CN1308255C - Method for manufacturing erbium-doped high silica infrared luminescent glass - Google Patents

Abstract

A method for manufacturing erbium-doped high-silicon oxide infrared luminescent glass comprises the following steps: ① selecting high-silicon oxide porous glass, wherein the content of _SiO2 in the glass is 95-98wt%; ② preparing a solution containing erbium ions, wherein the concentration of erbium ions is in the range of 0.02-0.42 mol/L; ③ immersing the high-silicon oxide porous glass in the solution containing erbium ions, so that the solution containing erbium ions is immersed in the high-silicon oxide porous glass, thereby forming high-silicon oxide porous glass containing erbium ions; ④ after drying, placing the high-silicon oxide porous glass containing erbium ions in a high-temperature furnace, and solid-phase sintering at a temperature of 1050-1200°C. The glass manufactured by the method of the present invention generates infrared luminescence near the frequency band of 1.53 microns, and can generate 1.54 micron laser in the laser resonant cavity.

Description

Manufacturing method of erbium-doped high-silica infrared luminescent glass

technical field

The invention relates to luminescent glass, in particular to a method for manufacturing erbium-doped high-silica infrared luminescent glass.

Background technique

Erbium-doped ion oxide glass can be used as the working material of active devices such as optical fiber amplifiers and planar optical waveguide amplifiers, and the laser wavelength of 1.54 microns in erbium-doped glass can be absorbed by water, which is suitable for distance measurement that is safe for human eyes Due to these application prospects, people have extensively studied the luminescence characteristics of erbium ions in silicate, phosphoric acid, boric acid, germanate and quartz glass, and the erbium-doped silica fiber amplifier (EDFA) has become the current It is an indispensable key component in optical fiber communication system. However, among the various glass systems mentioned above, only erbium ion-doped silica glass fiber has been practically used at present. The reason is that the optical loss of erbium-doped ion silica glass is much lower than that of other oxide glasses and has good stability. However, there are some disadvantages in erbium-doped quartz glass: first, the concentration of erbium ions is not high; this is because erbium ions tend to spontaneously form clusters in quartz glass, resulting in concentration extinction. A low concentration will make the gain per unit length of the optical fiber small, which is not conducive to the development of device miniaturization. The second is that the luminescence bandwidth of erbium ions in quartz glass is relatively narrow, which brings difficulties to the expansion of the amplification bandwidth. Therefore, although erbium-doped silica glass fibers have been applied in optical fiber communication systems, if a suitable matrix material or preparation method can be found through research, not only the basic characteristics of silica glass can be maintained, but also relatively High erbium ion doping concentration and wide emission bandwidth, if so, can undoubtedly make up for the deficiency of the current erbium-doped quartz glass, which has important practical value.

Contents of the invention

The object of the present invention is to provide a method for manufacturing erbium-doped high-silica infrared luminescent glass, so as to obtain infrared luminescence near the frequency band of 1.53 microns, and generate laser light of 1.54 microns in the laser resonant cavity.

Technical solution of the present invention is as follows:

A method for manufacturing erbium-doped high-silica infrared luminescent glass, characterized in that the method comprises the following steps:

1. Select high-silica porous glass, the content of _SiO in the glass is 95-98wt%, the aperture of the small hole is 1.0-10 nanometers, and the small hole accounts for 23-28% of the volume of the glass;

②Preparing a solution containing erbium ions, the concentration range of erbium ions is 0.02～0.42 mol/liter;

③ immerse the high-silica porous glass in the solution containing erbium ions, so that the solution containing erbium ions is immersed in the high-silica porous glass to form a high-silica porous glass containing erbium ions. Glass;

④ After drying, put the high-silica porous glass containing erbium ions into a high-temperature furnace, and solid-state sintering at a temperature of 1050-1200°C: the heating rate from room temperature to 400°C is ≤ 5°C per minute, from 400°C to 900°C The heating rate of ℃ is 10 ℃ per minute, the heating rate from 950 ℃ to 1050-1200 ℃ is ≤ 5 ℃ per minute, keep warm at 1050-1200 ℃ for more than 30 minutes, and then cool down to room temperature.

The solution containing erbium ions also contains ytterbium ions/aluminum ions co-dissolved, the concentration range of ytterbium ions is 0.27-0.71 mol/liter, and the concentration range of aluminum ions is 0.11-0.53 mol/liter Lift.

The solvent of the solution containing erbium ions is water, acid, alcohol or acetone.

Described acid is nitric acid, hydrochloric acid or sulfuric acid.

Described high silica porous glass adopts the porous glass prepared by borosilicate glass phase separation method, and the _SiO2 content of this glass is 95～98wt% (percentage by weight), because the acid treatment in the preparation process can not dissolve completely Other components are removed, so 1-3wt% of B ₂ O ₃ and 1-2wt% of Al ₂ O ₃ remain in the glass. The pore diameter of the porous glass is 1.0-10 nanometers, and the small pores account for 23-28% of the volume of the glass.

After drying, the high-silica porous glass containing erbium ions is put into a high-temperature furnace, and sintered at a high temperature of 1050-1200°C for 0.5-2 hours, and the porous glass becomes non-porous transparent infrared luminescent glass. The luminescent properties of the glass continue to sinter at high temperature no longer change. After polishing, the high-silica glass doped with erbium ions can produce infrared luminescence near the frequency band of 1.53 microns under the laser pumping of 808nm, and the high-silica glass co-doped with erbium and ytterbium ions can be pumped at 980nm; At the same time, co-doping aluminum ions can significantly enhance the luminous intensity near the 1.53 micron frequency band. This glass can be further processed into optical fibers and planar optical waveguides, which can produce 1.54 micron laser light in the laser resonator.

Described erbium ion solution is that erbium nitrate or erbium oxide, erbium chloride, erbium acetate etc. can be dissolved completely by water, acid (comprising nitric acid solution, hydrochloric acid solution, sulfuric acid solution), ethanol and acetone solution, and can The material that completely decomposes and forms erbium ion oxide is dissolved in the above solution to prepare water and acid solution doped with erbium ion solution, including nitric acid solution, hydrochloric acid solution, sulfuric acid solution, ethanol solution and acetone solution.

In order to improve the luminescent performance of erbium ions, ytterbium Yb ³⁺ and aluminum ions Al ³⁺ can also be introduced at the same time as erbium ions are introduced by the solution method. The weight percentage of these ions in the glass after sintering is about 0.1-4.0 wt% can be introduced simultaneously or separately. The upper limit condition for introducing erbium, ytterbium and aluminum ions is that the glass does not devitrify after sintering. After these ions are introduced, the content of silicon dioxide in the glass composition exceeds 91%. The introduction of ytterbium ions and aluminum ions is the same as that of erbium ions, and the nitrate compounds, chlorides or acetic acid compounds of ytterbium and aluminum are dissolved in water, acids (including nitric acid solutions, hydrochloric acid solutions, sulfuric acid solutions), ethanol and acetone solutions to prepare them. aqueous solution, acid solution, ethanol solution and acetone solution. After introducing erbium ions, ytterbium and aluminum ions, the high-silica porous glass doped with these ions is placed in a high-temperature furnace, and undergoes high-temperature solid-state sintering at 1050-1200°C to eliminate micropores and become dense and transparent high-silica glass. During the sintering process, the temperature should be raised slowly from room temperature to 400°C, at a speed of less than 5°C per minute, to avoid cracking of the porous glass, and the temperature should be raised slowly from about 950°C to 1050-1200°C, at a speed of less than 5°C per minute , to avoid glass deformation. After reaching the sintering temperature (1050-1200°C), keep it warm for 0.5-2 hours, and the porous glass becomes non-porous glass. Therefore, the luminescent properties of the glass will not change when the high-temperature sintering continues.

Experiments show that after sintering the erbium-doped and erbium-, aluminum-, and ytterbium-ion-doped high-silica glass, after polishing, it can produce infrared luminescence near the frequency band of 1.53 microns under the laser pump of 808nm or 980nm. Laser light of 1.54 microns can be generated in the resonator.

Description of drawings

Fig. 1 is the luminescent spectrum of the erbium-doped high-silica glass manufactured by the method of the present invention under the laser excitation with a wavelength of 808nm

Fig. 2 is the luminescent spectrum of the erbium-doped high-silica glass manufactured by the method of the present invention under the excitation of a laser with a wavelength of 980nm

Fig. 3 is the luminescent spectrum of the erbium-doped high-silica glass manufactured by the method of the present invention under the laser excitation with a wavelength of 980nm

Detailed ways

The present invention will be further described below in conjunction with embodiment.

Example 1

Put 2.32g of analytically pure Er(NO ₃ ) ₃ 5H ₂ O equivalent to 1.0g of Er ₂ O ₃ after decomposition into 25 milliliters of deionized aqueous solution, after completely dissolving, the Er ³⁺ ion concentration is formulated as 0.21 mol/liter solution, and then put the porous glass with a size of 5×5×3mm and _a SiO content of 97wt% into the solution and soak for more than 10 minutes; after that, the high-silica porous glass doped with erbium ions Put it into a high-temperature furnace and undergo solid-state sintering at 1150°C in air or oxygen to eliminate micropores and become dense and transparent high-silica glass doped with Er ₂ O ₃ with a concentration of about 1.0%. During the sintering process, after rising from room temperature to 400°C at a speed of less than 5°C per minute, it rises to around 950°C at a speed of 10°C per minute, and then rises from this temperature at a speed of below 5°C per minute. After reaching 1150°C and keeping the temperature at this temperature for more than 30 minutes, turn off the power of the high-temperature furnace and let the glass cool with the furnace. Under the excitation of 808nm laser, the glass can emit infrared light centered at 1530nm. Curve (1) in Fig. 1 is exactly the luminescence spectrum curve of this glass.

Example 2

Put 0.23g of analytically pure Er(NO ₃ ) ₃ 5H ₂ O equivalent to 0.1g of Er ₂ O ₃ after decomposition into 25 ml of ethanol solution, and after completely dissolving, the Er ³⁺ ion concentration is 0.02 mol/liter solution, and then put the porous glass with a size of 5×5×3mm and a _SiO2 content of 98wt% into the solution and soak for more than 10 minutes; after that, put the high-silica microporous glass into a high-temperature furnace In the air or oxygen, after solid-phase sintering at a temperature of 1200°C, micropores are eliminated to become dense and transparent high-silica glass doped with Er ₂ O ₃ with a concentration of about 0.1%. During the sintering process, after rising from room temperature to 400°C at a speed of less than 5°C per minute, it rises to around 950°C at a speed of 10°C per minute, and then rises from this temperature at a speed of below 5°C per minute. After reaching 1200°C and keeping the temperature at this temperature for more than 30 minutes, turn off the power of the high-temperature furnace and let the glass cool down with the furnace. Under the excitation of 808nm laser, the glass can emit infrared light centered at 1530nm.

Example 3

2.32g of analytically pure Er(NO ₃ ) ₃ 5H ₂ O and 5.0g of analytically pure Al(NO ₃ ) ₃ .9H ₂ O _equivalent to 1.0g of Er ₂ O 3 after decomposition were put into 25 ml of 1 In the hydrochloric acid solution of one equivalent, after completely dissolving, be made into the solution that Er ³⁺ ion concentration is 0.21 mol/liter, Al ³⁺ ion concentration is 0.53 mol/liter, then the size is 5×5×3mm, SiO ₂ The porous glass with a content of 97wt% is immersed in the solution for more than 10 minutes; after that, the high-silica microporous glass doped with these ions is placed in a high-temperature furnace, and undergoes solid-state sintering at a temperature of 1120°C in air or oxygen , Eliminate micropores and become dense and transparent high-silica glass. During the sintering process, the temperature is raised from room temperature to 400°C at a speed of less than 5°C per minute, and then raised to 950°C at a speed of 10°C per minute. Then, raise from 950°C to 1120°C at a speed of less than 5°C per minute and keep the temperature at 1120°C for more than 30 minutes, then turn off the power of the high-temperature furnace and let the glass cool with the furnace. Under the excitation of 808nm laser, the glass can emit infrared light centered at 1530nm. Curve 2 in Fig. 1 is the luminescence spectrum curve of the glass.

Example 4

2.32g of analytically pure Er(NO ₃ ) ₃ 5H ₂ O equivalent to 1.0g of Er ₂ O ₃ after decomposition and 3.2g of analytically pure Yb(NO ₃ ) equivalent to 1.35g of Yb ₂ O ₃ after decomposition ) _{3.6H 2} O is put into 25 milliliters of 1 equivalent of nitric acid solution, after completely dissolving, be made into the solution that Er ³⁺ ion concentration is 0.21 mol/liter, Yb ³⁺ ion concentration is 0.27 mol/liter, and then Put a porous glass with a size of 5×5×3mm and a _SiO2 content of 97wt% into the solution and soak for more than 10 minutes; after that, put the high-silicon-oxygen microporous glass doped with these ions into a high-temperature furnace, in the air Or undergo solid-state sintering at a temperature of 1100°C in oxygen to eliminate micropores and become dense and transparent high-silica glass. During the sintering process, the temperature is raised from room temperature to 400°C at a speed of less than 5°C per minute, and then raised to 950°C at a speed of 10°C per minute. Then, raise the temperature from 950°C to 1100°C at a rate of less than 5°C per minute and keep the temperature at 1100°C for more than 30 minutes, then turn off the power supply of the high-temperature furnace and let the glass cool down with the furnace. Under the excitation of 980nm laser, the glass can emit infrared light centered at 1530nm. Curve 2 in Fig. 2 is the luminescence spectrum curve of the glass.

Example 5

2.32g of analytically pure Er(NO ₃ ) ₃ 5H ₂ O equivalent to 1.0g of Er ₂ O ₃ after decomposition and 3.2g of analytically pure Yb(NO ₃ ) equivalent to 1.35g of Yb ₂ O ₃ after decomposition ) ₃ ·6H ₂ O and 5.0g of analytically pure Al(NO ₃ ) ₃ ·9H ₂ O were put into 25 ml of 1 N sulfuric acid solution, and after they were completely dissolved, the Er ³⁺ ion concentration was 0.21 mol/ liters, Yb ³⁺ ion concentration is 0.27 mol/liter, Al ³⁺ ion concentration is 0.53 mol/liter solution, then put the porous glass with the size of 5×5×3mm and _SiO content of 96wt% into the solution After that, put the high-silica microporous glass doped with these ions into a high-temperature furnace, and undergo solid-phase sintering at a temperature of 1080°C in air or oxygen to eliminate micropores and become dense and transparent high-silica glass. Glass. During the sintering process, the temperature is raised from room temperature to 400°C at a speed of less than 5°C per minute, and then raised to 950°C at a speed of 10°C per minute. Then, raise the temperature from 950°C to 1080°C at a speed of less than 5°C per minute and keep the temperature at 1080°C for more than 30 minutes, then turn off the power of the high-temperature furnace and let the glass cool down with the furnace. Under the excitation of 980nm laser, the glass can emit infrared light centered at 1530nm. Curve 2 in Fig. 3 is the luminescence spectrum curve of the glass.

Example 6

4.64g of analytically pure Er(NO ₃ ) ₃ 5H ₂ O equivalent to 2.0g of Er ₂ O ₃ after decomposition and 4.74g of analytically pure Yb(NO ₃ ) equivalent to 2.0g of Yb ₂ O ₃ after decomposition ) ₃ ·6H ₂ O and 2.5g of analytically pure Al(NO ₃ ) ₃ ·9H ₂ O were put into 25 ml of 1 N hydrochloric acid solution, and after they were completely dissolved, the Er ³⁺ ion concentration was 0.42 mol/ liter, Yb ³⁺ ion concentration is 0.4 mole/liter, Al ³⁺ ion concentration is 0.28 mole/liter solution, then put the porous glass with size 5×5×3mm and _SiO content of 96wt% into the solution After that, put the high-silica microporous glass doped with these ions into a high-temperature furnace, and undergo solid-phase sintering at a temperature of 1070°C in air or oxygen to eliminate micropores and become dense and transparent high-silica glass. Glass. During the sintering process, after rising from room temperature to 400°C at a speed of less than 5°C per minute, the temperature rises from room temperature to 950°C at a speed of 10°C per minute. Then, raise the temperature from 950°C to 1070°C at a speed of less than 5°C per minute and keep the temperature at 1070°C for more than 30 minutes, then turn off the power of the high-temperature furnace and let the glass cool down with the furnace. Under the excitation of 980nm laser, the glass can emit infrared light centered at 1530nm.

Example 7

1.2g of analytically pure Er(NO ₃ ) ₃ 5H ₂ O equivalent to 0.5g of Er ₂ O ₃ after decomposition and 8.3g of analytically pure Yb(NO ₃ ) equivalent to 3.5g of Yb ₂ O ₃ after decomposition ) ₃ 6H ₂ O and 1.0 g of analytically pure Al(NO ₃ ) ₃ 9H ₂ O were put into 25 ml of ethanol and acetone solution, and after they were completely dissolved, the Er ³⁺ ion concentration was 0.11 mol/liter. A solution with a concentration of Yb ³⁺ ions of 0.71 mol/liter and a concentration of Al ³⁺ ions of 0.11 mol/liter, and then put a porous glass with a size of 5×5×3mm and a content of SiO ₂ of 95wt% into the solution for soaking More than 10 minutes; after that, put the high-silica microporous glass doped with these ions into a high-temperature furnace, and undergo solid-state sintering at a temperature of 1050°C in air or oxygen to eliminate micropores and become dense and transparent high-silica glass. During the sintering process, the temperature is raised from room temperature to 400°C at a speed of less than 5°C per minute, and then raised to 950°C at a speed of 10°C per minute. Then, raise the temperature from 950°C to 1050°C at a speed of less than 5°C per minute and keep the temperature at 1050°C for more than 30 minutes, then turn off the power of the high-temperature furnace and let the glass cool down with the furnace. Under the excitation of 980nm laser, the glass can emit infrared light centered at 1530nm.

As can be seen from the figure, curve 1 in Fig. 1 is the luminescence spectrum of the high-silica glass doped with erbium ions in embodiment 1 only under laser excitation with a wavelength of 808 nm, and curve 2 is the high-silicon glass of embodiment 3 co-doped with erbium and aluminum ions. The luminescence spectrum of silica glass excited by a laser with a wavelength of 808nm, after co-doping aluminum ions, the luminescence intensity increases by about 1 times. Curve 1 in Fig. 2 is the same spectrum as curve 1 in Fig. 1, and curve 2 in Fig. 2 is the luminescence spectrum of the high silica glass co-doped with erbium and ytterbium ions in embodiment 4 under the laser excitation of 980nm wavelength, Under the laser excitation of the same power, the luminous intensity of the erbium and ytterbium ion co-doped glass increases by more than 12 times. In addition, the half maximum width of the emission spectrum of the high silica glass doped with erbium ions and the high silica glass co-doped with erbium and aluminum ions is about 30nm, while the half maximum width of the emission spectrum of the high silica glass co-doped with erbium and ytterbium ions The width is about 74nm, more than doubled. Curve 1 in Fig. 3 is the same curve as curve 2 in Fig. 2, and curve 2 in Fig. 3 is the luminescent spectrum of embodiment 5 erbium, ytterbium and aluminum three kinds of ion co-doped glass under the laser excitation of wavelength 980nm, After co-doping aluminum ions, the luminous intensity increased by about 1 times, and the full width at half maximum of the luminescent spectrum remained at about 70nm. This kind of erbium ion-doped high-silica glass infrared light-emitting glass has been improved from single-doped erbium to co-doped with three ions of erbium, ytterbium and aluminum. Under the same power laser excitation, its luminous intensity increases by about 25%.

Claims (4)

1, a kind of manufacture method of erbium doped high silicon oxygen infrared luminous glass is characterized in that this method comprises the following steps:

1. choose high silica porous glass, SiO in this glass ₂Content be 95～98wt%, the aperture of aperture is 1.0～10 nanometers, the volume that aperture accounts for glass is 23～28%;

2. preparation contains the solution of erbium ion, and its concentration range is 0.02～0.42 mol;

3. described high silica porous glass is immersed in the described solution that contains erbium ion,, forms the high silica porous glass that contains erbium ion so that the described solution that contains erbium ion immerses in this high silica porous glass;

4. through super-dry, this high silica porous glass that contains erbium ion is put into High Temperature Furnaces Heating Apparatus, solid state sintering under 1050～1200 ℃ of temperature: from 5 ℃ of the temperature rise rate≤per minutes of room temperature to 400 ℃, from 400 ℃ to 900 ℃ temperature rise rates is 10 ℃ of per minutes, from 5 ℃ of temperature rise rate≤per minutes of 950 ℃ to 1050～1200 ℃, more than 30 minutes, be cooled to room temperature 1050～1200 ℃ of insulations then.

2, the manufacture method of erbium doped high silicon oxygen infrared luminous glass according to claim 1, it is characterized in that the described solution that contains erbium ion, it is molten altogether wherein also to contain ytterbium ion or aluminum ion or ytterbium ion and aluminum ion, the concentration range of described ytterbium ion is 0.27～0.71 mol, and described aluminum ions concentration range is 0.11～0.53 mol.

3, the manufacture method of erbium doped high silicon oxygen infrared luminous glass according to claim 2 is characterized in that the described solvent that contains the solution of erbium ion is water, acid, alcohol or acetone.

4, the manufacture method of erbium doped high silicon oxygen infrared luminous glass according to claim 3 is characterized in that described acid is nitric acid, hydrochloric acid or sulfuric acid.

Images