阅读说明：本技术 一种高掺铒中红外3.5微米激光玻璃及其制备方法 (High erbium-doped mid-infrared 3.5-micron laser glass and preparation method thereof ) 是由 黄飞飞 王政 徐时清 叶仁广 蔡沐之 于 2021-10-21 设计创作，主要内容包括：本发明涉及发光玻璃技术领域,具体涉及一种高掺铒中红外3.5微米激光玻璃及其制备方法；所述高掺铒中红外3.5微米激光玻璃,为掺铒氧卤的碲酸盐玻璃,原料包括卤化物和氧化物。本发明提供的高掺铒中红外3.5微米激光玻璃具有较高的机械性能、硬度以及热稳定性,Er～(3+)的摩尔百分比能达到4mol％,实现了Er～(3+)的高浓度掺杂,经测试该氧卤玻璃差热曲线图玻璃熔点Tg在250℃附近,具有较低的玻璃转变温度；制备过程中熔制温度降至800℃,更节能,且制作工艺简单,绿色环保,生产成本也较低,容易制备获得高光学质量玻璃。(The invention relates to the technical field of luminescent glass, in particular to high erbium-doped mid-infrared 3.5 micron laser glass and a preparation method thereof; the high erbium-doped mid-infrared 3.5 micron laser glass is erbium-doped oxyhalide tellurate glass, and the raw materials comprise halide and oxide. The high erbium-doped mid-infrared 3.5-micron laser glass provided by the invention has higher mechanical property, hardness and thermal stability, and Er 3+ The mol percent of the Er can reach 4mol percent, and the Er is realized 3+ The melting point Tg of the glass of the oxyhalogen glass differential thermal curve graph is tested to be near 250 ℃, and the glass has lower glass transition temperature; the melting temperature is reduced to 800 ℃ in the preparation process, the energy is saved, the preparation process is simple, the environment is protected, the production cost is low, and the glass with high optical quality is easy to prepare.)

1. The high erbium-doped mid-infrared 3.5 micron laser glass is characterized by being tellurite glass doped with erbium oxyhalide.

2. The high erbium-doped mid-infrared 3.5-micron laser glass according to claim 1, wherein the tellurate glass is TeO₂-GeO₂-ZnO-Na₂O; the raw materials of the high erbium-doped mid-infrared 3.5 micron laser glass comprise halide and oxide, wherein the halide is ZnCl₂、NaCl、ErCl₃One or more combinations of; the oxide is TeO₂、GeO₂ZnO and Na₂O, or a combination of one or more thereof.

3. The high erbium-doped mid-infrared 3.5 micron laser glass according to claim 1, wherein the high erbium-doped mid-infrared 3.5 micron laser glass comprises the following components in mole percent:

TeO₂：60％；GeO₂：10％；ZnO：5～15％；ZnCl₂：0～10％；Na₂O：5～15％；NaCl：0～10％；ErCl₃：1～4％。

4. a method of making a high erbium doped mid-infrared 3.5 micron laser glass according to any of claims 1-3, comprising the steps of:

melting a mixture obtained by uniformly grinding the raw material components until the mixture is homogenized and clarified to obtain glass liquid; pouring the molten glass into a preheated mold, annealing, and cooling to room temperature to obtain the high erbium-doped mid-infrared 3.5 micron laser glass.

5. The method of making a high erbium-doped mid-infrared 3.5 micron laser glass as claimed in claim 4, wherein said melting conditions are: melting at 800 deg.C in air atmosphere for 10-15min after homogenization and clarification.

6. The method for preparing the high erbium-doped mid-infrared 3.5 micron laser glass as claimed in claim 4, wherein the preheating temperature is 250-300 ℃.

7. The method for preparing the high erbium-doped mid-infrared 3.5 micron laser glass according to claim 4, wherein the annealing conditions are as follows: 250 ℃ and 2-5 h.

8. The method for preparing the high erbium-doped mid-infrared 3.5 micron laser glass according to claim 4, wherein the cooling rate of the temperature to room temperature is reduced to room temperature, specifically 10 ℃/h.

9. Use of a high erbium-doped mid-infrared 3.5 μm laser glass according to any one of claims 1-3 as an optical fiber material.

Technical Field

The invention relates to the technical field of luminescent glass, in particular to high erbium-doped mid-infrared 3.5 micron laser glass and a preparation method thereof.

Background

The laser in the middle infrared band is positioned in two important transmission windows (1-3 microns and 3-5 microns) of the atmosphere, has strong water absorption capacity, and simultaneously, the heat radiation energy is mainly concentrated in the region, so that the middle infrared laser has wide application prospects in various fields such as remote sensing detection, military, medical treatment, communication and the like, and the laser material in the band has a great research value.

Erbium ions have rich energy levels and relatively high doping concentration, are important doping ions for mid-infrared luminescence, and have been widely researched by researchers. In particular for Er³⁺Based on⁴I_11/2→⁴I_3/2The report of 2.7 μm luminescence is endless. However, based on Er³⁺：⁴F_9/2→⁴I_9/2The 3.5 μm luminescence studies are still rare. In 1991, Tobben reports Er for the first time³⁺3449 and 3478nm, and Er is doped³⁺The fluorozirconate glass fiber of (a) obtained an output of 8.5 mW. In 2015, Henderson-Sapir et al excited Er using 985nm and 1976nm dual wavelength pumping³⁺ZBLAN, also achieving a continuous laser output of 3.5 μm.

At present, Er doping is concerned³⁺The 3.5 μm of (B) emits light and is mainly fluoride glass. However, fluoride glass has limited improvement of laser power due to its inherent defects, poor chemical stability and mechanical strength, harsh preparation conditions, susceptibility to water erosion, poor devitrification resistance (Δ T ≦ 85 ℃), and the like. Although silicate glass has high thermal stability and strong tensile resistance, excellent luminescence performance is difficult to obtain due to high phonon energy and low rare earth ion solubility, and multiphoton relaxation is reducedThe luminous efficiency thereof is improved. The energy of the phonon of the tellurate glass is low (700-750 cm)^-1) The rare earth luminescent material is beneficial to improving the rare earth radiation transition probability and has higher luminous efficiency. Therefore, it is necessary to provide a tellurite glass capable of emitting light in the infrared region of 3.5 μm.

Disclosure of Invention

Based on the content, the invention provides high erbium-doped mid-infrared 3.5 micron laser glass and a preparation method thereof.

One of the technical schemes of the invention is high erbium-doped mid-infrared 3.5 micron laser glass which is tellurate glass doped with erbium oxyhalide.

Further, the tellurate glass is TeO₂-GeO₂-ZnO-Na₂O。

The high erbium-doped mid-infrared 3.5 micron laser glass can obtain luminescence with the central wavelength of 3.5 mu m within the range of 3300-3700 nm under the pumping of a 650nm semiconductor laser, and is based on Er³⁺:⁴F_9/2→⁴I_9/2Radiative transitions between energy levels.

Furthermore, the raw materials of the high erbium-doped mid-infrared 3.5 micron laser glass comprise halide and oxide, wherein the halide is ZnCl₂、NaCl、ErCl₃One or more combinations of; the oxide is TeO₂、GeO₂ZnO and Na₂O, or a combination of one or more thereof.

Further, the high erbium-doped mid-infrared 3.5 micron laser glass comprises the following raw materials in percentage by mole:

TeO₂：60％；GeO₂：10％；ZnO：5～15％；ZnCl₂：0～10％；Na₂O：5～15％；NaCl：0～10％；ErCl₃：1～4％。

in the scheme, a proper amount of germanium oxide is added into the tellurate glass to replace part of tellurium oxide to serve as a glass forming body, so that the tellurate glass is formed, and the thermal stability and the mechanical property of the glass are improved. On the other hand, the proper amount of halide is added into the raw materials, and the mixture has lower phonon energy (200-300 cm)^-1) Introduction of chloride asFor the network modification, the structure of the glass network is changed to form [ ZnCl ]₄]The space tetrahedron is uniformly distributed in the glass network, so that the doping performance of the glass matrix to the rare earth ions can be further improved, and the physicochemical performance and the laser emission performance of the luminescent material are improved. And with Er³⁺High-concentration doping is carried out for doping ions, and the 3.5-micron mid-infrared luminescent glass with excellent luminescent performance and high gain is finally obtained. ZnCl₂Can improve the hardness and thermal stability of the glass and can provide a glass having a low T_gYet with a larger Δ T (T)_x-T_g) The glass of (2).

According to the second technical scheme, the preparation method of the high erbium-doped mid-infrared 3.5 micron laser glass comprises the following steps:

melting a mixture obtained by uniformly grinding the raw material components until the mixture is homogenized and clarified to obtain bubble-free glass liquid; pouring the molten glass into a preheated mold, annealing, and cooling to room temperature to obtain the high erbium-doped mid-infrared 3.5 micron laser glass.

Further, the melting conditions are as follows: melting at 800 deg.C in air atmosphere for 10-15min after homogenization and clarification. The melting temperature higher than 800 ℃ can cause the tellurium oxide to be volatilized seriously, which affects the product quality

Further, the preheating temperature is 250-300 ℃.

Further, the annealing conditions are as follows: 250 ℃ and 2-5 h.

Further, the temperature is reduced to the room temperature, specifically, the temperature reduction rate of 10 ℃/h is reduced to the room temperature.

According to the third technical scheme, the high erbium-doped mid-infrared 3.5-micron laser glass is applied as an optical fiber material.

Compared with the prior art, the invention has the beneficial effects that:

the high erbium-doped mid-infrared 3.5 micron laser glass provided by the invention has higher mechanical property, hardness and thermal stability, and germanate is added into a tellurate glass system, so that the network structure of the glass is relaxed, and the high erbium-doped mid-infrared 3.5 micron laser glass is more suitable for doping rare earth ions, thereby enabling Er to be doped³⁺Can reach the mol percentage4 mol% of Er is realized³⁺High concentration doping (Er under general conditions)³⁺Has a doping concentration of 0.5-2%), and the melting point T of the glass is measured according to the differential thermal curve diagram of the oxyhalogen glass_gThe glass transition temperature is lower at the temperature of 250 ℃; the melting temperature is reduced to 800 ℃ in the preparation process, the energy is saved, the preparation process is simple, the environment is protected, the production cost is low, and the glass with high optical quality is easy to prepare.

Drawings

FIG. 1 is a graph showing a differential thermal curve of a glass obtained in step (1) of the effect verification example of the present invention.

FIG. 2 is a graph showing a comparison of absorption spectra of glasses obtained in step (2) of the effect verification example of the present invention.

FIG. 3 is a comparison graph of the mid-infrared 3.5 μm fluorescence spectrum of the glass obtained in step (3) of the verification example of the effect of the present invention under the excitation of 650nm pump source.

FIG. 4 is a graph showing the gain of the glass obtained in step (4) of the verification example of the effect of the present invention in the mid-infrared region of 3.5 μm under the excitation of a 650nm pump source, wherein a is an absorption and emission cross-section view, and b is a gain graph.

Detailed Description

Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.

It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.

It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.

As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.

Examples 1 to 5

Calculating the weight of each corresponding component according to the mol percentage of the components of the formula glass in the table 1, and weighing each raw material component; grinding the raw materials uniformly to form a mixture, putting the mixture into a platinum crucible, placing the platinum crucible into a 800 ℃ silicon-carbon rod electric furnace to be melted for 30 minutes to obtain molten glass liquid, homogenizing and clarifying the mixture to obtain uniform bubble-free glass liquid, quickly pouring the uniform bubble-free glass liquid onto a mold preheated to 300 ℃, then putting the uniform bubble-free glass liquid into a muffle furnace heated to 250 ℃, preserving heat for 2-3 hours, reducing the temperature to room temperature at a cooling rate of 10 ℃/min, and completely cooling the glass sample and taking out the glass sample.

TABLE 1

	TeO2/％	GeO2/％	ZnO/％	ZnCl2/％	Na2O/％	NaCl/％	ErCl3/％
								Example 1	60	10	15	0	15	0	0
Example 2	60	10	5	10	5	9	1
								Example 3	60	10	5	10	5	8	2
Example 4	60	10	5	8	5	8	4
								Example 5	60	10	5	10	5	10	0

Example of Effect verification

(1) Samples of example 1 and example 5 after annealing were ground into fine powder with an agate mortar and subjected to differential thermal analysis, and the results are shown in fig. 1; the results show that the oxide glass of example 1(1#) has a melting point T_gAt around 303 ℃, the thermal stability is relatively poor at (T)_x-T_g) 111 ℃, further improvement is needed to be applied to the preparation and application of mid-infrared 3.5 μm laser glass and optical fiber materials; example 5(2#) glass melting Point T_gHas better thermal stability delta T (T) at the temperature of about 251 DEG C_x-T_g)＝186℃。

(2) The glasses of examples 2 to 4 were processed into 10X 20X 1 mm glass pieces and polished, followed by absorption spectroscopy as shown in FIG. 2; the results show that the glasses of examples 2-4 (corresponding to 2#, 3#, and 4#, respectively) are transparent, have no crystallization, and have obvious characteristics²G_11/2，²H_9/2，⁴F_5/2，⁴F_7/2，⁴F_9/2，⁴I_9/2，⁴I_11/2，⁴I_13/2Isoabsorbance peaks; significant mid-infrared 3.5 μm fluorescence can be obtained under 650nm wavelength laser diode pumping. Is suitable for the preparation and application of mid-infrared 3.5 mu m laser glass and optical fiber materials.

(3) On the basis of the step (2), testing the fluorescence spectrum of 3300-3700 nm wave band under the pumping of 650nm laser diode, as shown in fig. 3; as can be seen from fig. 3, the fluorescence intensity was significantly increased with the increase in the doping amount of erbium ion, and the fluorescence intensity was strongest in example 4 with the doping amount of 4% (4 #).

(4) The results of the absorption, emission cross section and gain coefficient calculations for example 4 according to McCumber and Fuchbauer-Ladenburger theories are shown in fig. 4; in fig. 4, (a) is an absorption and emission cross-sectional view, and (b) is a gain diagram.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.