阅读说明：本技术 近红外双波段超宽带发射的稀土掺杂玻璃及其制备方法 (Near-infrared dual-band ultra-wideband emission rare earth doped glass and preparation method thereof ) 是由 周亚训 沈欣杰 张雨 夏礼章 朱雅瑞 于 2019-10-28 设计创作，主要内容包括：本发明公开了一种近红外双波段超宽带发射的稀土掺杂玻璃及其制备方法,该稀土掺杂玻璃包括摩尔百分比为74～74.9mol％的TeO<Sub>2</Sub>、14.5～15mol％的ZnO、4.5～5mol％的WO<Sub>3</Sub>、4.5～5mol％的Bi<Sub>2</Sub>O<Sub>3</Sub>、0.01～0.5mol％的Pr<Sub>6</Sub>O<Sub>11</Sub>、0.01～0.1mol％的Nd<Sub>2</Sub>O<Sub>3</Sub>、0.01～0.4mol％的Er<Sub>2</Sub>O<Sub>3</Sub>；优点是其能够同时实现800～1100nm和1250～1650nm波长范围的两个近红外波段超宽带且相对平坦的光发射,所制备玻璃稳定、物化性能优良。(The invention discloses rare earth doped glass for near-infrared dual-waveband ultra-wideband emission and a preparation method thereof, wherein the rare earth doped glass comprises 74-74.9 mol% of TeO 2 14.5 to 15 mol% of ZnO, 4.5 to 5 mol% of WO 3 4.5 to 5 mol% of Bi 2 O 3 0.01 to 0.5 mol% of Pr 6 O 11 0.01 to 0.1 mol% of Nd 2 O 3 0.01 to 0.4 mol% of Er 2 O 3 (ii) a Has the advantages that the ultra-infrared dual-band ultra-infrared optical fiber can simultaneously realize the wavelength ranges of 800-1100 nm and 1250-1650 nmWide band and relatively flat light emission, and the prepared glass is stable and has excellent physical and chemical properties.)

1. The rare earth doped glass for near-infrared two-waveband ultra-wideband emission is characterized in that a matrix of the rare earth doped glass is tellurate glass, and the rare earth doped glass comprises the following components in percentage by mole:

2. the near-infrared dual band ultra-wideband emission rare earth-doped glass according to claim 1, wherein the component TeO₂、ZnO、WO₃、Bi₂O₃、Pr₆O₁₁、Nd₂O₃And Er₂O₃The purity of the product is 99.99 percent by mass.

3. The near-infrared dual-band ultra-wideband emission rare earth-doped glass according to claim 1 or 2, characterized in that the rare earth-doped glass comprises the following components in mole percent:

4. the near-infrared dual-band ultra-wideband emission rare earth-doped glass according to claim 1 or 2, characterized in that the rare earth-doped glass comprises the following components in mole percent:

5. a preparation method of rare earth doped glass for near-infrared dual-band ultra-wideband emission is characterized by comprising the following steps:

the method comprises the following steps: selecting a raw material formula according to the following components in percentage by mole, then calculating the weight percentage of each powdery raw material according to the total amount of the rare earth doped glass to be prepared, and weighing each powdery raw material;

step two: uniformly mixing all the weighed powdery raw materials, and pouring the mixture into a corundum crucible; then, the corundum crucible filled with the raw material mixture is moved into a precise temperature control muffle furnace, the furnace temperature of the precise temperature control muffle furnace is increased to 240-260 ℃ from room temperature, and dehumidification and drying are carried out for 0.8-1.2 hours;

step three: taking out the corundum crucible which is dehumidified and then filled with the raw material mixture from the precise temperature control muffle furnace, placing the corundum crucible in a silicon carbide rod electric furnace at the temperature of 880-920 ℃, melting the raw material mixture, standing for 8-12 minutes after the raw material mixture is completely melted, stirring for 14-16 minutes, continuing to melt at the temperature of 880-920 ℃ for 4-6 minutes, and clarifying to obtain a glass melt;

step four: taking out the corundum crucible filled with the glass melt from the silicon carbide rod electric furnace; then pouring the molten glass on a preheated copper plate mold;

step five: rapidly moving the copper plate mold poured with the molten glass to a precise temperature-controlled muffle furnace heated to 350-390 ℃ for annealing, and closing the precise temperature-controlled muffle furnace after the annealing is finished to obtain a tellurate glass sample;

step six: taking out the copper plate mould containing the tellurite glass sample from the precise temperature control muffle furnace; then processing the tellurate glass sample into a glass sample with double-sided polishing.

6. The method of claim 5, wherein the preheated copper plate mold is at a temperature of 280-320 ℃.

7. The method for preparing the near-infrared dual-band ultra-wideband emission rare earth doped glass according to claim 5 or 6, wherein the annealing process in the fifth step is as follows: after the copper plate mold poured with the glass melt is moved to a precise temperature-controlled muffle furnace heated to 350-390 ℃, the temperature is preserved for 1.5-2.5 hours, and then the temperature in the precise temperature-controlled muffle furnace is cooled to room temperature at the speed of 9-11 ℃/hour.

8. The method of claim 5 wherein in step one, TeO is used to form the rare earth doped glass₂、ZnO、WO₃、Bi₂O₃、Pr₆O₁₁、Nd₂O₃And Er₂O₃The purity of the product is 99.99 percent by mass.

9. The method for preparing the near-infrared dual-band ultra-wideband emission rare earth doped glass according to claim 5 or 8, wherein in the first step, the molar percentages of the components are as follows:

10. the method for preparing the near-infrared dual-band ultra-wideband emission rare earth doped glass according to claim 5 or 8, wherein in the first step, the molar percentages of the components are as follows:

Technical Field

The invention relates to rare earth doped glass used in the fields of medical imaging, optical fiber communication and the like and a preparation technology thereof, in particular to rare earth doped glass for near-infrared dual-band ultra-wideband emission and a preparation method thereof, wherein the rare earth doped glass is rare earth Pr³⁺-Nd³⁺-Er³⁺Ion-doped tellurite glass.

Background

The near-infrared band light source has very important application in a plurality of fields such as medical imaging, laser surgery, photovoltaic cells, component analysis, atmospheric remote sensing, optical fiber communication and the like. For example, in medical imaging, the 1.0 μm near infrared band is often referred to as the "bio-window" of human tissue because laser light in this wavelength range can penetrate deeper into biological tissue than in the ultraviolet and visible bands. The near infrared band of 1.53 μm is called a third communication window, is located in the lowest loss region of the quartz transmission fiber, and is the main optical carrier channel of the current Wavelength Division Multiplexing (WDM) communication system.

Due to the rich energy level structure of trivalent rare earth ions, rare earth doped glass and crystal materials are the most promising technical schemes for obtaining near-infrared band light sources at present. Thus, over the last decades, numerous researchers have passed through rare earth elements such as Er³⁺、Tm³⁺、Nd³⁺、Yb³⁺、Ho³⁺And Pr³⁺The ion single-doping, double-doping or triple-doping forms develop near-infrared band light sources in different wavelength ranges on different substrate materials. However, for a given doped glass material, under the excitation of a single pump light, the near infrared band spectrum obtained at present has a bandwidth range which is not ideal or only has one limitation on the obtained broadband near infrared band spectrum. Broadband near infrared band spectroscopy is highly desirable in many applications. For example, in the operation of Optical Coherence Tomography (OCT), the wider the spectrum of the 1.0 μm near-infrared band, the more axially resolved OCT images can be obtained. Also, in WDM communication systems, the wider the 1.53 μm near-infrared band spectrum, the more optical carrier channels can be provided to carry increasing communication capacity. While the spectral bandwidth of the near infrared band is narrow and singleThe spectrum of the broadband near-infrared band limits the application range of rare earth doped glass and crystal materials.

Disclosure of Invention

The invention aims to solve the technical problem of providing rare earth doped glass for near-infrared dual-band ultra-wideband emission and a preparation method thereof, wherein the rare earth doped glass can simultaneously realize the ultra-wideband emission of two near-infrared bands in the wavelength ranges of 800-1100 nm and 1250-1650 nm, and is stable and excellent in physical and chemical properties.

The technical scheme adopted by the invention for solving the technical problems is as follows: the rare earth doped glass for near-infrared two-waveband ultra-wideband emission is characterized in that a matrix of the rare earth doped glass is tellurate glass, and the rare earth doped glass comprises the following components in percentage by mole:

the component TeO₂、ZnO、WO₃、Bi₂O₃、Pr₆O₁₁、Nd₂O₃And Er₂O₃The purity of the product is 99.99 percent by mass.

The rare earth doped glass comprises the following components in percentage by mole:

the rare earth doped glass comprises the following components in percentage by mole:

a preparation method of rare earth doped glass for near-infrared dual-band ultra-wideband emission is characterized by comprising the following steps:

the method comprises the following steps: selecting a raw material formula according to the following components in percentage by mole, then calculating the weight percentage of each powdery raw material according to the total amount of the rare earth doped glass to be prepared, and weighing each powdery raw material;

step two: uniformly mixing all the weighed powdery raw materials, and pouring the mixture into a corundum crucible; then, the corundum crucible filled with the raw material mixture is moved into a precise temperature control muffle furnace, the furnace temperature of the precise temperature control muffle furnace is increased to 240-260 ℃ from room temperature, and dehumidification and drying are carried out for 0.8-1.2 hours;

step three: taking out the corundum crucible which is dehumidified and then filled with the raw material mixture from the precise temperature control muffle furnace, placing the corundum crucible in a silicon carbide rod electric furnace at the temperature of 880-920 ℃, melting the raw material mixture, standing for 8-12 minutes after the raw material mixture is completely melted, stirring for 14-16 minutes, continuing to melt at the temperature of 880-920 ℃ for 4-6 minutes, and clarifying to obtain a glass melt;

step four: taking out the corundum crucible filled with the glass melt from the silicon carbide rod electric furnace; then pouring the molten glass on a preheated copper plate mold;

step five: rapidly moving the copper plate mold poured with the molten glass to a precise temperature-controlled muffle furnace heated to 350-390 ℃ for annealing, and closing the precise temperature-controlled muffle furnace after the annealing is finished to obtain a tellurate glass sample;

step six: taking out the copper plate mould containing the tellurite glass sample from the precise temperature control muffle furnace; then processing the tellurate glass sample into a glass sample with double-sided polishing.

In the fourth step, the temperature of the preheated copper plate die is 280-320 ℃.

The annealing process in the fifth step is as follows: after the copper plate mold poured with the glass melt is moved to a precise temperature-controlled muffle furnace heated to 350-390 ℃, the temperature is preserved for 1.5-2.5 hours, and then the temperature in the precise temperature-controlled muffle furnace is cooled to room temperature at the speed of 9-11 ℃/hour.

In the step one, TeO₂、ZnO、WO₃、Bi₂O₃、Pr₆O₁₁、Nd₂O₃And Er₂O₃The purity of the product is 99.99 percent by mass.

In the first step, the mole percentage of each component is as follows:

in the first step, the mole percentage of each component is as follows:

compared with the prior art, the invention has the advantages that:

1) the invention introduces rare earth Pr into tellurate glass³⁺Ion, rare earth Nd³⁺Ion and rare earth Er³⁺The rare earth doped glass realizes the ultra-wideband light emission of two near infrared wave bands in the wavelength ranges of 800-1100 nm and 1250-1650 nm simultaneously under the excitation of the pump light with the wavelength of 488nm through the optimization of the co-doping concentration of three rare earth ions, the full width at half maximum (FWHM) of the fluorescence of the rare earth doped glass respectively reaches 225nm and 296nm, and the spectrum is relatively flat.

2) The rare earth doped tellurate glass is stable and has excellent physical and chemical performance.

3) The invention adopts a common temperature control muffle furnace and a silicon-carbon rod electric furnace to prepare the rare earth doped tellurate glass, requires less equipment and has simple process, and is very suitable for application in actual production.

Drawings

FIG. 1a is a fluorescence emission spectrum of a near infrared band in a wavelength range of 800-1100 nm measured by a glass sample of the first embodiment and the second embodiment under excitation of pump light with a wavelength of 488 nm;

FIG. 1b is a fluorescence emission spectrum of a near infrared band in a wavelength range of 1250-1650 nm measured by a glass sample of the first embodiment and the second embodiment under excitation of pump light with a wavelength of 488 nm;

FIG. 2a shows fluorescence emission spectra of three rare earth doped glasses in the near infrared band of 800-1100 nm wavelength range measured under the excitation of the pump light of 488nm wavelength;

FIG. 2b shows fluorescence emission spectra of near infrared band in wavelength range of 1250-1650 nm measured by the pump light excitation of 488nm wavelength for three kinds of rare earth doped glass.

Detailed Description

The invention is described in further detail below with reference to the accompanying examples.