阅读说明：本技术 一种Ho3+/Eu3+共掺杂的可产生3.9μm中红外波段荧光的氟铟玻璃 (Ho3+/Eu3+Co-doped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence ) 是由 王鹏飞 张志� 贾世杰 于 2021-01-26 设计创作，主要内容包括：本发明公开了一种Ho～(3+)/Eu～(3+)共掺杂的可产生3.9μm中红外波段荧光的氟铟玻璃,涉及玻璃光纤技术领域。本发明提供的氟铟玻璃按摩尔百分比组成表示的化学式为25.5InF-3-15ZnF-2-18BaF-2-11.5GaF-3-8SrF-2-12PbF-2-5LiF-1.75YF-3-(1.75-x)LaF-3-1.5Ho～(3+)-xEu～(3+),x＝0～0.1。本发明提供的Ho～(3+)/Eu～(3+)共掺杂的可产生3.9μm中红外波段荧光的氟铟玻璃声子能量低,透过率高,发光效率高,而且具有良好的化学稳定性和热稳定性,且制备工艺简单,可以作为3.9μm中红外波段光纤激光器增益介质。(The invention discloses a Ho 3+ /Eu 3+ Co-doped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence, and relates to the technical field of glass optical fibers. The chemical formula of the fluorine indium glass provided by the invention expressed by the mole percentage composition is 25.5InF 3 ‑15ZnF 2 ‑18BaF 2 ‑11.5GaF 3 ‑8SrF 2 ‑12PbF 2 ‑5LiF‑1.75YF 3 ‑(1.75‑x)LaF 3 ‑1.5Ho 3+ ‑xEu 3+ And x is 0 to 0.1. Ho provided by the invention 3+ /Eu 3+ The codoped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence has low phonon energy, high transmittance, high luminous efficiency, good chemical stability and thermal stability, and simple preparation processAs a gain medium of a 3.9 mu m mid-infrared band fiber laser.)

1. Ho³⁺/Eu³⁺Co-doped fluoroindium glass capable of generating 3.9 mu m mid-infrared band fluorescence, characterized in that the chemical formula expressed in mol percent composition is 25.5InF₃-15ZnF₂-18BaF₂-11.5GaF₃-8SrF₂-12PbF₂-5LiF-1.75YF₃-(1.75-x)LaF₃-1.5Ho³⁺-xEu³⁺X is 0-0.1, and the sum of the mole percentages of the components is 100%.

2. The Ho of claim 1, wherein³⁺/Eu³⁺Co-doped InF glass capable of generating fluorescence in the 3.9 μm mid-IR band, wherein x is 0, 0.005, 0.01, 0.015, 0.02, 0.05 or 0.1.

3. The Ho of claim 1, wherein³⁺/Eu³⁺Co-doped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence, characterized in that Eu³⁺By EuF₃The form is doped.

4. The Ho of claim 1, wherein³⁺/Eu³⁺The codoped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence is characterized in that Ho³⁺By HoF₃The form is doped.

5. The Ho of any of claims 1-4³⁺/Eu³⁺The co-doped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence is characterized in that the preparation method comprises the following steps:

(1) weighing high-purity raw materials according to a ratio, and fully mixing in a grinding bowl to obtain a mixture;

(2) putting the mixture into a platinum crucible, and melting in a high-temperature furnace at 800-900 ℃;

(3) pouring the melt glass on a preheated brass mould to form a glass sample;

(4) the glass sample is placed in an annealing furnace at the temperature of 200-300 ℃ for annealing treatment and then cooled to the room temperature.

6. The Ho of any of claims 1-4³⁺/Eu³⁺The codoped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence is characterized in that fluorescence emission of 3.9 mu m mid-infrared band is realized under the excitation of 888nm laser pumping.

7. The Ho of any of claims 1-4³⁺/Eu³⁺Codoped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence at 3.9 mu mThe gain medium of the m mid-infrared band fiber laser.

8. A mid-infrared laser comprising the Ho of any one of claims 1 to 4³⁺/Eu³⁺And co-doped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence.

Technical Field

The invention relates to the technical field of glass optical fibers, in particular to a Ho³⁺/Eu³⁺And co-doped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence.

Background

The mid-infrared (2-20 μm) laser is located in the absorption band of the vibration energy level of many gas molecules and organic molecules, namely the so-called molecular fingerprint region, so that the mid-infrared laser has important application prospect in the fields of disease diagnosis, trace gas detection, molecular spectroscopy and the like. For example, water molecules have strong absorption peaks near 3 μm, so that the laser can be used for laser surgery with small wound surface and good hemostatic property in a new generation. In addition, three transparent windows exist in the space atmosphere, and the windows are respectively 2-2.7 micrometers, 3-5 micrometers and 8-13 micrometers, so that the mid-infrared laser has important application potential in the military fields of laser radar, laser ranging, atmosphere communication, laser guidance, remote sensing measurement and control, photoelectric countermeasure and the like.

Compared with a fiber laser, the traditional semiconductor laser has poor beam quality, a nonlinear frequency conversion system is complex, the requirement on the adjustment precision of a light path is high, the gas laser is large in size, and most of gas is corrosive or even toxic. To dope with rare earth ions (Ho)³⁺，Yb³⁺，Pr³⁺，Er³⁺，Nd³⁺，Tm³⁺) The fiber laser using the glass fiber as the gain medium has the advantages of good beam quality, low threshold pump power, high conversion efficiency, strong adaptability, easy integration, good heat dissipation and the like. Among them, fluoride glass has attracted much attention because of its low phonon energy, wide transmission spectrum range and high solubility of rare earth ions, as compared with glass matrix materials such as silicate glass, phosphate glass and borate glass. In addition, the energy level of rare earth ions in fluoride glass has longer service life, lower inherent loss and longer infrared cut-off wavelength than silicate glass, so the fluoride glass is considered as an extremely promising glass matrix material for fiber lasers by extensive researchers.

In 1995, Schneider et al utilized Ho³⁺：⁵I₅→⁵I₆In ZBLAN (ZrF)₄-BaF₂-LaF₃-AlF₃NaF) fiber, which is also the maximum wavelength achievable to date with rare earth doped fiber lasers. However, the multiphoton relaxation of rare earth ions in fluorozirconate glass limits its emission efficiency at 3.9 μm, and fluorozirconic acidThe sharp decrease in transmittance of the salt glass in the vicinity of 4 μm also hinders the possibility of realizing long-wavelength laser output.

In 2018, f.maes et al utilized holmium-doped ions (Ho)³⁺) The double-clad fluorine-indium optical fiber obtains 3.92 mu m laser output with output power and slope efficiency of 197mW and 10.2 percent respectively. Indium fluoride glass has lower phonon energy, wider infrared transmission window and can also be drawn into low loss optical fiber compared to fluorozirconate glass.

However, holmium ion (Ho)³⁺) Energy level structure and corresponding energy level transition⁵I₆→⁵I₈，⁵I₇→⁵I₈，⁵I₆→⁵I₇，⁵I₅→⁵I₆Can generate near-infrared and mid-infrared luminescence of 1.2 mu m,2.0 mu m,2.9 mu m and 3.9 mu m. Due to the upper energy level of the generated fluorescence with the wave band of 3.9 mu m⁵I₅The energy level life is far less than that of the lower energy level⁵I₆Cause to make⁵I₅→⁵I₆The transition self-terminates, resulting in a weak and difficult to obtain 3.9 μm band emission intensity.

Disclosure of Invention

The invention aims to solve the technical problem of how to realize the fluorescent emission of a 3.9 mu m middle infrared band by using the fluorine indium glass and improve the emission efficiency.

In order to solve the above problems, the present invention proposes the following technical solutions:

the invention provides a Ho³⁺/Eu³⁺Co-doped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence, and the chemical formula is 25.5InF expressed by the mole percentage composition₃-15ZnF₂-18BaF₂-11.5GaF₃-8SrF₂-12PbF₂-5LiF-1.75YF₃-(1.75-x)LaF₃-1.5HoF₃-xEuF₃X is 0-0.1, and the sum of the mole percentages of the components is 100%.

The technical scheme is that x is 0, 0.005, 0.01, 0.015, 0.02, 0.05 or 0.1.

It further comprisesThe technical proposal is that Eu³⁺By EuF₃The form is doped.

The further technical proposal is that Ho³⁺By HoF₃The form is doped.

The further technical proposal is that Ho³⁺/Eu³⁺The preparation method of the co-doped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence comprises the following steps:

(1) weighing high-purity raw materials according to a ratio, and fully mixing in a grinding bowl to obtain a mixture;

(2) putting the mixture into a platinum crucible, and putting the platinum crucible into a high-temperature furnace at 800-900 ℃ for melting for 2-3 h;

(3) pouring the melt glass on a preheated brass mould to form a glass sample;

(4) and (3) placing the glass sample in an annealing furnace with the temperature of 200-300 ℃ for annealing treatment, wherein the annealing time is 2-4h, and then cooling to room temperature to obtain the glass.

The Ho provided by the invention³⁺/Eu³⁺The co-doped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence can realize 3.9 mu m mid-infrared band fluorescence emission under the excitation of 888nm laser pumping.

Further, the invention provides the Ho³⁺/Eu³⁺The codoped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence is applied to a gain medium of a 3.9 mu m mid-infrared band optical fiber laser.

The invention also provides a mid-infrared laser, which comprises the Ho³⁺/Eu³⁺And co-doped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence.

Note that holmium ions (Ho)³⁺) Energy level structure and corresponding energy level transition⁵I₆→⁵I₈，⁵I₇→⁵I₈，⁵I₆→⁵I₇，⁵I₅→⁵I₆And can generate near-infrared and mid-infrared luminescence of 1.2 mu m,2.0 mu m,2.9 mu m and 3.9 mu m (see figure 1). Due to the generation of 3.9 μm waveUpper energy level of segmental fluorescence⁵I₅The energy level life is far less than that of the lower energy level⁵I₆Cause to make⁵I₅→⁵I₆The transition self-terminates, resulting in a weak and difficult to obtain 3.9 μm band emission intensity. The invention utilizes Ho³⁺：⁵I₆→Eu³⁺：⁷F₆Reduced lower energy level⁵I₆Particle number constructs a Ho³⁺/Eu³⁺The codoped system is indium fluoride-based glass, so that the luminescence enhancement at 3.9 mu m is obtained.

Ho³⁺Ion absorption of 888nm can directly pump particles to⁵I₅Energy level, thereby improving the transition probability of 3.9 μm mid-infrared radiation. Therefore, the 888nm semiconductor laser is adopted as a pumping source for pumping.

In the invention, the fluoride glass is prepared by a traditional melting quenching method, medicines are weighed according to the pre-designed glass components, raw materials are ground and fully mixed, the fluoride glass is prepared in a reducing atmosphere, after a sample reaches a complete melting state, the sample is quickly transferred to a low-temperature muffle furnace for annealing to remove residual stress, the sample is naturally cooled to room temperature to obtain a glass sample, and then the glass sample is cut into a shape of 10 x 1.5mm and polished for subsequent tests.

Compared with the prior art, the invention can achieve the following technical effects: ho provided by the invention³⁺/Eu³⁺Co-doped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence by blending each component and utilizing Ho³⁺：⁵I₆→Eu³⁺：⁷F₆Reduced lower energy level⁵I₆Particle number to obtain a mid-infrared fluorescence emission of 3.9 μm. Ho provided by the invention³⁺/Eu³⁺The codoped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence has the advantages of low phonon energy, high transmittance, high luminous efficiency, good chemical stability and thermal stability, simple preparation process and capability of being used as a gain medium of a 3.9 mu m mid-infrared band optical fiber laser.

The glass provided by the invention can generate middle infrared band fluorescence of 1.2 mu m,1.6 mu m,2.0 mu m,2.9 mu m and 3.9 mu m under the excitation of 888nm semiconductor laser, especially has higher fluorescence intensity of 3.9 mu m, and the wavelength has important application value in various fields such as sensing, spectroscopy, remote sensing, medical treatment, environmental protection, military and the like.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 shows Ho³⁺/Eu³⁺Co-doping system energy level diagram;

FIG. 2 shows 888nm pumping of different Hos³⁺/Eu³⁺The codoped concentration fluorine indium glass 1110-1250nm waveband luminescence spectrum;

FIG. 3 shows 888nm pumping of different Hos³⁺/Eu³⁺Co-doped fluorine indium glass with concentration 1500-;

FIG. 4 shows 888nm pumping of different Hos³⁺/Eu³⁺Co-doped fluorine indium glass 1800-doped 2200nm waveband luminescence spectrum;

FIG. 5 shows 888nm pumping of different Hos³⁺/Eu³⁺Co-doped fluorine indium glass 2600-;

FIG. 6 shows 888nm pumping of different Hos³⁺/Eu³⁺And the luminescent spectrum of the 3700 and 4200nm wave bands of the codoped fluorine indium glass.

Detailed Description

The technical solutions in the embodiments will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, wherein like reference numerals represent like elements in the drawings. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention. As used in the description of embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

Examples

The embodiment of the invention provides Ho³⁺/Eu³⁺The codoped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence comprises the following components in percentage by weight:

1. weighing high-purity raw materials according to the following mol percentage, and fully mixing in a grinding bowl: 25.5InF₃-15ZnF₂-18BaF₂-11.5GaF₃-8SrF₂-12PbF₂-5LiF-1.75YF₃-(1.75-x)LaF₃-1.5HoF₃-xEuF₃(x＝0,0.005,0.01,0.015,0.02,0.05,0.1)

2. Placing the mixture into a platinum crucible, adding a cover, melting for 2h at 850 ℃ in a glove box high-temperature furnace, then pouring molten glass liquid onto a preheated brass mold, and placing the mold into an annealing furnace for annealing for 3h at 240 ℃ to eliminate stress generated in the glass, thereby obtaining a final glass sample.

3. The prepared glass samples were cut to a size of 10mm by 1.5mm and both sides were finely polished for testing at room temperature.

4. Exciting with 888nm semiconductor laser, setting its power to 2.5W, and testing different concentrations Ho³⁺/Eu³⁺The ion-doped fluorine indium glass is 1.2 μm,1.6 μm,2.0 μm and 2.9 μmAnd a fluorescence spectrum at 3.9 μm, see FIGS. 2-6.

From the results of FIGS. 2-6, it can be seen that Ho provided by the embodiments of the present invention³⁺/Eu³⁺The codoped fluorine indium glass capable of generating 3.9 mu m mid-infrared band fluorescence realizes the mid-infrared fluorescence emission of 1.2 mu m,1.6 mu m,2.0 mu m,2.9 mu m and 3.9 mu m under the excitation of 888nm pump.

The invention focuses on researching different concentrations of Eu in the fluorine indium matrix glass under 888nm excitation³⁺To Ho³⁺Influence of luminescence characteristics of respective fluorescence bands to realize high-efficiency 3.9 μm mid-infrared fluorescence output, and the results show that when Eu is used³⁺Has the highest luminous intensity at 3.9 μm at a doping concentration of 0.02 mol% (see inset in fig. 6). The research method and the result of the invention have important reference value and guiding significance for further researching the intermediate infrared glass material and the intermediate infrared laser.

In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.

While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.