Thulium-doped tellurate glass as well as preparation method and application thereof

Abstract

The invention provides thulium-doped tellurate glass as well as a preparation method and application thereof, and belongs to the technical field of luminescent glass. In the thulium-doped tellurate glass provided by the invention, boron can form topological units of [BO3] and [BO4], so that the density and refractive index of the tellurate glass and the complexity of a rare earth ion coordination environment are improved; bismuth utilizes the special electronic structure and the low-valence luminescence characteristic of bismuth to promote the laser glass to emit light at the nearly 1.8 mu m wave band; zinc ions are combined with free oxygen to form [ZnO4] and [ZnO6], and then participate in the formation of a glass network, so that the density of the glass is further improved, and the formation of zinc-oxygen tetrahedrons and zinc-oxygen hexahedrons enables network bond angles to be twisted, opened and closed, so that more coordination environments are provided for rare earth ions, and the luminous intensity of the rare earth ions is improved; by controlling the doping amount of thulium, the luminescent characteristic of thulium ions can be fully played, so that the glass has higher fluorescence intensity.

Description

Technical Field

[0001] This invention belongs to the field of luminescent glass technology, specifically relating to a thulium-doped tellurite glass, its preparation method, and its application. Background Technology

[0002] Lasers in the near 1.8μm band are within the safe working range for the human eye and have advantages such as high bandwidth transmission and low loss. They have great application potential in signal transmission, environmental monitoring, instrumentation, aerospace, medical imaging, 1.8μm band lasers, and multi-core photonic crystal fibers.

[0003] Fiber lasers are laser devices that use rare-earth-doped optical fibers as the gain medium. The core component, the rare-earth-doped fiber, determines the laser's output wavelength. Thulium, a rare-earth element, has a rich energy level distribution in its partially electron-free 4f shell. Excited rare-earth ions transition between the 4f and 4f energy levels, exhibiting characteristics such as easy excitation, concentrated emission wavelength, stable emission centers, and long fluorescence lifetime, enabling the emission of laser light in the near-1.8 μm wavelength range. Simultaneously, the luminescence characteristics of rare-earth ions, such as fluorescence lifetime, energy transfer efficiency, and fluorescence branching ratio in the near-1.8 μm wavelength range, depend to some extent on the type of fiber matrix (glass).

[0004] Currently, rare-earth ion-doped silicate glasses can serve as the main substrate for Stokes and anti-Stokes luminescence, but their low rare-earth ion solubility limits their ability to emit strong laser beams. Tellurate glasses, on the other hand, have high rare-earth ion solubility and a lower maximum phonon energy (10^77 cm^-3). -1 Due to its rich microstructure, tellurate glass possesses characteristics such as a high thermal damage threshold, high refractive index (1.93–1.99), high optical homogeneity, and high rare-earth ion solubility. Compared to traditional silicate materials, tellurate glass not only achieves higher laser emission capabilities but also enables mass production and application in actual manufacturing.

[0005] However, fiber lasers fabricated from tellurate glass still exhibit high losses in the near-infrared band, resulting in relatively low laser emission capabilities in the near 1.8 μm band. For example, the maximum absorption and emission cross-sections of thulium-doped TeO2-B2O3-Al2O3-Na2O glass only reach 6.0 × 10⁻⁶. -21 cm 2 9.0×10 -21 cm 2 The maximum gain coefficient is 1.75cm. -1 This makes it difficult to meet the requirements for high-intensity laser emission. Summary of the Invention

[0006] The purpose of this invention is to provide a thulium-doped tellurate glass, its preparation method, and its applications. The thulium-doped tellurate glass provided by this invention exhibits strong laser emission capability in the near-1.8 μm wavelength range, meeting the requirements for high-intensity laser emission.

[0007] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0008] This invention provides a thulium-doped tellurite glass with the chemical formula aTeO2-bBi2O3-cB2O3-dZnO:xTm2O3 in oxide form, wherein a is 76-84%, b is 4-6%, c is 4-6%, d is 8-12%, and a+b+c+d=100%; x is 2-6%.

[0009] Preferably, the chemical formula of the thulium-doped tellurate glass, in oxide form, is aTeO2-bBi2O3-cB2O3-dZnO:xTm2O3, wherein a is 80%, b is 5%, c is 5%, d is 10%, and x is 2-6%.

[0010] The present invention also provides a method for preparing thulium-doped tellurite glass as described in the above technical solution, comprising:

[0011] TeO2, Bi2O3, B2O3, ZnO and Tm2O3 are mixed and melted to obtain a glass melt; the glass melt is cast and annealed to obtain thulium-doped tellurite glass.

[0012] Preferably, the melting temperature is 950–1050°C, and the holding time is 30–40 min.

[0013] Preferably, the annealing temperature is 360–380°C, and the holding time is 4–6 hours.

[0014] Preferably, the annealing cooling rate is 4–6 °C / min.

[0015] Preferably, the mixing method is grinding.

[0016] Preferably, the grinding is unidirectional grinding, and the grinding time is not less than 30 minutes.

[0017] Preferably, the particle size of TeO2 is 80-90 nm; the particle size of Bi2O3 is 20-30 nm; the particle size of B2O3 is 200-600 nm; the particle size of ZnO is 50-70 nm; and the particle size of Tm2O3 is 70-90 nm.

[0018] The present invention also provides the application of the thulium-doped tellurate glass described in the above technical solution in fiber lasers.

[0019] This invention provides a thulium-doped tellurate glass with the chemical formula aTeO2-bBi2O3-cB2O3-dZnO:xTm2O3, where a is 76-84%, b is 4-6%, c is 4-6%, d is 8-12%, and a+b+c+d=100%; x is 2-6%. In the thulium-doped tellurate glass provided by this invention, boron can form [BO3] and [BO4] topological units, thereby improving the density, refractive index, and complexity of the rare-earth ion coordination environment of the tellurate glass; bismuth utilizes its special electronic structure ([Xe]4f... 14 5d 10 6s 2 6p 3 ), and its low-price state (Bi + Bi 3+ The thulium doping properties promote the luminescence of laser glass in the near 1.8 μm wavelength range. Zinc ions combine with free oxygen to form [ZnO4] and [ZnO6], which then participate in the formation of the glass network, further increasing the density of the glass. The formation of zinc-oxygen tetrahedra and hexahedrons causes the network bond angles to twist and open, providing more coordination environments for rare earth ions and increasing their luminescence intensity. Furthermore, the addition of ZnO significantly lowers the melting temperature of the system, making large-scale fabrication of multi-component tellurate laser glasses and the drawing of laser fibers possible. By controlling the doping amount of thulium, the luminescence properties of thulium ions can be fully utilized, resulting in high fluorescence intensity in the glass. The results of the embodiments show that the thulium-doped tellurate glass provided by this invention achieves a transmittance of 82% in the near 1.8 μm wavelength range, with a maximum absorption cross-section and a maximum emission cross-section of 7.1 × 10⁻⁶. -21 cm 2 1.43×10 -20 cm 2 The maximum gain coefficient is 27.3cm. -1 . Attached Figure Description

[0020] Figure 1 These are actual images of the glass samples from Examples 1 to 5 of the present invention;

[0021] Figure 2 This is a physical image of the glass sample of Comparative Example 1 of the present invention;

[0022] Figure 3 The absorption spectra of glass samples from Examples 1-5 of this invention under diode-pumped excitation are shown.

[0023] Figure 4 The fluorescence spectra of glass samples from Examples 1 to 5 of this invention are shown below.

[0024] Figure 5The XRD spectrum of the glass sample in Example 4 of this invention;

[0025] Figure 6 This is a transmittance diagram of the glass sample in Example 4 of the present invention;

[0026] Figure 7 The DSC spectrum of the glass sample in Example 4 of this invention;

[0027] Figure 8 The images show the absorption-emission cross-section and gain curve of the glass sample in Example 4 of this invention at a depth of approximately 1.8 μm under excitation by an 808 nm pump source. (a) shows the absorption and emission cross-sections, and (b) shows the gain coefficient. Detailed Implementation

[0028] All raw materials used in this invention are not particularly limited in their source; they can be purchased from the market or prepared using conventional methods known to those skilled in the art.

[0029] This invention provides a thulium-doped tellurite glass with the chemical formula aTeO2-bBi2O3-cB2O3-dZnO:xTm2O3 in oxide form, wherein a is 76-84%, b is 4-6%, c is 4-6%, d is 8-12%, and a+b+c+d=100%; x is 2-6%.

[0030] The thulium-doped tellurate glass provided by this invention has the chemical formula aTeO2-bBi2O3-cB2O3-dZnO:xTm2O3 in oxide form. Here, a, b, c, and d represent the molar percentage of each oxide in the tellurate glass, and x represents the amount of rare earth element doping in the tellurate glass, expressed as a molar percentage.

[0031] In this invention, the chemical formula of the doped tellurate glass contains 76-84% a, preferably 78-82%; as one embodiment of this invention, the chemical formula of the thulium-doped tellurate glass can contain 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, or 84% a. TeO2 is the matrix material of the tellurate glass, and its molar content within the above range can form a three-dimensional network structure of the glass, ensuring the basic properties of the tellurate glass; moreover, it can form [TeO3], [TeO2], etc. 3+1 [TeO4] and other elements form topological units that are intertwined and connected to each other, creating a complex microscopic coordination environment that can increase Tm. 3+ exist 3 The quantum population of the F4 level is increased, thereby improving the fluorescence intensity in the near 1.8 μm band.

[0032] In this invention, the thulium-doped tellurate glass has a b content of 4-6%, preferably 5%, in its chemical formula. The molar content of Bi₂O₃ is within the above range, utilizing the unique electronic structure of bismuth ([Xe]₄f). 14 5d 10 6s 2 6p 3 ), and its low-price state (Bi + Bi 3+ The light-emitting properties promote the light emission of laser glass in the near 1.8μm wavelength range.

[0033] In this invention, the thulium-doped tellurate glass has a carbon content of 4-6%, preferably 5%, in its chemical formula. When the molar content of B2O3 is within the above range, topological units of [BO3] and [BO4] can be formed, thereby improving the density, refractive index, and complexity of the rare-earth ion coordination environment of the tellurate glass.

[0034] In this invention, the chemical formula of the thulium-doped tellurate glass has a d content of 8-12%, preferably 9-11%, and more preferably 10%. When the molar content of ZnO is within the above range, zinc ions combine with free oxygen to form [ZnO4] and [ZnO6], which then participate in the formation of the glass network. This further increases the density of the glass. Furthermore, the formation of zinc-oxygen tetrahedra and zinc-oxygen hexahedrons causes the network bond angles to twist and open, providing more coordination environments for rare earth ions and increasing their luminescence intensity. The addition of ZnO significantly lowers the melting temperature of the system, making large-scale preparation of multi-component tellurate laser glasses and the drawing of laser fibers possible.

[0035] In this invention, the chemical formula of the thulium-doped tellurate glass is a+b+c+d=100%.

[0036] In this invention, the chemical formula of the thulium-doped tellurate glass contains x of 2-6%, preferably 3-5%. As one embodiment of this invention, the chemical formula of the thulium-doped tellurate glass can contain x of 2%, 3%, 4%, 5%, or 6%. Tm₂O₃ is the doping material for the tellurate glass, and its molar content within the above range can fully utilize the luminescent properties of thulium ions, resulting in a glass with high fluorescence intensity.

[0037] In the thulium-doped tellurate glass provided by this invention, boron can form [BO3] and [BO4] topological units, thereby improving the density, refractive index, and complexity of the rare earth ion coordination environment of the tellurate glass; bismuth utilizes its special electronic structure ([Xe]4f 14 5d 10 6s 2 6p 3 ), and its low-price state (Bi + Bi3+ The luminescence properties of thulium promote the luminescence of laser glass in the near 1.8 μm wavelength range. Zinc ions combine with free oxygen to form [ZnO4] and [ZnO6], which then participate in the formation of the glass network. This further improves the density of the glass. The formation of zinc-oxygen tetrahedra and zinc-oxygen hexahedrons causes the network bond angles to twist and open, providing more coordination environments for rare earth ions and increasing their luminescence intensity. The addition of ZnO significantly lowers the melting temperature of the system, making it possible to prepare multi-component tellurate laser glasses on a large scale and to draw laser fibers. By controlling the amount of thulium doping, the luminescence properties of thulium ions can be fully utilized, giving the glass a high fluorescence intensity.

[0038] The present invention also provides a method for preparing thulium-doped tellurite glass as described in the above technical solution, comprising:

[0039] TeO2, Bi2O3, B2O3, ZnO and Tm2O3 are mixed and melted to obtain a glass melt; the glass melt is cast and annealed to obtain thulium-doped tellurite glass.

[0040] This invention involves mixing TeO2, Bi2O3, B2O3, ZnO and Tm2O3 and then melting them to obtain a glass melt.

[0041] In this invention, the particle size of TeO2 is preferably 80-90 nm, more preferably 85 nm; the particle size of Bi2O3 is preferably 20-30 nm, more preferably 25 nm; the particle size of B2O3 is preferably 200-600 nm, more preferably 400 nm; the particle size of ZnO is preferably 50-70 nm, more preferably 60 nm; and the particle size of Tm2O3 is preferably 70-90 nm, more preferably 80 nm. Having particle sizes within the above ranges is beneficial for uniform mixing of the raw materials, further improving the uniformity and fluorescence stability of the glass.

[0042] In one embodiment of the present invention, the purity of TeO2, Bi2O3, B2O3, ZnO and Tm2O3 can be independently not less than 99.9% or 99.99%.

[0043] In this invention, the mixing method is preferably grinding, and the grinding is preferably unidirectional grinding; as one embodiment of this invention, the grinding can be clockwise. Grinding can make the raw materials mix evenly, and unidirectional grinding can further improve the uniformity of mixing.

[0044] In this invention, the grinding time is preferably not less than 30 minutes, more preferably 30 to 35 minutes; as one embodiment of this invention, the grinding time can be 30 minutes, 31 minutes, 32 minutes, 33 minutes, 34 minutes, or 35 minutes. Grinding times within the above ranges are beneficial for uniform mixing of raw materials.

[0045] In one embodiment of the present invention, the grinding can be carried out in an agate mortar.

[0046] In this invention, the melting temperature is preferably 950–1050°C, more preferably 980–1020°C; as one embodiment of this invention, the melting temperature can be 960°C, 970°C, 990°C, 1000°C, 1010°C, 1030°C, or 1040°C. Melting temperatures within the above ranges facilitate complete melting of the raw materials, further improving the uniformity and fluorescence stability of the glass.

[0047] In this invention, the holding time for melting is preferably 30-40 min, more preferably 33-37 min; as one embodiment of this invention, the holding time for melting can be 31 min, 32 min, 34 min, 35 min, 36 min, 38 min, or 39 min. A holding time within the above range facilitates complete melting of the raw materials, further improving the uniformity and fluorescence stability of the glass.

[0048] In one embodiment of the present invention, the melting can be carried out by placing the ground raw material in an alumina crucible, placing the crucible in a pit furnace, and performing the melting in a nitrogen atmosphere.

[0049] After obtaining the molten glass, the present invention casts the molten glass into a mold and then anneals it to obtain thulium-doped tellurite glass.

[0050] The present invention does not impose any particular limitation on the specific casting operation; conventional casting operations in the art can be used.

[0051] In this invention, the annealing temperature is preferably 360–380°C, more preferably 365–375°C; as one embodiment of this invention, the annealing temperature can be 363°C, 366°C, 369°C, 370°C, 373°C, 376°C, or 379°C. Annealing temperatures within the above ranges are beneficial for eliminating internal stress, improving tissue uniformity, and further enhancing fluorescence performance.

[0052] In this invention, the annealing holding time is preferably 4-6 hours, more preferably 4.5-5.5 hours, and even more preferably 5 hours. Annealing holding time within the above range is beneficial for eliminating internal stress, improving tissue uniformity, and further enhancing fluorescence properties.

[0053] In this invention, the cooling rate of the annealing is preferably 4-6 °C / min, more preferably 5 °C / min. An annealing cooling rate within this range is beneficial for eliminating internal stress, improving tissue uniformity, and further enhancing fluorescence performance.

[0054] In one embodiment of the present invention, the annealing can be carried out in a muffle furnace.

[0055] In one embodiment of the present invention, the mold can be placed in a muffle furnace, the muffle furnace can be heated to the annealing temperature, the molten glass can be poured onto the mold, and annealing can be performed directly after the casting is completed.

[0056] The preparation method provided by this invention is simple, easy to implement, and easy to control, which is conducive to large-scale production.

[0057] The present invention also provides the application of the thulium-doped tellurate glass described in the above technical solution in fiber lasers.

[0058] The present invention does not particularly limit the specific application method of the described method; conventional application methods in the field can be used.

[0059] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0060] Example 1

[0061] A thulium-doped tellurite glass, designated 1#, has the chemical formula aTeO2-bBi2O3-cB2O3-dZnO:xTm2O3 in oxide form, wherein a is 80%, b is 5%, c is 5%, d is 10%, and x is 2%.

[0062] Raw materials: TeO2 with a particle size of 85nm and a purity of 99.99%; Bi2O3 with a particle size of 25nm and a purity of 99.99%; B2O3 with a particle size of 400nm and a purity of 99.99%; ZnO with a particle size of 60nm and a purity of 99.99%; Tm2O3 with a particle size of 80nm and a purity of 99.99%.

[0063] The preparation method is as follows:

[0064] Weigh each raw material according to the proportions in the chemical formula and pour it into an agate mortar. The total weight of the raw materials is 5g. Grind in a clockwise direction for 30 minutes and then transfer it to an alumina crucible. Place the crucible in a pit furnace and heat it to 1000℃ in a nitrogen atmosphere. Hold it at that temperature for 35 minutes. Place the mold in a muffle furnace at 370℃ and pour the resulting molten glass onto the mold. Anneal the glass and hold it at that temperature for 4.5 hours. Then, cool it to room temperature at a cooling rate of 5℃ / min. Remove the glass to obtain thulium-doped tellurite glass.

[0065] Example 2

[0066] A thulium-doped tellurite glass, designated as 2#, has the chemical formula aTeO2-bBi2O3-cB2O3-dZnO:xTm2O3 in oxide form, wherein a is 80%, b is 5%, c is 5%, d is 10%, and x is 3%.

[0067] Example 3

[0068] A thulium-doped tellurite glass, designated 3#, has the chemical formula aTeO2-bBi2O3-cB2O3-dZnO:xTm2O3 in oxide form, wherein a is 80%, b is 5%, c is 5%, d is 10%, and x is 4%.

[0069] Example 4

[0070] A thulium-doped tellurite glass, designated 4#, has the chemical formula aTeO2-bBi2O3-cB2O3-dZnO:xTm2O3 in oxide form, wherein a is 80%, b is 5%, c is 5%, d is 10%, and x is 5%.

[0071] Example 5

[0072] A thulium-doped tellurite glass, designated 5#, has the chemical formula aTeO2-bBi2O3-cB2O3-dZnO:xTm2O3 in oxide form, wherein a is 80%, b is 5%, c is 5%, d is 10%, and x is 6%.

[0073] Comparative Example 1

[0074] A thulium-doped tellurite glass has the chemical formula aTeO2-bBi2O3-cB2O3-dZnO:xTm2O3 in oxide form, wherein a is 85%, b is 4%, c is 4%, d is 7%, and x is 5%.

[0075] Physical images of the glass samples in Examples 1-5 are shown below. Figure 1 As shown, Figure 1 From left to right, the images show glass samples from Examples 1 to 5; a physical image of the glass sample from Comparative Example 1 is shown below. Figure 2 As shown. Comparison Figure 1 and Figure 2 It can be seen that, due to the change in the ratio of raw materials, the sample obtained in Comparative Example 1 is opaque and cannot be used as laser glass.

[0076] Test Example 1

[0077] The glass samples from Examples 1-5 were cut and polished into 10mm × 10mm × 2mm glass sheets, and then their absorption spectra were measured under 808nm laser diode pumping. The test results are as follows: Figure 3 As shown. From Figure 3 It can be seen that the glass samples in Examples 1-5 are... 1 G4 3 F2+ 3 F3 3 H4 3 H5 3 The F4 energy level exhibits a distinct absorption peak; a clear absorption band is obtained at 808 nm, which is beneficial for the excitation of laser glass and is suitable for the preparation and application of laser glass and fiber materials in the near 1.8 μm wavelength band.

[0078] Test Example 2

[0079] The fluorescence intensity of the glass samples from Examples 1-5 in the 1300-2200 nm wavelength range under 808 nm laser diode-pumped excitation was measured using a fluorophotometer. The results are as follows: Figure 4 As shown. From Figure 4 It can be seen that as the doping amount of thulium increases, the fluorescence intensity of the glass first increases and then decreases, with the strongest fluorescence intensity when the molar doping amount is 5%.

[0080] Test Example 3

[0081] The glass sample from Example 4 was examined using an X-ray diffractometer, and the results are as follows: Figure 5 As shown. From Figure 5 It can be seen that the XRD spectrum does not contain sharp crystal peaks, and there are two diffuse peaks near 2θ equal to 30° and 50°, indicating that there is no periodic arrangement of atoms, the glass is amorphous, and no crystallization will occur.

[0082] Test Example 4

[0083] The transmittance of the glass sample in Example 4 was measured using a UV-Vis-NIR spectrophotometer, and the results are as follows: Figure 6 As shown. From Figure 6 It can be seen that the transmittance reaches 82% at the 1800nm ​​band, indicating that the glass sample has high transmittance and improves the optical properties of the glass.

[0084] Test Example 5

[0085] The glass sample from Example 4 was tested using a differential scanning calorimeter, and the results are as follows: Figure 7 As shown. From Figure 7 It can be seen that the glass transition temperature T of the glass sample in Example 4 is... g The temperature at which crystallization begins is 396℃. x The temperature is 524℃, and the difference between the two is ΔT = T. x -T g The temperature is 128℃, which is much higher than 100℃, and it has good thermal stability and glass-forming properties.

[0086] Test Example 6

[0087] The absorption, emission cross section and gain coefficient of the glass sample of Example 4 were calculated based on the McCumber and Fuchtbauer-Ladenburg theory. The calculations are expressed by the following formulas (1), (2) and (3).

[0088]

[0089] In the formula, N is the rare earth ion concentration, OD(λ) is the optical density (determined by the intensity of the absorption spectral line), and L is the sample thickness. The sample thickness L in this invention is 2 mm.

[0090]

[0091] In the formula, λ is the wavelength, and A rad Let λ be the spontaneous transition probability, c be the speed of light, n be the refractive index, and I(λ) be the fluorescence intensity at wavelength λ.

[0092] G(λ)=N[Pσ emi (λ)-(1-P)σ abs (λ)] (3)

[0093] In the formula, N represents the concentration of rare earth ions, P is the population reversal factor, and σ abs (λ) and σ emi (λ) represent the absorption and emission cross sections at wavelength λ, respectively. The calculation results are as follows: Figure 8 As shown. From Figure 8 It can be seen that the glass sample in Example 4 has a high emission cross-section, with the maximum absorption cross-section and maximum emission cross-section reaching 7.1 × 10⁻⁶. -21 cm 2 1.43×10 -20 cm 2 The maximum gain coefficient is 27.3cm. -1This facilitates laser emission in the near 1.8 μm band; and when the inversion factor P reaches 0.1 or higher, positive gain in the near 1.8 μm band can be achieved. The low inversion factor indicates that thulium-doped tellurate glass has a lower pump threshold in the near 1.8 μm band, making it easier to achieve laser output in this band.

[0094] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A thulium-doped tellurate glass, characterized in that, The chemical formula, expressed in oxide form, is aTeO2-bBi2O3-cB2O3-dZnO:xTm2O3, wherein a is 76-84%, b is 4-6%, c is 4-6%, d is 8-12%, and a+b+c+d=100%; x is 2-6%.

2. The thulium-doped tellurate glass according to claim 1, characterized in that, The chemical formula, expressed in oxide form, is aTeO2-bBi2O3-cB2O3-dZnO:xTm2O3, where a is 80%, b is 5%, c is 5%, d is 10%, and x is 2-6%.

3. The method for preparing the thulium-doped tellurite glass according to claim 1 or 2, characterized in that, Includes the following steps: The glass melt is obtained by mixing and melting TeO2, Bi2O3, B2O3, ZnO and Tm2O3. After the molten glass is cast into shape, it is annealed to obtain thulium-doped tellurite glass.

4. The preparation method according to claim 3, characterized in that, The melting temperature is 950–1050°C, and the holding time is 30–40 minutes.

5. The preparation method according to claim 3, characterized in that, The annealing temperature is 360–380°C, and the holding time is 4–6 hours.

6. The preparation method according to claim 5, characterized in that, The annealing cooling rate is 4–6 °C / min.

7. The preparation method according to claim 3, characterized in that, The mixing method is grinding.

8. The preparation method according to claim 7, characterized in that, The grinding is unidirectional grinding, and the grinding time is not less than 30 minutes.

9. The preparation method according to claim 3, characterized in that, The particle size of the TeO2 is 80-90 nm; the particle size of the Bi2O3 is 20-30 nm; the particle size of the B2O3 is 200-600 nm; the particle size of the ZnO is 50-70 nm; and the particle size of the Tm2O3 is 70-90 nm.

10. The application of the thulium-doped tellurate glass according to claim 1 or 2, or the thulium-doped tellurate glass prepared by any one of claims 3 to 9, in fiber lasers.

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