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CN-117756408-B - Fluorophosphate laser glass with long fluorescence lifetime and preparation method and application thereof

CN117756408BCN 117756408 BCN117756408 BCN 117756408BCN-117756408-B

Abstract

The invention belongs to the field of laser glass, and discloses a fluorophosphate laser glass with long fluorescence lifetime, a preparation method and application thereof, wherein the molar percentage composition of the glass is Zn (PO 3 ) 2 ：10-50％,Ba(PO 3 ) 2 ：1-35％,KF：30-70％,AlF 3 : 0-20 percent), the Zn is doped (YbF 3 with 2-10mol percent of PO 3 ) 2 、Ba(PO 3 ) 2 、KF、AlF 3 raw materials is formed, the laser glass is prepared by a melt cooling method, the laser glass has a large component adjustable range, higher rare earth solubility and lower nonlinear refractive index, under 980nm laser diode pumping, 1.0 mu m luminescence can be obtained in the glass, the fluorescence lifetime reaches 2.67ms, and the glass is higher than that of the prior ytterbium-doped fluorophosphate laser glass, and the glass is suitable for the preparation and application of 1.0 mu m rare earth-doped laser glass, glass optical fibers and optical fiber lasers.

Inventors

  • WANG WEICHAO
  • Duan Taiyu
  • JI YAO
  • YANG CHANGSHENG

Assignees

  • 华南理工大学

Dates

Publication Date
20260505
Application Date
20231201

Claims (9)

  1. 1. The fluorophosphate laser glass with long fluorescence lifetime is characterized in that the laser glass comprises the following components in percentage by mole: Zn(PO 3 ) 2 : 10-50%, Ba(PO 3 ) 2 : 5-35%, KF: 30-70%, AlF 3 : 0-20%; The Zn (PO 3 ) 2 、Ba(PO 3 ) 2 、KF 、AlF 3 raw material composition 2-10 mol% YbF 3 ) is externally doped.
  2. 2. The long fluorescence lifetime fluorophosphate laser glass according to claim 1, wherein the laser glass comprises the following components in mole percent: Zn(PO 3 ) 2 : 15-35%, Ba(PO 3 ) 2 : 5-25%, KF: 50-60%, AlF 3 : 0-10%; The Zn (PO 3 ) 2 、Ba(PO 3 ) 2 、KF 、AlF 3 raw material composition 5-10 mol% YbF 3 ) is externally doped.
  3. 3. The method for preparing the fluorophosphate laser glass with long fluorescence lifetime as claimed in claim 1 or 2, comprising the following steps: (1) Weighing, namely calculating the weight of the corresponding raw materials according to the mole percentage of the raw material formula, accurately weighing all the raw materials, and grinding and mixing to obtain a mixture; (2) Melting, namely placing the mixture into a platinum crucible, heating and melting the mixture in a silicon carbide rod electric furnace at 1150-1200 ℃, and clarifying and homogenizing the mixture to obtain glass liquid; (3) Pouring, namely pouring molten glass into a preheated graphite mould; (4) Annealing, heat preservation, cooling to room temperature, and obtaining the laser glass after complete cooling.
  4. 4. The method for producing a long-fluorescence-lifetime fluorophosphate laser glass according to claim 3, wherein said melting time in step (2) is 20 to 30 minutes.
  5. 5. The method for preparing long-fluorescence-lifetime fluorophosphate laser glass according to claim 3, wherein the preheating temperature of the preheated graphite mould in step (3) is 400-500 ℃.
  6. 6. The method for preparing a long-fluorescence-lifetime fluorophosphate laser glass according to claim 3, wherein said incubation time in step (4) is 2 to 4 hours.
  7. 7. A method for producing a long-fluorescence-lifetime fluorophosphate laser glass according to claim 3, wherein said cooling rate in step (4) is 5 to 7 ℃.
  8. 8. Use of the long fluorescence lifetime fluorophosphate laser glass of claim 1 or 2 in a fiber laser.
  9. 9. Use of the long fluorescence lifetime fluorophosphate laser glass of claim 1 or 2 in an optical fiber amplifier.

Description

Fluorophosphate laser glass with long fluorescence lifetime and preparation method and application thereof Technical Field The invention belongs to the field of laser glass, and particularly relates to a fluorophosphate laser glass with long fluorescence lifetime, and a preparation method and application thereof. Background In recent years, a Yb 3+ -doped fiber laser with the emission wavelength in a 1.0 μm wave band attracts great attention, and the Yb 3+ energy level structure is simple, the quantum efficiency is higher, and the fiber laser is suitable for high-power laser output. The fiber laser has wide application prospect in the fields of biomedical treatment, material processing, laser radar, advanced remote sensing, national defense and military industry and the like. The laser device is the core of laser science and technology, and the solid laser using rare earth doped laser glass or optical fiber as gain medium has the advantages of compact structure, long service life, convenient maintenance, high power, lower cost and the like, and thus, the solid laser has a great deal of attention. Compared with commercial quartz glass, the phosphate glass has higher rare earth solubility, and the high rare earth solubility brings higher optical fiber gain, thereby being beneficial to the miniaturization and compact development of optical fiber laser devices. The fluorophosphate glass obtained by introducing fluoride into the phosphate glass has the advantages of high rare earth solubility, good machining performance, low refractive index and nonlinear refractive index. The fluorophosphate glass has wide application prospect in the fields of ultra-short pulse high-energy laser glass, ultraviolet transmitting material, achromatic optical glass, optical fiber laser and optical fiber amplifier. Yb 3+ has lower pumping threshold in the fluorophosphate glass matrix, large emission section and effective line width, flat gain curve, and is very suitable for ultra-short pulse laser output. The fluorescence lifetime level of the commercial ytterbium-doped fluorophosphate laser glass reported by the prior FCD-10 reported by Hoya corporation in Japan and the commercial ytterbium-doped fluorophosphate laser glass reported by Schott corporation in Germany is 1.50-2.12 ms, the fluorescence lifetime influences the reversed particle number, so that the magnitude of the unit gain is reflected, the laser gain can be improved due to long fluorescence lifetime, and the pumping threshold is reduced. Therefore, the Yb 3+ fluorine-phosphorus doped glass with high doping concentration and long fluorescence lifetime is hopeful to become a novel ultrashort pulse laser matrix material. Disclosure of Invention In order to overcome the defects and shortcomings of the prior art, the primary purpose of the invention is to provide a fluorophosphate laser glass with long fluorescence lifetime, which has a large adjustable range of components, high rare earth solubility and low nonlinear refractive index, and can obtain luminescence with long lifetime of 1.0 μm under 980nm laser diode pumping. It is still another object of the present invention to provide a method for preparing a long fluorescence lifetime fluorophosphate laser glass, which is prepared by a melt cooling method. It is a further object of the present invention to provide the use of the long fluorescence lifetime fluorophosphate laser glass described above. The technical scheme of the invention is as follows: The fluorophosphate laser glass with long fluorescence lifetime comprises the following components in percentage by mole: The Zn (PO 3)2、Ba(PO3)2、KF、AlF3 raw material composition of 2-10mol% of RF 3 is doped, wherein R is one of rare earth elements Yb, er, tm and Ho). Preferably, the laser glass comprises the following components in mole percent: The Zn (PO 3)2、Ba(PO3)2、KF、AlF3 raw material composition 5-10mol% YbF 3) is externally doped. A preparation method of fluorophosphate laser glass with long fluorescence lifetime comprises the following steps: (1) Weighing, namely calculating the weight of the corresponding raw materials according to the mole percentage of the raw material formula, accurately weighing all the raw materials, and grinding and mixing to obtain a mixture; (2) Melting, namely placing the mixture into a platinum crucible, heating and melting the mixture in a silicon carbide rod electric furnace at 1150-1200 ℃, and clarifying and homogenizing the mixture to obtain glass liquid; (3) Pouring, namely pouring molten glass into a preheated graphite mould; (4) Annealing, namely preserving heat in a muffle furnace, cooling to room temperature, and obtaining the laser glass after complete cooling. Preferably, the melting time in the step (2) is 20-30min. Preferably, in the step (3), the preheated graphite mould is placed in a muffle furnace and preheated to 400-500 ℃ along with furnace temperature rise. Preferably, the heat preservation time in the step (4) is 2-4