Neodymium-doped near-infrared broadband emission germanate glass, preparation method and application thereof

Abstract

The application belongs to the technical field of laser glass and optical fiber, and discloses a neodymium-doped near-infrared broadband emission germanate glass as well as a preparation method and application thereof.The neodymium-doped near-infrared broadband emission germanate glass comprises, in terms of molar percentage, 20-40% of R2O / RO, 5-15% of Nb2O5, 60-75% of GeO2, and the total percentage of the above components is 100%, and 0.5-1.5% of Nd2O3 is doped outside; R is another metal element.The glass has the advantages of easy preparation, wide fluorescence half-height width, good anti-crystallization stability and the like, and can be used in a high-peak-power and high-energy-pulse laser medium.

Description

Technical Field

[0001] This invention belongs to the field of laser glass and fiber technology, and specifically relates to a neodymium-doped near-infrared broadband emission germanate glass, its preparation method and application. Background Technology

[0002] With the development of optical sensing and optical communication technologies, high-power, high-stability, and wide-bandwidth light sources have important applications in optical communication and fiber optic gyroscopes. Doped broadband glass fiber light sources have attracted widespread scientific research due to their advantages such as stable emission spectrum, wide bandwidth, high power, low cost, and easy coupling with fiber optic communication systems. Furthermore, ultrashort and ultra-intense laser technology can be applied to generate extreme physical conditions at the laboratory scale, which is of great significance in fundamental research such as strong-field laser physics and cutting-edge applications such as high-energy particle acceleration. One type of petawatt laser device built around the world uses neodymium glass as the main amplification medium to achieve 1053nm band petawatt laser output, suitable for fusion-related high peak power ultra-high energy devices. Peak power is generally increased by increasing pulse energy or compressing the pulse width in the time domain; however, excessively increasing pulse energy can easily cause nonlinear phenomena such as self-focusing effects, and even damage laser components. If peak power is to be increased by compressing the pulse width, the gain medium needs to have the widest possible emission bandwidth.

[0003] Currently, the gain medium is mainly based on neodymium glass, and the glass matrix includes phosphate, silicate, germanate, and aluminate glasses. 3+ The effective linewidths of the fluorescence spectra are 22-35 nm, 34-55 nm, 36-43 nm, and 33-44 nm, respectively. Commercial neodymium glass (phosphate) typically has an emission bandwidth of less than 30 nm. By mixing silicate and phosphate neodymium glasses, their gain bandwidth can be broadened, increasing the peak power of laser devices. To further broaden the overall bandwidth to meet the application requirements of 10 PW laser systems, researchers have explored aluminate glasses with wider bandwidths. However, aluminate glasses require higher melting temperatures, and their strong crystallization tendency hinders their development. Adding glass forging agents such as SiO2, GeO2, and B2O3 can increase glass-forming ability, but the effective linewidth of their fluorescence spectra remains limited to within 50 nm. Therefore, it is necessary to develop novel ultrawide-bandwidth neodymium glasses.

[0004] In order to overcome the shortcomings and deficiencies of the prior art, the primary objective of this invention is to provide a neodymium-doped near-infrared broadband emitting germanate glass.

[0005] Another objective of this invention is to provide a method for preparing the above-mentioned neodymium-doped near-infrared broadband emission germanate glass.

[0006] Another objective of this invention is to provide the application of the above-mentioned neodymium-doped near-infrared broadband emitting germanate glass in laser components.

[0007] The objective of this invention is achieved through the following solution:

[0008] A neodymium-doped near-infrared broadband emission germanate glass comprises, by molar percentage: 20–40% R₂O / RO, 5–15% Nb₂O₅, and 60–75% GeO₂, with the total percentage of the above components being 100%, and externally doped with 0.5–1.5% Nd₂O₃; R represents other metallic elements.

[0009] The R2O is at least one of Li2O, Na2O, and K2O.

[0010] The RO is at least one of CaO, SrO, and BaO.

[0011] The preparation method of the above-mentioned neodymium-doped near-infrared broadband emission germanate glass includes the following steps:

[0012] (1) Weigh the carbonate of R metal, Nb2O5, GeO2 and Nd2O3, grind them to form a mixed powder;

[0013] (2) Melt the mixed powder obtained in step (1) to obtain molten glass;

[0014] (3) Pour the molten glass into the mold, anneal, cool, and process and polish it into a glass sheet.

[0015] The melting in step (2) is carried out in an air atmosphere at 1350℃~1450℃ for 30min~40min.

[0016] Step (3) involves pouring molten glass onto a graphite mold at 400–700°C.

[0017] The annealing in step (3) is carried out in an air atmosphere at 400-600℃ for 2-10 hours.

[0018] The cooling in step (3) is to cool to room temperature at a rate of 6-10℃ / h after annealing.

[0019] Step (3) describes processing and polishing the glass sheet into a glass sheet by processing the annealed glass body into a glass sheet with a thickness of 1 to 2 mm.

[0020] The above-mentioned neodymium-doped near-infrared broadband emission germanate glass is used in laser components.

[0021] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0022] The neodymium-doped germanate laser glass of the present invention increases Nd by introducing Nb2O5. 3+ The Stark splitting and asymmetry ultimately increase Nd 3+ With a bandwidth of 1μm, this glass also has advantages such as easy preparation, good glass-forming ability, and good anti-crystallization stability, making it suitable for use as a laser medium for high peak power and high energy pulses. Attached Figure Description

[0023] Figure 1 The glass slides obtained in Examples 1-6 of this invention are Nd2 at room temperature. 3+ The fluorescence spectrum.

[0024] Figure 2 The glass slides obtained in Examples 1-6 of this invention are Nd2 at room temperature. 3+ The full width at half maximum (FWHM) and fluorescence bandwidth (Δλ) of the 1072 nm peak.

[0025] Figure 3 The DSC curves are of the glass sheets obtained in Examples 1-6 of this invention.

[0026] Figure 4 These are the anti-crystallization stability parameters of the glass sheets obtained in Examples 1-6 of this invention. Detailed Implementation

[0027] The present invention will be further described in detail below with reference to embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.

[0028] Unless otherwise specified, all reagents used in the examples are commercially available.

[0029] The composition ratio of neodymium-doped near-infrared broadband emission germanate glass is shown below:

[0030] Table 1: Component ratios of each embodiment

[0031] Example 1 <![CDATA[Li2O 20]]> 0 10 70 1 Example 2 <![CDATA[Na2O 20]]> 0 10 70 1 Example 3 <![CDATA[K2O 20]]> 0 10 70 1 Example 4 0 CaO 20 10 70 1 Example 5 0 SrO 20 10 70 1 Example 6 0 BaO 20 10 70 1

[0032] The glass composition here is a molar percentage, in which Nd2O3 is used as 1% of the externally doped glass composition, and the total weight of the glass composition (excluding the externally doped Nd2O3) is 20g.

[0033] The specific preparation process of Example 1 is as follows:

[0034] The raw materials for both R2O and RO components are corresponding carbonate substances. In Example 1, the raw material corresponding to component Li2O is Li2CO3. The amount of each raw material is calculated according to the composition in Table 1, as shown in Table 2.

[0035] Table 2. Mass of each raw material in Example 1

[0036] Raw material weight (g) 2.794 5.026 13.844 0.636

[0037] High-purity Li2CO3, Nb2O5, GeO2, and Nd2O3 powdered raw materials were weighed and ground evenly according to the weights in Table 2, and then placed in a corundum crucible. The mixture was melted in a high-temperature box furnace at 1400℃ for 40 minutes to obtain molten glass. The molten glass was then poured directly into a graphite mold preheated to 500℃ in an annealing furnace. After holding at 500℃ for 2 hours in the annealing furnace, the mixture was cooled to room temperature at a rate of 10℃ / h. The prepared glass precursor was then processed into glass sheets with a thickness of 1-2 mm. All of the above steps were completed in an air atmosphere.

[0038] Except for the raw material composition, the operation steps in Examples 2-6 are the same as those in Example 1.

[0039] The test results of the example are as follows: Figure 1 Nd2O3 of the glass sheets obtained in Examples 1-6 3+ Fluorescence spectrum in the 1000-1200 nm band. Figure 2 The calculated full width at half maximum (FWHM) of the fluorescence peak near 1072 nm is 43-49 nm, and the fluorescence bandwidth (Δλ) is 47-53 nm. Figure 3 The DSC curves are for the glass slides obtained in Examples 1-6. Figure 4 The anti-crystallization stability parameters (ΔT) of the glass sheets obtained in Examples 1-6 are shown. The anti-crystallization stability parameters of Examples 2-6 are greater than 100℃. A glass anti-crystallization stability exceeding 100℃ is beneficial for fiber drawing and application in high-energy pulsed, ultra-high peak power fiber lasers.

[0040] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A neodymium-doped near-infrared broadband emission germanate glass, characterized in that, The product comprises, by molar percentage: 20-40% R2O / RO, 5-15% Nb2O5, and 60-75% GeO2, with the total percentage of the above components being 100%, and externally doped with 0.5-1.5% Nd2O3; R2O is at least one of Li2O, Na2O, and K2O; and RO is at least one of CaO, SrO, and BaO. The preparation of the neodymium-doped near-infrared broadband emission germanate glass includes the following steps: (1) Weigh the carbonate of R metal, Nb2O5, GeO2 and Nd2O3, grind them to form a mixed powder; (2) Melt the mixed powder obtained in step (1) to obtain molten glass; (3) Pour the molten glass into the mold, anneal, cool, and process and polish it into a glass sheet; The melting in step (2) is carried out in an air atmosphere at 1350℃~1450℃ for 30 min~40 min.

2. The neodymium-doped near-infrared broadband emission germanate glass according to claim 1, characterized in that: Step (3) involves pouring molten glass onto a graphite mold at 400–700°C.

3. The neodymium-doped near-infrared broadband emission germanate glass according to claim 1, characterized in that: The annealing in step (3) is carried out in an air atmosphere at 400-600℃ for 2-10 h.

4. The neodymium-doped near-infrared broadband emission germanate glass according to claim 1, characterized in that: The cooling in step (3) is to cool to room temperature at a rate of 6-10°C / h after annealing.

5. The neodymium-doped near-infrared broadband emission germanate glass according to claim 1, characterized in that: Step (3) involves processing and polishing the glass body obtained after annealing into a glass sheet with a thickness of 1 to 2 mm.

6. The application of neodymium-doped near-infrared broadband emission germanate glass according to any one of claims 1-5 in laser components.

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