laser glass further comprises alkaline earth metal metaphosphate, alkali metal sulfate, fluoride, and rare earth ion oxide, with a total mass of 5-10 wt% of BaF2.

4. A method for preparing the highly doped, long-life, wide-bandwidth ion hybrid laser glass according to any one of claims 1 to 3, characterized in that: The steps include: (1) Weigh the raw materials according to the proportion, mix them evenly, and then move them into a tube furnace. Pass a mixture of reducing gas and nitrogen or inert gas to dry them; (2) High-temperature melting: placing the dried raw materials obtained in step (1) into a high-temperature electric furnace for melting; (3) Molding: Cooling the glass liquid obtained in step (2) and pouring it into a mold for molding; (4) Annealing: Annealing and heat preservation, cooling to room temperature to obtain ion hybrid laser glass.

5. The preparation method according to claim 4, characterized in that The volume ratio of the nitrogen or inert gas to the reducing gas is 70-80:20-30; The reducing gas is hydrogen.

6. The preparation method according to claim 4, characterized in that The drying temperature in step (1) is 150-300°C and the drying time is 8-14 hours; The high temperature melting temperature in step (2) is 1000-1250°C and the time is 20-120 minutes; The cooling in step (3) is to reduce the temperature of the glass liquid to 400-550°C; The annealing temperature in step (4) is 350-500°C, the holding time is 120-360 min, and the cooling rate is 4-8°C / h.

7. Use of the highly doped, long-life, wide-bandwidth ion hybrid laser glass according to any one of claims 1 to 3 in laser components.

8. Use of the highly doped, long-life, wide-bandwidth ion hybrid laser glass according to any one of claims 1 to 3 in fiber lasers and fiber amplifiers.

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