阅读说明：本技术 一种近红外波段宽带发射稀土掺杂铋酸盐光纤玻璃及其制备方法 (Near-infrared band broadband emission rare earth doped bismuthate optical fiber glass and preparation method thereof ) 是由 陈卫东 王传杰 张鹏 魏敏 张桂林 张明立 于 2021-02-06 设计创作，主要内容包括：本发明提供了一种近红外波段宽带发射稀土掺杂铋酸盐光纤玻璃及其制备方法,其解决了现有对于给定的玻璃基质,在单一泵浦光的激励下,得到的近红外波段光谱存在着放大带宽范围小或增益范围存在局限性的技术问题,按照摩尔百分比,该铋酸盐光纤玻璃包括以下原材料：74～75mol％的Bi-2O-3,19～20mol％的B-2O-3,4～5mol％的Na-2O,0.3～0.5mol％的Er-2O-3,0.8～1.2mol％的Yb-2O-3,0.2～0.4mol％的Pr-6O-(11),本发明还公开了近红外波段宽带发射稀土掺杂铋酸盐光纤玻璃的制备方法,可广泛应用于光纤通信材料领域。(The invention provides near-infrared band broadband emission rare earth doped bismuthate optical fiber glass and a preparation method thereof, which solve the technical problem that the near-infrared band spectrum obtained by a given glass substrate under the excitation of single pump light has small amplification bandwidth range or limited gain range, and the bismuthate optical fiber glass comprises the following raw materials in mol percent: 74 to 75 mol% of Bi 2 O 3 19 to 20 mol% of B 2 O 3 4 to 5 mol% of Na 2 O, 0.3-0.5 mol% Er 2 O 3 0.8 to 1.2 mol% of Yb 2 O 3 0.2 to 0.4 mol% of Pr 6 O 11 The invention also discloses a preparation method of the near-infrared band broadband emission rare earth doped bismuthate optical fiber glass, which can be widely applied to the field of optical fiber communication materials.)

1. The near-infrared band broadband emission rare earth doped bismuthate optical fiber glass is characterized in thatThe composite material comprises the following raw materials in percentage by mole: 74 to 75 mol% of Bi₂O₃19 to 20 mol% of B₂O₃4 to 5 mol% of Na₂O, 0.3-0.5 mol% Er₂O₃0.8 to 1.2 mol% of Yb₂O₃0.2 to 0.4 mol% of Pr₆O₁₁。

2. The near-infrared band broadband emission rare-earth doped bismuthate optical fiber glass according to claim 1, which comprises the following raw materials in mol percent: 75 mol% of Bi₂O₃19 mol% of B₂O₃4.4 mol% of Na₂O, 0.3 mol% Er₂O₃1.0 mol% of Yb₂O₃0.3 mol% of Pr₆O₁₁。

3. The near-infrared band broadband emission rare-earth doped bismuthate optical fiber glass according to claim 1, which comprises the following raw materials in mol percent: 74 mol% of Bi₂O₃20 mol% of B₂O₃4 mol% of Na₂O, 0.4 mol% Er₂O₃1.2 mol% of Yb₂O₃0.4 mol% of Pr₆O₁₁。

4. The near-infrared band broadband emission rare-earth doped bismuthate optical fiber glass according to any one of claims 1 to 3, wherein B is₂O₃With H₃BO₃Is doped with the form of Na₂O is Na₂CO₃Is incorporated in the form of (1).

5. A method for preparing the near-infrared band broadband emission rare-earth doped bismuthate optical fiber glass of any one of claims 1 to 4, which comprises the following steps:

(1) weighing the raw materials according to the mol percentage for later use;

(2) fully and uniformly mixing the raw materials weighed in the step (1), and heating and melting to obtain a glass solution;

(3) quenching and forming the glass solution obtained in the step (2) to obtain a glass sheet;

(4) and (4) annealing the glass sheet obtained in the step (3) to obtain bismuthate optical fiber glass.

6. The method of claim 5, wherein the step (2): fully grinding the weighed raw materials in the step (1), uniformly mixing, pouring into a corundum crucible, and placing in a high-temperature furnace at 1050-1100 ℃ for melting for 1h to obtain a glass solution.

7. The method of claim 6, wherein the step (3): and taking the corundum crucible filled with the glass solution out of the high-temperature furnace, and carrying out quenching forming on a preheated graphite mold to obtain the glass sheet.

8. The method of claim 7, wherein the step (4): and putting the graphite mold poured with the glass solution into a muffle furnace at 330-350 ℃ for annealing, and obtaining the bismuthate optical fiber glass after the annealing is finished.

9. The method of claim 8, wherein the annealing process is: and transferring the graphite mold with the glass liquid to a muffle furnace heated to 330-350 ℃, preserving heat for 2h, and then cooling to room temperature at the speed of 8-10 ℃/h.

10. The method according to claim 8 or 9, wherein the step (4): and taking out the graphite mold with the bismuthate optical fiber glass from the muffle furnace, and carrying out double-sided polishing treatment on the bismuthate optical fiber glass.

Technical Field

The application belongs to the field of optical fiber communication materials, and particularly relates to near-infrared band broadband emission rare earth doped bismuthate optical fiber glass and a preparation method thereof.

Background

The rare earth doped optical fiber amplifier is the most mature and widely applied optical amplifier at present, and converts the light energy of a Laser Diode (LD) pump to signal light by utilizing the energy level transition of rare earth ions doped in a transmission medium of the optical amplifier to realize the amplification function of the signal light. Different rare earth ions are doped to realize the amplification of optical signals with different wave bands. The working wavelength of the erbium-doped fiber amplifier is located in a C wave band (1530-1565 nm), the working wavelength corresponds to the lowest loss region of the optical fiber, and the wave band is applied to optical fiber communication at the earliest. And for the laid G.652 optical fiber, the zero dispersion is near 1.3 mu m, the dispersion influence is small, the dispersion compensation technology is not needed, and a large amount of investment can be saved. Therefore, in recent years, researchers and researchers have proposed Er as a rare earth ion³⁺、Pr³⁺、Ho³⁺And Tm³⁺And several ions are singly doped or co-doped to obtain near infrared band broadband emission of different bands. However, for a given glass matrix, under the excitation of a single pump light, the near infrared band spectrum obtained at present has the phenomenon that the amplification bandwidth range is small or the gain range is limited, so that the amplification range cannot cover the lowest loss region (1.5 μm) and the zero dispersion region (1.3 μm) of optical signal transmission, which also limits the rare earth-doped glass in the optical fiberApplication in communications.

Disclosure of Invention

The invention aims to solve the technical defects and provides the rare earth doped bismuthate optical fiber glass capable of emitting the near-infrared band broadband emission and the preparation method thereof.

In order to solve the technical problem, the invention provides a near-infrared band broadband emission rare earth doped bismuthate optical fiber glass which comprises the following raw materials in percentage by mole: 74 to 75 mol% of Bi₂O₃19 to 20 mol% of B₂O₃4 to 5 mol% of Na₂O, 0.3-0.5 mol% Er₂O₃0.8 to 1.2 mol% of Yb₂O₃0.2 to 0.4 mol% of Pr₆O₁₁。

Preferably, the raw materials comprise the following components in percentage by mole: 75 mol% of Bi₂O₃19 mol% of B₂O₃4.4 mol% of Na₂O, 0.3 mol% Er₂O₃1.0 mol% of Yb₂O₃0.3 mol% of Pr₆O₁₁。

Preferably, the raw materials comprise the following components in percentage by mole: 74 mol% of Bi₂O₃20 mol% of B₂O₃4 mol% of Na₂O, 0.4 mol% Er₂O₃1.2 mol% of Yb₂O₃0.4 mol% of Pr₆O₁₁。

Preferably, B₂O₃With H₃BO₃Form of (2) incorporation of Na₂O is Na₂CO₃Is incorporated in the form of (1). I.e. B₂O₃From twice the molar amount of H₃BO₃Instead of, Na₂O is formed from an equimolar amount of Na₂CO₃Instead. B is₂O₃Mainly adding B³⁺Action of Na₂O mainly adds Na⁺The function of (1). H₃BO₃Decomposition at elevated temperatures may give B₂O₃Reaction of (1), Na₂CO₃Decomposition at high temperature can produce Na₂Reaction of O, likewiseTo add B separately³⁺And Na⁺The function of (1).

The preparation method of the near-infrared band broadband emission rare earth doped bismuthate optical fiber glass comprises the following steps:

(1) weighing the raw materials according to the mol percentage for later use;

(2) fully and uniformly mixing the raw materials weighed in the step (1), and heating and melting to obtain a glass solution;

(3) quenching and forming the glass solution obtained in the step (2) to obtain a glass sheet;

(4) and (4) annealing the glass sheet obtained in the step (3) to obtain bismuthate optical fiber glass.

Preferably, step (2): fully grinding the weighed raw materials in the step (1), uniformly mixing, pouring into a corundum crucible, and placing in a high-temperature furnace at 1050-1100 ℃ for melting for 1h to obtain a glass solution.

Preferably, step (3): and taking the corundum crucible filled with the glass solution out of the high-temperature furnace, and carrying out quenching forming on a preheated graphite mold to obtain the glass sheet.

Preferably, step (4): and (3) putting the graphite mold poured with the glass solution into a muffle furnace at 330-350 ℃ for annealing, and obtaining the bismuthate optical fiber glass after the annealing is finished.

Preferably, the annealing process is as follows: and transferring the graphite mold with the glass liquid to a muffle furnace heated to 330-350 ℃, preserving heat for 2h, and then cooling to room temperature at the speed of 8-10 ℃/h.

Preferably, step (4): and taking out the graphite mold with the bismuthate optical fiber glass from the muffle furnace, and carrying out double-sided polishing treatment on the bismuthate optical fiber glass.

The invention has the beneficial effects that: the invention provides a near-infrared band broadband emission rare earth doped bismuthate optical fiber glass and a preparation method thereof, and the glass has the following outstanding characteristics and beneficial effects:

(1) er is introduced into bismuthate optical fiber glass³⁺、Pr³⁺And Yb³⁺Three kinds of rare earth ions are doped by the three kinds of ions and the concentration is excellentThe Er-Pr-Yb co-doped bismuthate optical fiber glass has two near-infrared broadband emissions in the ranges of 1200-1400 nm and 1450-1650 nm under the excitation of pump light with the wavelength of 980nm, the full width at half maximum (FWHM) of the fluorescence of the Er-Pr-Yb co-doped bismuthate optical fiber glass reaches 82nm and 84nm respectively, and the spectrum is relatively flat.

(2) The rare earth doped bismuthate optical fiber glass has simple preparation process and excellent physical and chemical properties.

(3) The invention adopts the silicon carbide rod electric furnace and the common temperature control muffle furnace to prepare the bismuthate optical fiber glass, needs less equipment and is very suitable for application in actual production.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.

FIG. 1 shows fluorescence emission spectra of bismuthate optical fiber glasses prepared in examples 1 and 2 in the near-infrared band in the wavelength range of 1200-1700 nm, measured under the excitation of pump light with the wavelength of 980 nm;

FIG. 2 shows fluorescence emission spectra of bismuthate optical fiber glasses prepared in examples 3 and 4 in the near-infrared band in the wavelength range of 1200-1700 nm, measured under the excitation of pump light with the wavelength of 980 nm.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application clearer, the present application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.

Example 1

The invention provides a near-infrared band broadband emission rare earth doped bismuthate optical fiber glass, which comprises the following steps:

(1) according to mol percentRespectively weighing the following raw materials: 75 mol% of Bi₂O₃19 mol% of B₂O₃4.4 mol% of Na₂O, 0.3 mol% Er₂O₃1.0 mol% of Yb₂O₃0.3 mol% of Pr₆O₁₁And is ready for use; wherein, the purity of each raw material is required to be 99.99 percent by mass.

(2) Fully grinding the weighed raw materials in the step (1), uniformly mixing, pouring into a corundum crucible, and placing in a high-temperature furnace at 1050 ℃ for melting for 1h to obtain a glass solution.

(3) Taking out the corundum crucible filled with the glass solution from the high-temperature furnace, and carrying out quenching forming on a preheated graphite mold to obtain a glass sheet; wherein the temperature of the graphite mold heated in advance is 300 ℃.

(4) Putting the graphite mold poured with the glass solution into a muffle furnace for annealing, wherein the annealing process comprises the following steps: and transferring the graphite mold with the glass liquid poured into the graphite mold into a muffle furnace heated to 350 ℃, preserving heat for 2h, then cooling to room temperature at the speed of 10 ℃/h, and obtaining bismuthate optical fiber glass after annealing.

(5) Taking out the graphite mold with bismuthate optical fiber glass from the muffle furnace, and performing double-sided polishing treatment on the bismuthate optical fiber glass to obtain the bismuthate optical fiber glass with two polished sides of 1.5cm multiplied by 1.5 mm.

Example 2

The invention provides a near-infrared band broadband emission rare earth doped bismuthate optical fiber glass, which comprises the following steps:

(1) weighing the following raw materials in percentage by mole: 75 mol% of Bi₂O₃19 mol% of B₂O₃4.5 mol% of Na₂O, 0.3 mol% Er₂O₃1.0 mol% of Yb₂O₃0.2 mol% of Pr₆O₁₁And is ready for use; wherein, the purity of each raw material is required to be 99.99 percent by mass.

(2) Fully grinding the weighed raw materials in the step (1), uniformly mixing, pouring into a corundum crucible, and placing in a high-temperature furnace at 1050 ℃ for melting for 1h to obtain a glass solution.

(3) Taking out the corundum crucible filled with the glass solution from the high-temperature furnace, and carrying out quenching forming on a preheated graphite mold to obtain a glass sheet; wherein the temperature of the graphite mold heated in advance is 300 ℃.

(4) Putting the graphite mold poured with the glass solution into a muffle furnace for annealing, wherein the annealing process comprises the following steps: and transferring the graphite mold with the glass liquid poured into the graphite mold into a muffle furnace heated to 350 ℃, preserving heat for 2h, then cooling to room temperature at the speed of 10 ℃/h, and obtaining bismuthate optical fiber glass after annealing.

(5) Taking out the graphite mold with bismuthate optical fiber glass from the muffle furnace, and performing double-sided polishing treatment on the bismuthate optical fiber glass to obtain the bismuthate optical fiber glass with two polished sides of 1.5cm multiplied by 1.5 mm.

Example 3

The invention provides a near-infrared band broadband emission rare earth doped bismuthate optical fiber glass, which comprises the following steps:

(1) weighing the following raw materials in percentage by mole: 74 mol% of Bi₂O₃20 mol% of B₂O₃4 mol% of Na₂O, 0.4 mol% Er₂O₃1.2 mol% of Yb₂O₃0.4 mol% of Pr₆O₁₁And is ready for use; wherein, the purity of each raw material is required to be 99.99 percent by mass.

(2) Fully grinding the weighed raw materials in the step (1), uniformly mixing, pouring into a corundum crucible, and placing in a high-temperature furnace at 1080 ℃ for melting for 1h to obtain a glass solution.

(3) Taking out the corundum crucible filled with the glass solution from the high-temperature furnace, and carrying out quenching forming on a preheated graphite mold to obtain a glass sheet; wherein the temperature of the graphite mold heated in advance is 300 ℃.

(4) Putting the graphite mold poured with the glass solution into a muffle furnace for annealing, wherein the annealing process comprises the following steps: and transferring the graphite mold with the glass liquid poured into the graphite mold into a muffle furnace heated to 330 ℃, preserving heat for 2h, then cooling to room temperature at the speed of 8 ℃/h, and obtaining bismuthate optical fiber glass after annealing.

(5) Taking out the graphite mold with bismuthate optical fiber glass from the muffle furnace, and performing double-sided polishing treatment on the bismuthate optical fiber glass to obtain the bismuthate optical fiber glass with two polished sides of 1.5cm multiplied by 1.5 mm.

Example 4

The invention provides a near-infrared band broadband emission rare earth doped bismuthate optical fiber glass, which comprises the following steps:

(1) weighing the following raw materials in percentage by mole: 74.2 mol% of Bi₂O₃19.3 mol% of B₂O₃5 mol% of Na₂O, 0.5 mol% Er₂O₃0.8 mol% of Yb₂O₃0.2 mol% of Pr₆O₁₁And is ready for use; wherein, the purity of each raw material is required to be 99.99 percent by mass.

(2) Fully grinding the weighed raw materials in the step (1), uniformly mixing, pouring into a corundum crucible, and placing in a high-temperature furnace at 1100 ℃ for melting for 1h to obtain a glass solution.

(3) Taking out the corundum crucible filled with the glass solution from the high-temperature furnace, and carrying out quenching forming on a preheated graphite mold to obtain a glass sheet; wherein the temperature of the graphite mold heated in advance is 300 ℃.

(4) Putting the graphite mold poured with the glass solution into a muffle furnace for annealing, wherein the annealing process comprises the following steps: and transferring the graphite mold with the glass liquid poured into the graphite mold into a muffle furnace heated to 340 ℃, preserving heat for 2h, then cooling to room temperature at the speed of 9 ℃/h, and obtaining bismuthate optical fiber glass after annealing.

(5) Taking out the graphite mold with bismuthate optical fiber glass from the muffle furnace, and performing double-sided polishing treatment on the bismuthate optical fiber glass to obtain the bismuthate optical fiber glass with two polished sides of 1.5cm multiplied by 1.5 mm.

The raw material B used in examples 1 to 4 was₂O₃Can be represented by H₃BO₃Form of (2) incorporation of Na₂O may be Na₂CO₃Is incorporated in the form of (A), i.e. B₂O₃From twice the molar amount of H₃BO₃Instead of, Na₂O is formed from an equimolar amount of Na₂CO₃Instead. Wherein H₃BO₃Decomposition at elevated temperatures may give B₂O₃Reaction of (1), Na₂CO₃Decomposition at high temperature can produce Na₂The reaction of O may likewise be effected by adding B separately³⁺And Na⁺The function of (1).

The tellurate optical fiber glasses prepared in the embodiments 1 to 4 are respectively subjected to performance tests, and the fluorescence emission spectrum of the near-infrared band within the wavelength range of 1200-1700 nm is obtained by measurement under the excitation of pump light with the wavelength of 980 nm.

As shown in FIGS. 1 and 2, the glass of example 1 was tested to obtain a fluorescence spectrum having a gain spectrum ranging from about 1200 nm to about 1700nm and a spectrum having two luminescence centers, Pr at 1320nm³⁺Emission Peak, Er at 1530nm³⁺Ion emission peaks, wherein the half width at half height of fluorescence at 1320nm is 82nm, the half width at half height of fluorescence at 1530nm is 84nm, the half width at half height of fluorescence at 1320nm of the bismuthate optical fiber glass of test example 2 is 78nm, the half width at half height of fluorescence at 1530nm is 80nm, the half width at half height of fluorescence at 1320nm of the bismuthate optical fiber glass of test example 3 is 84nm, the half width at half height of fluorescence at 1530nm is 76nm, the half width at half height of fluorescence at 1320nm of the bismuthate optical fiber glass of test example 4 is 76nm, the half width at half height at 1530nm is 86nm, the zero dispersion O (1260-1360 nm) wave band and the lowest loss region C (1530-1565 nm) wave band of optical signal transmission are covered, and the gain is relatively flat, the glass has good application value in an optical communication system, good glass stability and excellent physical and chemical properties, and is beneficial to realizing broadband and high-gain amplification of 1.3 mu m and 1.5 mu m dual-band by an optical fiber amplifier.

The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.