CN113480172A - Preparation method of holmium and neodymium co-doped fluorine-aluminum glass capable of realizing 3.9 micron luminescence - Google Patents

Preparation method of holmium and neodymium co-doped fluorine-aluminum glass capable of realizing 3.9 micron luminescence Download PDF

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CN113480172A
CN113480172A CN202110754317.4A CN202110754317A CN113480172A CN 113480172 A CN113480172 A CN 113480172A CN 202110754317 A CN202110754317 A CN 202110754317A CN 113480172 A CN113480172 A CN 113480172A
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holmium
luminescence
neodymium
raw materials
micron
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王鹏飞
张集权
王顺宾
王瑞聪
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Harbin Engineering University
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Harbin Engineering University
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
    • C03C3/325—Fluoride glasses

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  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Glass Compositions (AREA)

Abstract

The invention relates to a preparation method of holmium and neodymium codoped fluorine-aluminum glass capable of realizing 3.9 micron luminescence, which comprises the following steps: weighing and preparing chemical raw materials according to a certain mole percentage, and then fully grinding and mixing; putting the mixed raw materials into a crucible, and melting and firing the mixed raw materials in a glove box through a high-temperature furnace at 800-; pouring the molten liquid into a preheated mold at about 370 ℃, keeping for 3 hours, and then slowly cooling to room temperature to obtain holmium and neodymium codoped fluorine-aluminum glass with different concentrations; polishing the surface of the holmium and neodymium codoped fluorine-aluminum glass sample to optical quality to obtain a final glass sample capable of realizing 3.9 micron luminescence. The glass prepared by the invention has good deliquescence resistance; the preparation process is simple, and batch production can be realized; has good spectrum transmission width and transmission performance, and has no obvious visible transmittance reduction condition at the water molecule absorption position.

Description

Preparation method of holmium and neodymium co-doped fluorine-aluminum glass capable of realizing 3.9 micron luminescence
Technical Field
The invention belongs to the fields of mid-infrared glass luminescence, mid-infrared fiber laser, special optical materials and the like, and particularly relates to a preparation method of holmium-neodymium co-doped fluorine-aluminum glass capable of realizing 3.9 micron luminescence.
Background
In recent years, mid-infrared lasers operating at 3-5 microns have attracted considerable attention due to their use in atmospheric sensing, medicine and defense. In the 3-5 micron wave band, erbium (Er)3+) Dysprosium (Dy)3+) And holmium (Ho)3+) Are the most common dopants. After Henderson-Sapir proposed efficient dual wavelength pumping, Frederic increased the 3.55 micron laser power output to 5.6 watts in 2017 using 976 nm and 1976 nm pumping in erbium doped ZBLAN fibers. As for dysprosium ions, Vincent reported in 2019 a 3.24 micron fiber laser that achieved 10.1 watts in fluoride fiber. However, the holmium ion is at 3.9 microns (5I5→5I6) The development of a laser emitting light is far behind, and only 197 mw of output power was obtained in 888 nm pumped indium fluoride fiber reported previously. This is mainly due to the lack of commercially available laser diodes as pump sources to achieve 3.9 micron luminescence, and the lack of reliable low phonon energy host materials. Holmium ion emission requirement of 3.9 microns5I4The particle number of the energy level is distributed, but the commercial pumping source with low cost and high power of 793 nm, 808 nm or 980 nm is not suitable for pumping holmium ions. In 2017, it has been reported that neodymium ions (Nd) are introduced into holmium-doped lead fluoride crystals by pumping with 808-nanometer laser diodes3+) 3.9 micron luminescence is generated, and neodymium ions can be used as a sensitizer to transfer pumping energy to holmium5I4(ii) at energy level and depleting the population of particles at lower energy level by an energy transfer process5I5And5I6energy level). In 2020, Wangcong Fei teacher of Harbin Engineers reported that neodymium ion enhanced holmium ion luminescence in indium fluoride glass is 3.9 microns. However, similar to the well-known fluorozirconate glass (ZBLAN), the poor resistance to deliquescence and chemical stability of indium fluoride glass greatly increases the difficulty of developing long-term reliable lasers, thus limiting their development. For the reasons mentioned above, it is still necessary to find suitable lasing host materials in the range of 3-5 microns.
The fluorine-aluminum glass material has wide transparent window, high transmissivity, low phonon energy and good chemical stability, and is expected to realize high-power and stable optical fiber devices. In 2018, Gishijie obtained a laser output of 57 milliwatts at 2868 nm with an 84 cm long holmium-doped fluoroaluminium glass fiber, which also demonstrated a much better water resistance than ZBLAN. The Wang Shuin teacher of Harbin Engineers showed 2866 nm laser output in 19 cm long holmium praseodymium codoped fluorine aluminum glass fiber in 2020, and increased the output power to 173 milliwatts with a slope efficiency of 10.3%, which all indicate that fluorine aluminum glass is a strong candidate for mid-infrared laser material.
Therefore, based on the technical problems, the invention firstly provides that the fluorine-aluminum material is doped with two rare earths of holmium and neodymium, and 3.9 micron luminescence can be obtained under the pumping of a cheap 808 nanometer laser diode. Meanwhile, the preparation method of the holmium and neodymium co-doped fluor-aluminum glass capable of realizing 3.9 micron luminescence has a certain inspiring effect on the realization of 3.9 micron mid-infrared laser of the fluor-aluminum material.
Disclosure of Invention
The invention aims to solve the problem of realizing 3.9 micron mid-infrared luminescence in glass materials, and the glass with good luminescence performance at the position of 3.9 microns is obtained by selecting proper glass materials and proper rare earth ions.
A preparation method of holmium and neodymium co-doped fluorine-aluminum glass capable of realizing 3.9 micron luminescence comprises the following steps:
step 1: weighing and preparing chemical raw materials according to a certain mole percentage, and then fully grinding and mixing.
Step 2: the mixed raw materials are put into a crucible and melted and fired in a glove box through a high-temperature furnace at 800-.
And step 3: and pouring the molten liquid into a preheated mold at about 370 ℃ (-40 ℃), keeping the temperature for 3 hours, and then slowly cooling the mold to room temperature to obtain holmium and neodymium codoped fluoroaluminium glass with different concentrations.
And 4, step 4: polishing the surface of the holmium and neodymium codoped fluorine-aluminum glass sample to optical quality to obtain a final glass sample capable of realizing 3.9 micron luminescence.
The chemical raw materials comprise the following components in percentage by mole:
30AlF3-15BaF2-(20-x-y)YF3-25PbF2-10MgF2-xHoF3-yNdF3wherein x and y are each any positive number less than 20.
The invention has the beneficial effects that:
(1) the glass prepared by the invention has simple preparation process and can realize batch production;
(2) the glass prepared by the invention has good spectral transmission width and transmission performance, and has no obvious visible transmittance reduction condition at the water molecule absorption position;
(3) the glass prepared by the invention has the luminescent property of 3.9 microns, and the luminescence can be realized by simple and reliable 808-nanometer laser pumping;
(4) the glass prepared by the invention has important application prospect in the field of realizing high-power 3.9-micron optical fiber laser.
Drawings
FIG. 1 is a graph of the luminescence spectrum of 3.9 μm of fluorine-aluminum glass doped with holmium neodymium ions in different concentration ratios;
FIG. 2 is a transmission spectrum of a holmium-neodymium co-doped fluoroaluminium glass;
fig. 3 is an energy transfer diagram of holmium neodymium co-doped fluoroaluminium glass.
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
a preparation method of praseodymium and ytterbium co-doped fluorine-aluminum glass with a 3.5 micron luminescence broadband comprises the following steps:
step 1: weighing and preparing the chemical raw materials according to the following mol percentage, and then fully grinding and mixing the raw materials in an agate mortar: 30AlF3-15BaF2-(20-x-y)YF3-25PbF2-10MgF2-xHoF3-yNdF3(x＝0.2、0.5、1、1.5、2、3、4、5；y＝1).
Step 2: the mixed raw materials are filled into a crucible and melted and fired in a glove box through a high-temperature furnace at 930 ℃.
And step 3: and pouring the molten liquid into a copper plate mold preheated at 370 ℃, keeping for 3 hours, and then slowly cooling to room temperature to obtain the holmium and neodymium ion co-doped fluoroaluminium glass with different concentration ratios.
And 4, step 4: polishing the surfaces of the holmium and neodymium ion codoped fluorine-aluminum glass samples with different concentration ratios to optical quality to obtain the final glass sample capable of realizing 3.9 micron luminescence.
Further optical tests were performed on the glass samples prepared above.
FIG. 1 is a 3.9 micron luminescence spectrum of a sample of fluoroaluminium glass doped with holmium neodymium ions in different concentration ratios, which is detected by a ZolixOmni-lambda 300i fluorescence spectrometer under the condition of 808 nm laser diode pumping. At a 2 to 1 molar ratio of holmium to neodymium ions, the maximum intensity and the widest emission range are reached at 3.9 microns, with the total emission range being about 3.7 microns to 4.2 microns. The luminescence sites shown in FIG. 1 correspond to holmium ions5I5→5I6A transition in energy level. In some materials with high phonon energy, it is difficult to observe luminescence at this wavelength.
FIG. 2 is a transmission spectrum measured by a Perkin Elmer Lambda750 spectrophotometer (250-10000 nm) and a Perkin Elmer FT-IR spectrometer (1000-10000 nm) for our sample of fluoroaluminium glass with a holmium neodymium ion ratio of 2: 1. In a small inset4F5/2And2H9/2the absorption peak is the absorption peak of neodymium ions, and the absorption peaks of the two energy levels are overlapped to form a clearly visible absorption peak. The absorption peak indicates that a holmium and neodymium co-doped glass sample can absorb the pump light of a commercial laser diode with 808 nanometers. FIG. 2 also shows that the transmittance of the aluminum fluoride glass can reach 90% at the position of the non-absorption peak of 400-4200 nm. The infrared cutoff wavelength was 9 microns, demonstrating that this glass can be used for mid-infrared applications.
FIG. 3 isWe plot the energy transfer mechanism of the holmium and neodymium co-doped glass under the pumping condition of the 808 nm laser diode. The neodymium ions absorbed the pump light at 808 nm and reached4F5/2And2H9/2energy level at which a portion of the ions can reabsorb light at 808 nm to reach2D5/2Energy level and then gradually relax to2D3/2Energy level, emitting 464 nm of light. At the same time, is located at4F5/2And2H9/2may be radiationless relaxed to4F3/2The energy level, and transitions to other lower energy levels at this energy level, emitting light at 876 nanometers, 1.06 micrometers, 1.32 micrometers, and 1.81 micrometers. Some ions may also be4F3/2With energy transfer to holmium ions5I5Energy level (energy transfer 1 process). 3.92 micron luminescence, i.e. holmium ions5I5To5I6Is detected. In addition to this, there are5I6To5I8，5I6To5I7And are and5I7to5I8Emits light at 1.19, 2.88, and 2 microns. Due to holmium ions5I6And5I7of energy level with neodymium ions4I15/2And4I13/2the energy levels are similar, so the neodymium ion can absorb the particles at the two energy levels and consume5I6And5I7the energy level, and thus further promotes the 3.92 and 2.88 micron luminescence of holmium ions ( energy transfer 2 and 3 processes). The fact shows that neodymium ions are introduced into holmium-doped fluorine-aluminum glass, so that 3.9-micron luminescence can be realized, and a new research idea is provided for developing mid-infrared lasers.
The above description is directed to the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that may be easily made by those skilled in the art within the technical scope of the present invention will be included in the present invention. The specific protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (4)

1. A preparation method of holmium and neodymium co-doped fluorine-aluminum glass capable of realizing 3.9 micron luminescence is characterized by comprising the following steps:
step 1: weighing and preparing chemical raw materials according to the mol percentage, and then fully grinding and mixing;
step 2: putting the mixed raw materials into a crucible, and melting and firing the mixed raw materials in a glove box through a high-temperature furnace;
and step 3: pouring the molten liquid into a preheated mold, keeping the molten liquid for 3 hours, and then slowly cooling the molten liquid to room temperature to obtain holmium and neodymium codoped fluorine-aluminum glass with different concentrations;
and 4, step 4: polishing the surface of the holmium and neodymium codoped fluorine-aluminum glass sample to optical quality to obtain a final glass sample capable of realizing 3.9 micron luminescence.
2. The method of claim 1, wherein: the chemical raw materials comprise the following components in percentage by mole:
30AlF3-15BaF2-(20-x-y)YF3-25PbF2-10MgF2-xHoF3-yNdF3wherein x and y are each any positive number less than 20.
3. The method of claim 1, wherein: the raw materials are required to be melted and fired in a high-temperature furnace in a glove box, wherein the temperature of the high-temperature furnace is 800-1000 ℃.
4. The method of claim 1, wherein: the molten glass is required to be annealed at the temperature of 330-410 ℃.
CN202110754317.4A 2021-07-05 2021-07-05 Preparation method of holmium and neodymium co-doped fluorine-aluminum glass capable of realizing 3.9 micron luminescence Pending CN113480172A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114836831A (en) * 2022-04-11 2022-08-02 同济大学 Er and Dy co-doped lead fluoride mid-infrared laser crystal and preparation method and application thereof

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN111377609A (en) * 2020-03-20 2020-07-07 苏州凯文堡尼光电科技有限公司 Preparation method of transparent glass with mid-infrared 3.9 mu m luminescence property at room temperature
CN112028480A (en) * 2020-09-09 2020-12-04 哈尔滨工程大学 Preparation method of praseodymium and ytterbium co-doped fluorine-aluminum glass with 3.5-micrometer luminescence broadband

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111377609A (en) * 2020-03-20 2020-07-07 苏州凯文堡尼光电科技有限公司 Preparation method of transparent glass with mid-infrared 3.9 mu m luminescence property at room temperature
CN112028480A (en) * 2020-09-09 2020-12-04 哈尔滨工程大学 Preparation method of praseodymium and ytterbium co-doped fluorine-aluminum glass with 3.5-micrometer luminescence broadband

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Title
RUICONG WANG ET AL.: "3.9 μm emission and energy transfer in ultra-low OH , Ho3+ /Nd3+ co-doped fluoroindate glasses", 《JOURNAL OF LUMINESCENCE》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114836831A (en) * 2022-04-11 2022-08-02 同济大学 Er and Dy co-doped lead fluoride mid-infrared laser crystal and preparation method and application thereof
CN114836831B (en) * 2022-04-11 2024-02-27 同济大学 Er, dy co-doped lead fluoride mid-infrared laser crystal and preparation method and application thereof

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