Er < 3 + >-doped dual-frequency excitation up-conversion luminescent glass and preparation method thereof

Abstract

The invention discloses Er < 3 + >-doped dual-frequency excitation up-conversion luminescent glass and a preparation method thereof, and the luminescent glass comprises the following components by molar percentage: 50 to 80 mol% of TeO2, 15 to 25 mol% of ZnO, 0.3 to 2 mol% of luminescent ion ErF3, 0.5 to 10 mol% of cosolvent Li2CO3, 0 to 15 mol% of PbF2, 0 to 15 mol% of Bi2O3, and 0 to 40 mol% of GeO2. The luminescent glass provided by the invention can realize dual-frequency excitation up-conversion luminescence at the intersection point of 850nm and 1550nm laser, and by adding luminescent ions, the luminescent intensity and the luminescent efficiency are improved.

Description

Technical Field

[0001] This invention relates to the field of luminescent materials technology, specifically to an Er 3+ Doped dual-frequency excited upconversion luminescent glass and its preparation method. Background Technology

[0002] Upconversion luminescent materials are materials that absorb two or more low-energy photons and emit high-energy photons. Dual-frequency upconversion luminescence refers to the absorption of two or more low-energy photons of different wavelengths and the subsequent emission of high-energy photons. Dual-frequency excitation technology has attracted much attention due to its potential applications in many fields such as ultraviolet upconversion luminescence, dynamic 3D displays, solar cells, and photodiodes.

[0003] Scandium (Sc) does not contain 4f electrons in its electronic structure, while the luminescence of rare earth ions is mainly determined by the filling state of these 4f electrons. Therefore, scandium is not as closely related to other rare earth elements, exhibiting optical inertness and making it well-suited as a matrix for luminescent materials. In 2012, Teng et al. successfully synthesized Na with excellent luminescent properties for the first time using a thermal decomposition method. x ScF 3+x :Ln 3+ Upconversion nanocrystals. In 2018, Deng et al. designed a novel KSc2F7:Yb nanocrystal. 3+ / Er 3+ Fluorescent nanoprobes, when excited by a 980nm laser, not only exhibit excellent upconversion luminescence performance (Deng Z M. A high performance Sc-based nanoprobe for through-skull fluorescence imaging of brain vessels beyond 1500nm[J].Nanoscale,2018,10(19):9393-9400.). In 2019, Peng Yongzhao et al. reported a glass-ceramic composite material inlaid with KSc2F7 and KLn2F7 nanocrystals in a glass matrix, and the red, yellow, and green colors could be controlled by adjusting the proportion of rare earth doping (CN 110204209 A). In summary, the research on scandium element, whether in nanocrystals or glass-ceramic composite materials, is mainly single-frequency excitation upconversion luminescence, while research on dual-frequency excitation upconversion luminescence is still rarely reported.

[0004] Bismuthate glasses, as a novel upconversion matrix system, possess excellent chemical and thermal stability, a high refractive index, a wide transmission range, and lower phonon energy than conventional oxide glasses. This is combined with tellurate glasses, which exhibit low phonon energy, excellent chemical stability, low melting point, and high rare-earth solubility. Therefore, Er... 3+Doped tellurite bismuthate microcrystalline glass holds promise for achieving efficient green light output. CaF₂ with a fluorite structure is often used to improve the high single-frequency excitation luminescence efficiency of rare-earth ions. For example, Qiao X et al. (Luminescence behavior of Er) 3+ Er(II) in glass-ceramics containing CaF2 nanocrystals. Journal of Non-Crystalline Solids, 2005, 351(5):357-363.) reported on the Er(II) in fluoride-oxygen glass containing CaF2 nanocrystals. 3+ Upconversion luminescence and near-infrared luminescence. Under excitation by a 980nm laser, Er in the microcrystalline glass... 3+ The upconversion luminescence intensity of ions increases significantly. For example, Cai J et al. (Up-conversion luminescence and optical thermometry properties of transparent glass ceramics containing CaF2:Yb) 3+ / Er 3+ (Nanocrystals. Ceramics International, 2016: 13990-13995.) reported CaF2:Yb 3+ / Er 3+ Co-doped silicate transparent glass exhibits maximum emission intensity under 980 nm laser excitation, producing strong red, green, and blue upconversion emission. However, research on using CaF2 doping to enhance dual-frequency excited upconversion luminescence is rarely reported.

[0005] Gallium telluride germanate glass and gallium telluride germanate sulfide glass are frequently used in research on far-infrared lasers. In 2019, Zhang Qinyuan et al. prepared rare-earth ion Er... 3+ Doped gallium zinc telluride laser glass exhibited strong 2.7 μm fluorescence under 808 nm and 980 nm laser diode (LD) pumping, and the decay lifetime of the 2.7 μm fluorescence could be directly monitored (CN 109369007 A). In 2019, Lu Xiaosong et al. reported Tm... 3+ The doped chalcogenide microcrystalline glass shows that Tm under 808 nm laser excitation 3+ The ions exhibit strong mid-infrared luminescence at 3.7 μm (Distribution of Tm). 3+ and Ni 2+In chalcogenide glass ceramics containing Ga2S3 nanocrystals: Influence on photoluminescence properties, Journal of the European Ceramic Society, 39, 7, 2580-2584, 2019.). However, there are currently few reports, both domestically and internationally, on dual-frequency upconversion luminescence of rare-earth ion-doped gallium telluride germanate glasses.

[0006] Yttrium does not contain 4f electrons in its electronic structure, while the luminescence of rare earth ions is mainly determined by the filling state of 4f electrons. Therefore, yttrium is not as closely related to other rare earth elements, exhibiting optical inertness, making it well-suited as a matrix for luminescent materials. In 2011, Leonidov I et al. demonstrated that adjusting the molar composition of Y in the composition could effectively improve Er... 3+ Upconversion luminescence in Er 3+ / Yb 3+ codopedY2CaGe4O 12 Journal of Alloys & Compounds, 2011, 509(5): 1339-1346. A 2019 study by Dan HK et al. showed that Y... 3+ It can effectively enhance Bi+-Er 3+ Near-infrared emission intensity of transparent silicate microcrystalline glass for co-doped optical amplifiers. (Effects of Y) 3+ on the enhancement NIR emission of Bi + -Er 3+ Co-doped in transparent silicate glass-ceramics for Erbium-doped fiber amplifier (EDFA). Journal of Luminescence, 2019, 219: 116942. In summary, some progress has been made in the research on using rare earth ions (Y) to improve the efficiency of single-frequency upconversion luminescence or downconversion luminescence. However, research on using rare earth ions (Y) to improve dual-frequency excitation upconversion luminescence is still rarely reported. Summary of the Invention

[0007] This invention aims to at least solve one of the technical problems existing in the prior art. Therefore, the object of this invention is to propose an Er... 3+Doped dual-frequency excited upconversion luminescent glass and its preparation method.

[0008] To achieve its objective, the present invention employs the following technical solution:

[0009] The first aspect of the present invention provides an Er 3+ The doped dual-frequency excitation upconversion luminescent glass, by molar percentage, comprises the following components: 50-80% molar TeO2, 15-25% molar ZnO, 0.3%-2% molar luminescent ions ErF3, 0.5%-10% molar cosolvent Li2CO3, 0-15% molar PbF2, 0-15% molar Bi2O3, and 0-40% molar GeO2.

[0010] The above Er 3+ Doped dual-frequency excitation upconversion luminescent glass can be one of four types of luminescent glass:

[0011] The first type is the aforementioned luminescent glass, Er. 3+ ,Sc 3+ The co-doped dual-frequency upconversion luminescent glass, by molar percentage, comprises the following components: 50–70 mol of TeO2, 15–25 mol of ZnO, 0.3–2 mol of ErF3, 0.5–10 mol of Li2CO3, 3–15 mol of PbF2, 5–20 mol of GeO2, and 0.1–2 mol of ScF3;

[0012] The preferred composition includes the following components: 50-65% moles of TeO2, 17-23% moles of ZnO, 0.4-0.8% moles of ErF3, 0.5-5% moles of Li2CO3, 4-12% moles of PbF2, 7-13% moles of GeO2, and 0.5-2% moles of ScF3;

[0013] The preferred composition includes the following components: 55-61% molar TeO2, 19-21% molar ZnO, 0.5-0.6% molar ErF3, 0.5-1.5% molar Li2CO3, 6-8% molar PbF2, 9-11% molar GeO2, and 0.5-2% molar ScF3;

[0014] The preferred composition includes the following components: 56-61% moles of TeO2, 20% moles of ZnO, 0.55% moles of ErF3, 1% moles of Li2CO3, 7% moles of PbF2, 10% moles of GeO2, and 0.5-2% moles of ScF3.

[0015] The second type is the aforementioned luminescent glass, Er. 3+The doped bismuth telluride microcrystalline glass comprises, by molar percentage, the following components: 60–70 mol of TeO2, 15–25 mol of ZnO, 5–15 mol of Bi2O3, 0.5–2 mol of ErF3, 3–10 mol of Li2CO3, and 0.1–2 mol of CaF2;

[0016] Preferably, it includes the following components: 60-70% moles of TeO2, 17-23% moles of ZnO, 6-10% moles of Bi2O3, 0.5-1% moles of ErF3, 3-8% moles of Li2CO3, and 0.1-2% moles of CaF2;

[0017] Preferably, it includes the following components: 65-67% moles of TeO2, 19-21% moles of ZnO, 7-9% moles of Bi2O3, 0.6-0.7% moles of ErF3, 4-6% moles of Li2CO3, and 0.5-2% moles of CaF2;

[0018] The preferred composition includes the following components: 65-67% moles of TeO2, 20% moles of ZnO, 8% moles of Bi2O3, 0.65% moles of ErF3, 5% moles of Li2CO3, and 0.5-1.5% moles of CaF2.

[0019] 50–80 mol TeO2, 15–25 mol ZnO, 0.3%–2 mol ErF3, 0.5%–10 mol Li2CO3, 1–15 mol PbF2, and 5–40 mol GeO2

[0020] The third type is a monochromatic dual-frequency upconversion gallium telluride germanate glass, which, by molar percentage, comprises the following components: 50-80% moles of TeO2, 10-25% moles of ZnO, 0.5-9% moles of gallium compound, 5-20% moles of GeO2, 0.3-2% moles of ErF3, 0.5-10% moles of Li2CO3, and 3-15% moles of PbF2; wherein the gallium compound is Ga2O3 or Ga2S3.

[0021] Preferably, it comprises the following components: 50-65% molar TeO2, 18-22% molar ZnO, 0.5-7% molar gallium compound, 7-13% molar GeO2, 0.3-0.8% molar ErF3, 0.5-2% molar Li2CO3, and 5-12% molar PbF2;

[0022] Preferably, the composition includes the following components: 54-62% molar TeO2, 19-21% molar ZnO, 0.5-7% molar gallium compound, 9-11% molar GeO2, 0.5-0.6% molar ErF3, 0.9-1.1% molar Li2CO3, and 6-8% molar PbF2;

[0023] The preferred composition includes the following components: 54-61.5% molar TeO2, 20% molar ZnO, 5-7% molar gallium compound, 10% molar GeO2, 0.55% molar ErF3, 1% molar Li2CO3, and 7% molar PbF2.

[0024] Fourthly, the aforementioned luminescent glass is made of rare earth ions (Er). 3+ Y 3+ The co-doped dual-frequency upconversion luminescent telluride germanate microcrystalline glass comprises, by molar percentage: 50–70 mol of TeO2, 15–25 mol of ZnO, 0.5–10 mol of Ga2O3, 5–20 mol of GeO2, 0.3–2 mol of ErF3, 0.5–10 mol of Li2CO3, 3–15 mol of PbF2, and 0.1–5 mol of Y2O3;

[0025] The preferred composition includes the following components: 40–60 mol of TeO2, 18–22 mol of ZnO, 3–9 mol of Ga2O3, 7–13 mol of GeO2, 0.3–0.8 mol of ErF3, 0.5–2 mol of Li2CO3, 5–12 mol of PbF2, and 0.1–3 mol of Y2O3;

[0026] The preferred composition includes the following components: 50-60% moles of TeO2, 19-21% moles of ZnO, 4-7% moles of Ga2O3, 8-12% moles of GeO2, 0.5-0.6% moles of ErF3, 0.8-1.3% moles of Li2CO3, 6-8% moles of PbF2, and 0.3-1.5% moles of Y2O3;

[0027] The preferred composition includes the following components: 54-57% moles of TeO2, 20% moles of ZnO, 5-6% moles of Ga2O3, 10% moles of GeO2, 0.55% moles of ErF3, 1% moles of Li2CO3, 7% moles of PbF2, and 0.5-1.0% moles of Y2O3.

[0028] The second aspect of the present invention provides the above-described Er 3+ The preparation method of doped dual-frequency excitation upconversion luminescent glass involves weighing each raw material component according to the ratio and preparing it by melt cooling.

[0029] The above preparation method includes the following steps:

[0030] S1. Weigh each raw material component according to the proportion, grind and mix thoroughly to obtain a mixture;

[0031] S2. Melt the mixture in step S1 in a high-temperature sintering furnace to melt the raw materials into a liquid state and homogenize the glass liquid to obtain a uniform molten glass liquid.

[0032] S3. Pour the molten glass from step S2 into the mold and allow the glass to cool and solidify.

[0033] S4. Anneal the cooled and shaped glass obtained in step S3.

[0034] S5. Polish the glass from step S4.

[0035] Preferably, the preparation method is as follows:

[0036] In step S1, after the raw material components are mixed and initially ground to ensure uniformity, anhydrous ethanol is added and grinding is continued to ensure that the materials are fully mixed and uniform. Then, the raw materials are heated and dried.

[0037] In step S2, the melting temperature is 900-1100℃, and the temperature is held for 30-80 minutes to homogenize the glass melt.

[0038] In step S3, the molten glass from step S2 is poured into a preheated graphite mold and left to stand in air for 10 to 100 seconds.

[0039] In step S5, the glass is ground flat using water grinding, and then polished using CeO2 as the polishing agent.

[0040] The annealing method in step S4 is as follows:

[0041] Transfer the mold containing the molten glass from step S3 to a precision temperature-controlled muffle furnace at 280℃~320℃ and hold for 4 hours. Then, reduce the temperature of the precision temperature-controlled muffle furnace to room temperature at a rate of 1℃ / min; alternatively, the annealing method is as follows:

[0042] The graphite mold containing the molten glass is transferred to a precision temperature-controlled muffle furnace at 280℃~320℃ and held for 4 hours. Then, the temperature is increased to 320℃~350℃ at a rate of 1℃ / min and held for 2 hours. Finally, the temperature of the precision temperature-controlled muffle furnace is reduced to room temperature at a rate of 1℃ / min. Holding at 320℃~350℃ for 2 hours allows fluorides in samples containing fluorides such as CaF2 to form microcrystals, thereby reducing the phonon energy near the luminescence center and increasing the luminescence intensity of the sample. Glass samples without additional fluoride doping do not require secondary annealing.

[0043] The temperature range for the two annealing methods described above is determined based on the measured glass transition temperature and crystallization temperature of the glass sample.

[0044] Preferably, the preparation method further includes step S6:

[0045] S6. The cold-processed glass was subjected to a dual-frequency excitation luminescence performance test. The laser wavelengths for dual-frequency excitation were 850nm and 1550nm, respectively.

[0046] The beneficial effects of this invention are:

[0047] 1. The Er of this invention 3+ ,Sc 3+ Co-doped dual-frequency upconversion light-emitting glass

[0048] An Er is prepared by melt cooling method. 3+ ,Sc 3+ Erbium-scandium co-doped glass was excited sequentially using two near-infrared lasers of different wavelengths (1550nm and 850nm). The rare earth ions Er in the glass composition... 3+ As the luminescent center, it sequentially absorbs photon energy at wavelengths of 850nm and 1550nm, reaching... 4 F 7 / 2 , 4 S 3 / 2 The excited state returns to the source through photon radiation. 4 I 15 / 2 In the ground state, dual-frequency upconversion luminescence is achieved at the intersection of 850nm and 1550nm lasers. ScF3 in the glass composition significantly improves the dual-frequency upconversion luminescence efficiency. Specifically,

[0049] (1) Tellurium oxide (TeO2), which has high solubility of rare earth ions, is the main component of the glass. At the same time, a certain amount of germanium oxide (GeO2) and zinc oxide (ZnO) are added to improve the glass's forming ability and physicochemical stability.

[0050] (2) The scandium fluoride (ScF3) component in the glass forms nanocrystals, which helps to change the luminescent center Er. 3+ The environment in which it is located can effectively reduce the Er of rare earth ions. 3+ This increases the nonradiative transition probability, thereby improving the dual-frequency upconversion luminescence efficiency.

[0051] (3) When the microcrystalline glass is excited at dual frequencies of 1550 nm and 850 nm, the luminescent center Er 3+ After absorbing photon energy, it reaches 4 F 7 / 2 , 4 S 3 / 2The excited state emits monochromatic strong green light at the intersection of 850nm and 1550nm lasers, exhibiting high contrast. Specifically, it does not emit light when excited by a single frequency at 1550nm, while it emits very weak green light when excited by a single frequency at 850nm.

[0052] 2. The Er of the present invention 3+ Doped tellurium bismuthate microcrystalline glass

[0053] Currently, there are few reports on the use of CaF2 doping to improve the upconversion luminescence efficiency of telluride bismuthate glass crystals. This invention provides an Er 3+ Doped tellurium bismuthate glass-ceramics were prepared by melt cooling. Two near-infrared laser beams of different wavelengths (1550 nm and 850 nm) were used to sequentially excite the tellurium bismuthate glass-ceramics. The rare earth ions Er in the tellurium bismuthate glass-ceramic composition... 3+ As the luminescent center, it sequentially absorbs photon energy at wavelengths of 850nm and 1550nm, reaching... 4 F 7 / 2 , 4 S 3 / 2 The excited state returns to the source through photon radiation. 4 I 15 / 2 The ground state exhibits dual-frequency excitation upconversion luminescence at the intersection of 850nm and 1550nm lasers. CaF2 in the tellurium bismuthate microcrystalline glass can promote Er... 3+ The dual-frequency excitation upconversion luminescence efficiency of ions. Specifically,

[0054] (1) In the tellurium bismuthate microcrystalline glass of the present invention, tellurium oxide (TeO2) with high solubility of rare earth ions is used as the main component of germanium gallium tellurate glass, and a certain amount of bismuth trioxide (Bi2O3) component and zinc oxide (ZnO) component are added to improve the glass forming ability and physicochemical stability.

[0055] (2) An Er of the present invention 3+ The calcium fluoride (CaF2) component in doped tellurium bismuthate glass-ceramics has lower phonon energy, which can reduce the rare earth ion Er. 3+ This increases the nonradiative transition probability, thereby improving the dual-frequency upconversion luminescence efficiency.

[0056] (3) An Er of the present invention 3+ When doped tellurium bismuthate glass crystals are excited at dual frequencies of 1550 nm and 850 nm, the luminescent centers Er 3+ After absorbing photon energy, it reaches 4 F 7 / 2 , 4 S 3 / 2The excited state emits monochromatic strong green light at the intersection of 850nm and 1550nm lasers. The 1550nm single-frequency excitation does not emit light, while the 850nm single-frequency excitation emits weak light. The intersection emission has high contrast.

[0057] 3. The monochromatic dual-frequency upconversion luminescent gallium telluride germanate glass of the present invention

[0058] Currently, there are few reports on the upconversion luminescence of rare-earth ion-doped gallium telluride germanate glass. This invention relates to a monochromatic dual-frequency upconversion luminescence gallium telluride germanate glass, prepared by a melt-cooling method. The gallium telluride germanate glass is sequentially excited by two near-infrared lasers of different wavelengths (1550 nm and 850 nm). The rare-earth ions Er in the gallium telluride germanate glass composition... 3+ As the luminescent center, it sequentially absorbs photon energy at wavelengths of 850nm and 1550nm, reaching... 4 F 7 / 2 , 4 S 3 / 2 The excited state returns to the source through photon radiation. 4 I 15 / 2 In the ground state, monochromatic dual-frequency upconversion luminescence is achieved at the intersection of 850nm and 1550nm lasers. Specifically,

[0059] (1) In the gallium telluride germanate glass of the present invention, tellurium oxide (TeO2) with high solubility of rare earth ions is used as the main component of gallium telluride germanate glass, and a certain amount of germanium oxide (GeO2) component and gallium trioxide (Ga2O3) component are added to improve the glass forming ability and physicochemical stability.

[0060] (2) In a monochromatic dual-frequency upconversion luminescent gallium telluride germanate glass of the present invention, the lead fluoride (PbF2) component and the gallium trioxide (Ga2O3) component have lower phonon energies, which can reduce the rare earth ion Er. 3+ This increases the nonradiative transition probability, thereby improving the dual-frequency upconversion luminescence efficiency.

[0061] (3) A gallium telluride germanate glass of the present invention exhibits monochromatic dual-frequency upconversion luminescence. When the microcrystalline glass is excited at 1550nm and 850nm dual frequencies, the luminescence center Er 3+ After absorbing photon energy, it reaches 4 F 7 / 2 , 4 S 3 / 2 The excited state emits monochromatic strong green light at the intersection of 850nm and 1550nm lasers. The 1550nm single-frequency excitation does not emit light, while the 850nm single-frequency excitation emits weak light. The intersection emission has high contrast.

[0062] 4. The rare earth ion Er of the present invention 3+ Y3+ Co-doped dual-frequency upconversion luminescent telluride germanate microcrystalline glass

[0063] Currently, there are few reports on the use of rare earth ions (Y) to improve the upconversion luminescence efficiency of dual-frequency excitation in telluride germanate microcrystalline glass. The rare earth ion Er... (The sentence is incomplete and requires further context to be fully translated.) 3+ Y 3+ Co-doped dual-frequency upconversion luminescent telluride germanate microcrystalline glass was prepared by melt cooling method, and rare earth ions Er were sequentially excited using two near-infrared lasers of different wavelengths, 1550 nm and 850 nm. 3+ Y 3+ Co-doped tellurium germanate glass-ceramics, with rare earth ions Er in the tellurium germanate glass-ceramic composition. 3+ As the luminescent center, it sequentially absorbs photon energy at wavelengths of 850nm and 1550nm, reaching... 4 F 7 / 2 , 4 S 3 / 2 The excited state returns to the source through photon radiation. 4 I 15 / 2 The ground state achieves dual-frequency excitation upconversion luminescence at the intersection of 850nm and 1550nm lasers. Specifically,

[0064] (1) In the tellurium germanate glass of the present invention, tellurium oxide (TeO2) with high solubility of rare earth ions is used as the main component of tellurium germanate microcrystalline glass. At the same time, the addition of a certain amount of germanium oxide (GeO2), gallium trioxide (Ga2O3), zinc oxide (ZnO) and yttrium trioxide (Y2O3) can improve the glass forming ability and physicochemical stability.

[0065] (2) The tellurium germanate microcrystalline glass of the present invention contains Y 3+ Ions and Er 3+ Ions with similar ionic radii and the same valence state are more likely to occupy similar positions in a glass network. 3+ It is more conducive to replacing Y in crystals 3+ Ions, by placing themselves in a localized field with lower phonon energy, can effectively reduce the luminescence center Er. 3+ The nonradiative transition probability of ions is increased, effectively improving the upconversion luminescence intensity of dual-frequency excitation at 850 nm and 1550 nm.

[0066] (3) In the tellurium germanate microcrystalline glass of the present invention, when the microcrystalline glass is excited at dual frequencies of 1550nm and 850nm, the luminescent center Er 3+ After absorbing photon energy, it reaches 4 F 7 / 2 , 4 S 3 / 2The excited state emits monochromatic strong green light at the intersection of 850nm and 1550nm lasers.

[0067] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0068] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0069] Figure 1 The images show digital images of the luminescent glass obtained in Experimental Group 1-1 of Example 1, exhibiting single and dual-frequency excitation at 850nm and 1550nm.

[0070] Figure 2 To implement the fluorescence spectra of upconversion luminescence of microcrystalline glass obtained by single-frequency and dual-frequency excitation at 850nm and 1550nm in experimental groups 1-5 of implementation 1.

[0071] Figure 3 The fluorescence spectra of the microcrystalline glass obtained by dual-frequency excitation upconversion luminescence at 850nm and 1550nm in experimental groups 1-1 to 1-5 in Example 1 are shown.

[0072] Figure 4 This is a digital image of the 850nm and 1550nm dual-frequency excitation luminescence of the telluride bismuthate microcrystalline glass obtained in experimental group 2-1 of Example 2.

[0073] Figure 5 The fluorescence spectra of the telluride bismuthate microcrystalline glass obtained in Experimental Group 2-2 of Example 2 are those of single-frequency and dual-frequency excitation upconversion luminescence at 850nm and 1550nm.

[0074] Figure 6 The fluorescence spectra of 850nm and 1550nm dual-frequency excitation upconversion luminescence of telluride bismuthate microcrystalline glass obtained in the four experimental groups in Example 2 are shown.

[0075] Figure 7 This is a digital image of gallium telluride germanate glass obtained in experimental group 3-1 of Example 3, showing dual-frequency excitation emission at 850nm and 1550nm.

[0076] Figure 8 The fluorescence spectra of gallium telluride germanate glass obtained in experimental group 3-2 of Example 3 are those of single-frequency and dual-frequency excitation upconversion luminescence at 850nm and 1550nm.

[0077] Figure 9The fluorescence spectra of gallium telluride germanate glass obtained by dual-frequency excitation upconversion luminescence at 850nm and 1550nm in experimental groups 3-1 to 3-4 of Example 3 are shown.

[0078] Figure 10 The fluorescence spectra of gallium telluride germanate glass obtained in experimental groups 3-5 of Example 3 are those of upconversion luminescence at 850nm and 1550nm single and dual frequency excitation.

[0079] Figure 11 This is a digital photograph of the tellurium germanate glass of Experiment 4-1 in Example 4, which is a dual-frequency up-conversion light-emitting glass at 850nm and 1550nm.

[0080] Figure 12 The fluorescence spectra of tellurium germanate glass obtained in Experimental Group 4-2 of Example 4 are those of single-frequency and dual-frequency excitation upconversion luminescence at 850nm and 1550nm.

[0081] Figure 13 The fluorescence spectra of germanium gallium tellurate glass obtained from dual-frequency excitation upconversion luminescence at 850 nm and 1550 nm in the four experimental groups in Example 4 are shown. Detailed Implementation

[0082] The embodiments of the present invention are described in detail below, and the embodiments described with reference to the accompanying drawings are exemplary.

[0083] Unless otherwise specified, the experimental methods described in the following examples are conventional methods.

[0084] The raw materials used in the examples are as follows:

[0085]

[0086]

[0087] Example 1, an Er 3+ ,Sc 3+ Co-doped dual-frequency upconversion light-emitting glass

[0088] A type of Er 3+ ,Sc 3+ The co-doped dual-frequency upconversion luminescent glass was prepared according to the following steps:

[0089] S1. Weigh the glass phase components by molar percentage: TeO2: 0-80%, ZnO: 0-25%, PbF2: 0-15%, ScF3: 0-2%, GeO2: 0-40%, ErF3: 0-2%, Li2CO3: 0-10%; the purity of TeO2, GeO2, and ScF3 is 99.99%, and the purity of ZnO, ErF3, PbF2, and Li2CO3 is analytical grade; the total molar percentage of each component of the glass is 100%. Weigh each raw material component into an agate mortar and grind for 30 minutes to initially mix the raw materials. Then add an appropriate amount of anhydrous ethanol and continue grinding for 30 minutes to fully mix the materials. Then use a blower to heat the agate mortar for auxiliary drying. After that, put the well-mixed material into a platinum crucible. Blower-assisted heating drying refers to using a blower to heat the agate mortar, thereby evaporating the anhydrous ethanol and drying the glass raw materials.

[0090] S2. Place the platinum crucible from step S1 into a high-temperature sintering furnace (e.g., a muffle furnace) for melting. Melt the raw material into a liquid state and keep it at a constant temperature for a period of time. The firing atmosphere is air, the melting temperature is 900-1100℃ (960℃ for all 5 experimental groups), and the holding time is 30-80 minutes (50 minutes for all 5 experimental groups). The purpose of holding the temperature is to homogenize the glass melt and obtain a uniform, bubble-free molten glass melt.

[0091] S3. Pour the molten glass from step S2 into a preheated graphite mold and allow the glass to cool and solidify.

[0092] S4. Transfer the graphite mold containing the molten glass from step S3 to a precision temperature-controlled muffle furnace at 280℃~320℃ for annealing. After annealing, turn off the precision temperature-controlled muffle furnace and remove the obtained glass. The annealing process is as follows: transfer the graphite mold containing the molten glass to a precision temperature-controlled muffle furnace at 280℃~320℃ (290℃ for experimental groups 1-1~1-4, and 280℃ for experimental groups 1-5) and keep it at that temperature for 4 hours (to eliminate the internal stress of the glass sample and prevent the glass from breaking). Then, reduce the temperature of the precision temperature-controlled muffle furnace to room temperature at a rate of 1℃ / min.

[0093] S5. Grind and polish the glass from step S4 on a metallographic grinding and polishing machine; use water grinding to grind the glass flat, and then polish it with CeO2 as the polishing agent.

[0094] Following the above method, Er was prepared in experimental groups 1-1 to 1-5. 3+ ,Sc 3+ The specific composition of each experimental group of co-doped dual-frequency upconversion luminescent glass is shown in Table 1:

[0095] Table 1

[0096] experimental group <![CDATA[Er 3+ ,Sc 3+ Composition (mol%) of co-doped dual-frequency upconversion luminescent glass Experimental group 1-1 <![CDATA[59.95 TeO2-20 ZnO-1.5ScF3-10GeO2-7 PbF2-0.55 ErF3-1 Li2CO3]]> Experimental group 1-2 <![CDATA[60.45 TeO2-20 ZnO-1 ScF3-10GeO2-7 PbF2-0.55 ErF3-1 Li2CO3]]> Experimental groups 1-3 <![CDATA[59.45 TeO2-20 ZnO-2 ScF3-10GeO2-7 PbF2-0.55 ErF3-1 Li2CO3]]> Experimental groups 1-4 <![CDATA[60.95 TeO2-20 ZnO-0.5 ScF3-10 GeO2-7 PbF2-0.55 ErF3-1 Li2CO3]]> Experimental groups 1-5 <![CDATA[56.45 TeO2-20 ZnO-10 GeO2-7 PbF2-0.55 ErF3-1 Li2CO3]]>

[0097] The glass samples prepared in Experimental Groups 1-1 to 1-5 were processed into fully polished glass samples with dimensions of 21mm × 21mm × 10mm. Dual-frequency excitation upconversion luminescence tests at 850nm and 1550nm were performed. Bright green light was emitted at the intersection of the 850nm and 1550nm lasers within the glass sample. Single-frequency excitation at 1550nm produced no light, single-frequency excitation at 850nm produced very weak green light, and dual-frequency excitation at 850nm and 1550nm produced green light at the intersection, with a single-frequency to dual-frequency luminescence intensity ratio of 1:73. Digital images of the luminescent glass from Experimental Group 1-1 emitting light under single and dual-frequency excitation at 850nm and 1550nm are shown below. Figure 1 As shown.

[0098] Compared to experimental groups 1-5, experimental group 1-1, with the introduction of 1.5 mol% scandium fluoride, showed a 25.13% increase in the intensity of green light emitted by dual-frequency excitation at 850 nm and 1550 nm; experimental group 1-2, with the introduction of 1% mol% scandium fluoride, showed a 16.31% increase in the intensity of green light emitted by dual-frequency excitation at 850 nm and 1550 nm; experimental group 1-3, with the introduction of 2 mol% scandium fluoride, showed a 23.93% increase in the intensity of green light emitted by dual-frequency excitation at 850 nm and 1550 nm; and experimental group 1-4, with the introduction of 0.5 mol% scandium fluoride, showed a 10.63% increase in the intensity of green light emitted by dual-frequency excitation at 850 nm and 1550 nm. Figure 2 The fluorescence spectra of the luminescent glasses in experimental groups 1-5 under single-frequency and dual-frequency excitation at 850 nm and 1550 nm, respectively, are shown. Figure 3 The fluorescence spectra of upconversion luminescence under dual-frequency excitation at 850 nm and 1550 nm for experimental groups 1-1 to 1-5 are shown.

[0099] Example 2, an Er 3+ Doped tellurium bismuthate microcrystalline glass

[0100] A type of Er 3+ Doped tellurium bismuthate microcrystalline glass was prepared according to the following steps:

[0101] S1. Accurately weigh the glass phase components by molar percentage: TeO2: 0–80%, ZnO: 0–25%, Bi2O3: 0–15%, CaF2: 0–5%, ErF3: 0–2%, Li2CO3: 0–10%. The purity of TeO2 and Bi2O3 is 99.99%, and ZnO, ErF3, CaF2, and Li2CO3 are all analytical grade; the total molar percentage of each component of the glass is 100%. Grind the above raw materials thoroughly for 30 minutes, then mix them with anhydrous ethanol to ensure uniform distribution. Finally, use a blower to assist in heating and drying. Place the uniformly mixed telluride-bismuthate glass raw material into a platinum crucible. Blower-assisted heating and drying refers to using a blower to heat an agate mortar, thereby evaporating the anhydrous ethanol and drying the glass raw material.

[0102] S2. Place the platinum crucible from step S1 into a high-temperature sintering furnace for melting. Melt the raw material into a liquid state and keep it at a constant temperature for a period of time. The firing atmosphere is air, the melting temperature is 900-1100℃ (960℃ for all 4 experimental groups), and the holding time is 30-80min (50min for all 4 experimental groups). The purpose of holding the temperature is to homogenize the glass melt.

[0103] S3. Pour the molten glass from step S2 into a preheated graphite mold and let it remain in air for 10-100 seconds. The residence time of the molten glass in air after being poured into the preheated graphite mold is related to the quality of the fired bismuth telluride microcrystalline glass.

[0104] S4. Transfer the graphite mold containing the glass molten metal from step S3 to a precision temperature-controlled muffle furnace at 280℃~300℃ for stress-relief annealing. Then, raise the temperature to 320~350℃ for microcrystallization annealing. After annealing, turn off the precision temperature-controlled muffle furnace and remove the initially obtained bismuth telluride microcrystalline glass. The specific annealing process is as follows: transfer the graphite mold containing the glass molten metal to a precision temperature-controlled muffle furnace at 280℃~320℃ and hold it at that temperature for 4 hours. Then, raise the temperature to 320℃ at a rate of 1℃ / min.

[0105] Hold at ~350℃ for 2 hours, then reduce the temperature of the precision temperature-controlled muffle furnace to room temperature at a rate of 1℃ / min.

[0106] S5. Grind and polish the tellurium bismuthate microcrystalline glass from step S4 on a metallographic grinding and polishing machine: use water grinding to grind the tellurium bismuthate microcrystalline glass flat, and then polish it with CeO2 as the polishing agent.

[0107] Following the method described above, Er from experimental groups 2-1 to 2-5 was prepared. 3+ The specific composition of each experimental group of doped tellurium bismuthate microcrystalline glass is shown in Table 2:

[0108] Table 2

[0109] experimental group <![CDATA[Er 3+ Composition (mol%) of doped bismuth telluride microcrystalline glass Experimental group 2-1 <![CDATA[66.35 TeO2-20 ZnO-8 Bi2O3-0.65 ErF3-5 Li2CO3]]> Experimental group 2-2 <![CDATA[65.85 TeO2-20 ZnO-8 Bi2O3-0.65 ErF3-5 Li2CO3-0.5 CaF2]]> Experimental group 2-3 <![CDATA[65.35 TeO2-20 ZnO-8 Bi2O3-0.65 ErF3-5 Li2CO3-1 CaF2]]> Experimental groups 2-4 <![CDATA[65.85 TeO2-20 ZnO-8 Bi2O3-0.65 ErF3-5 Li2CO3-1.5 CaF2]]>

[0110] The glasses prepared in Experimental Groups 2-1 to 2-4 were processed into fully polished glass samples with dimensions of 21mm × 21mm × 10mm, and upconversion luminescence tests were performed using dual-frequency excitation at 850nm and 1550nm. A digital photograph of the dual-frequency upconversion luminescent glass of the bismuth tellurate microcrystalline glass in Experimental Group 2-1 is shown below. Figure 1 As shown, the 850nm and 1550nm lasers emit bright green light at the intersection point within the tellurium bismuthate glass. The dual-frequency upconversion emission spectrum of the microcrystalline glass in experimental group 2-2 is shown in the attached figure. Figure 2 As shown, the fluorescence spectra of 850nm and 1550nm dual-frequency excited upconversion luminescence of bismuth telluride microcrystalline glass obtained in the four experimental groups are as follows: Figure 3 As shown.

[0111] Compared to experimental group 2-1, the addition of 0.5% mol CaF2 to the molar composition of the microcrystalline glass in experimental group 2-2 increased the upconversion luminescence intensity at 850 nm and 1550 nm by 3.28%; the addition of 1% mol CaF2 to the molar composition of the microcrystalline glass in experimental group 2-3 increased the upconversion luminescence intensity at 850 nm and 1550 nm by 6.88%; and the microcrystalline glass in experimental group 2-4 with 1.5% mol CaF2 added to its molar composition exhibited the highest dual-frequency excitation luminescence intensity, which increased by 12.21% compared to the undoped microcrystalline glass.

[0112] Example 3: A gallium telluride germanate glass with monochromatic dual-frequency upconversion luminescence

[0113] A monochromatic dual-frequency upconversion luminescent gallium telluride germanate glass is prepared according to the following steps:

[0114] S1. Accurately weigh the glass phase components by molar percentage: TeO2: 0–80%, ZnO: 0–25%, PbF2: 0–15%, Ga2O3: 0–7%, GeO2: 0–40%, ErF3: 0–2%, Li2CO3: 0–10%. The purity of TeO2, GeO2, and Ga2O3 is 99.99%, and the purity of ZnO, ErF3, PbF2, and Li2CO3 is analytical grade. The total molar percentage of all components in the glass is 100%. Grind the above raw materials thoroughly for 30 minutes, then mix them with anhydrous ethanol to ensure uniform distribution. Finally, use a blower to assist in heating and drying. Place the uniformly mixed glass raw material into a platinum crucible. Blower-assisted drying refers to using a blower to heat an agate mortar, thereby evaporating the anhydrous ethanol and drying the glass raw material.

[0115] S2. Place the platinum crucible from step S1 into a high-temperature sintering furnace for melting. Melt the raw material into a liquid state and keep it at a constant temperature for a period of time. The firing atmosphere is air, the melting temperature is 900-1100℃ (960℃ for all 5 experimental groups), and the holding time is 30-80min (50min for all 5 experimental groups). The purpose of holding the temperature is to homogenize the glass melt.

[0116] S3. Pour the molten glass from step S2 into a preheated graphite mold and let it remain in air for 10-100 seconds. The time the molten glass remains in air after being poured into the preheated graphite mold is related to the quality of the gallium telluride germanate glass being fired.

[0117] S4. Transfer the graphite mold containing the molten glass from step S3 to a precision temperature-controlled muffle furnace at 280℃~320℃ for annealing. After annealing, turn off the precision temperature-controlled muffle furnace and remove the obtained glass. The annealing process is as follows: transfer the graphite mold containing the molten glass to a precision temperature-controlled muffle furnace at 280℃~320℃ (290℃ for experimental groups 3-1~3-4, and 280℃ for experimental group 3-5) and keep it at that temperature for 4 hours. Then, reduce the temperature of the precision temperature-controlled muffle furnace to room temperature at a rate of 1℃ / min.

[0118] S5. Grind and polish the gallium telluride germanate glass from step S4 on a metallographic grinding and polishing machine: use water grinding to grind the gallium telluride germanate glass flat, and then polish it with CeO2 as the polishing agent.

[0119] Following the above method, gallium telluride germanate glasses for experimental groups 3-1 to 3-5 were prepared. The specific composition of each experimental group is shown in Table 3.

[0120] Table 3

[0121] experimental group Composition (mol%) of monochromatic dual-frequency upconversion luminescent gallium telluride germanate glass Experimental group 3-1 <![CDATA[56.45 TeO2-20 ZnO-5 Ga2O3-10 GeO2-7 PbF2-0.55 ErF3-1 Li2CO3]]> Experimental group 3-2 <![CDATA[55.45 TeO2-20 ZnO-6 Ga2O3-10 GeO2-7 PbF2-0.55 ErF3-1 Li2CO3]]> Experimental group 3-3 <![CDATA[54.45 TeO2-20 ZnO-7 Ga2O3-10 GeO2-7 PbF2-0.55 ErF3-1 Li2CO3]]> Experimental group 3-4 <![CDATA[61.45 TeO2-20 ZnO-10 GeO2-7 PbF2-0.55 ErF3-1 Li2CO3]]> Experimental group 3-5 <![CDATA[60.95 TeO2-20 ZnO-10 GeO2-0.5 Ga2S3-7 PbF2-0.55 ErF3-1 Li2CO3]]>

[0122] The glass samples obtained from experimental groups 3-1 to 3-5 were processed into fully polished glass samples with dimensions of 21mm × 21mm × 10mm, and then subjected to upconversion luminescence tests at dual frequencies of 850nm and 1550nm. Figure 7 The image shows the luminescence of gallium telluride germanate glass obtained by experimental group 3-1 under dual-frequency excitation at 850nm and 1550nm. The 850nm and 1550nm lasers emit bright green light at the intersection of the gallium telluride germanate glass. Figure 8 The fluorescence spectra of gallium telluride germanate glass obtained by experimental group 3-2 at 850 nm and 1550 nm single-frequency and dual-frequency excitation upconversion luminescence are shown. Figure 9 The fluorescence spectra of gallium telluride germanate glass obtained by dual-frequency excitation upconversion luminescence at 850 nm and 1550 nm obtained in experimental groups 3-1 to 3-4 are shown. Figure 10 The fluorescence spectra of gallium telluride germanate glass obtained at 850 nm and 1550 nm for single and dual-frequency excitation upconversion luminescence are shown in experimental groups 3-5. The results show that using Ga2S3 instead of Ga2O3 in experimental groups 3-5 can still improve the efficiency of dual-frequency upconversion luminescence to a certain extent.

[0123] In Experiment 3-2, the glass emitted weak green light upon single-frequency excitation at 850nm, but did not emit light upon excitation with a 1550nm laser. The green light intensity upon dual-frequency excitation at 850nm and 1550nm was 85 times that of the green light upon single-frequency excitation at 850nm. The dual-frequency upconversion luminescence intensity of the glass in Experiment 3-3 was lower than that of the gallium telluride germanate glass in Experiment 3-2.

[0124] Compared to experimental groups 3-4, the introduction of Ga2O3 into the glass composition of experimental groups 3-1 to 3-3 can significantly improve the efficiency of dual-frequency upconversion luminescence. Among them, the luminescence efficiency of experimental group 3-2 is 31% higher than that of experimental group 3-4.

[0125] Example 4: A rare earth ion Er 3+ Y 3+ Co-doped dual-frequency upconversion luminescent telluride germanate microcrystalline glass

[0126] A rare earth ion Er 3+ Y 3+ Co-doped dual-frequency upconversion luminescent telluride germanate glass crystals were prepared according to the following steps:

[0127] S1. Accurately weigh the glass phase components by molar percentage: TeO2: 0–80%, ZnO: 0–25%, PbF2: 0–15%, Ga2O3: 0–7%, GeO2: 0–40%, ErF3: 0–2%, Y2O3: 0–2%, Li2CO3: 0–10%. The purity of TeO2, GeO2, and Ga2O3 is 99.99%, and ZnO, ErF3, Y2O3, PbF2, and Li2CO3 are all analytical grade; the total molar percentage of each component of the glass is 100%. Grind the above raw materials thoroughly for 30 minutes, then mix them with anhydrous ethanol to ensure uniform distribution. Finally, use a blower to assist in heating and drying. Place the uniformly mixed glass raw material into a platinum crucible. Blower-assisted heating and drying refers to using a blower to heat an agate mortar, thereby evaporating the anhydrous ethanol and drying the glass raw material.

[0128] S2. Place the platinum crucible from step S1 into a high-temperature sintering furnace for melting. Melt the raw material into a liquid state and keep it at a constant temperature for a period of time. The firing atmosphere is air, the melting temperature is 900-1100℃ (960℃ for all 5 experimental groups), and the holding time is 30-80min (50min for all 5 experimental groups). The purpose of holding the temperature is to homogenize the glass melt.

[0129] S3. Pour the molten glass from step S2 into a preheated graphite mold and let it remain in air for 10-100 seconds. The time the molten glass remains in air after being poured into the preheated graphite mold is related to the quality of the fired tellurium germanate microcrystalline glass.

[0130] S4. Transfer the graphite mold containing the molten glass from step S3 to a precision temperature-controlled muffle furnace at 280℃~300℃ for stress-relief annealing, followed by microcrystallization annealing at 320℃~350℃. After annealing, turn off the precision temperature-controlled muffle furnace and remove the obtained tellurium germanate microcrystalline glass. The specific annealing process is as follows: transfer the graphite mold containing the molten glass to a precision temperature-controlled muffle furnace at 280℃~300℃ and hold for 4 hours, then raise the temperature to 320℃~350℃ at a rate of 1℃ / min and hold for 2 hours, and then lower the temperature of the precision temperature-controlled muffle furnace to room temperature at a rate of 1℃ / min.

[0131] S5. Grind and polish the tellurium germanate microcrystalline glass from step S4 on a metallographic grinding and polishing machine: use water grinding to grind the tellurium germanate microcrystalline glass flat, and then polish it with CeO2 as the polishing agent.

[0132] Following the above method, tellurium germanate microcrystalline glasses of experimental groups 4-1 to 4-5 were prepared. The specific composition of each experimental group is shown in Table 4.

[0133] Table 4

[0134] experimental group Composition (mol%) of telluride germanate microcrystalline glass co-doped with rare earth ions Er3+ and Y3+ for dual-frequency upconversion luminescence. Experimental group 4-1 <![CDATA[56.45 TeO2-20 ZnO-5 Ga2O3-10 GeO2-7 PbF2-0.55 ErF3-1 Li2CO3]]> Experimental group 4-2 <![CDATA[55.45 TeO2-20 ZnO-6 Ga2O3-10 GeO2-7 PbF2-0.55 ErF3-1 Li2CO3-0.5 Y2O3]]> Experimental group 4-3 <![CDATA[54.65 TeO2-20 ZnO-6 Ga2O3-10 GeO2-7 PbF2-0.55 ErF3-1 Li2CO3-0.8 Y2O3]]> Experimental group 4-4 <![CDATA[54.45 TeO2-20 ZnO-6 Ga2O3-10 GeO2-7 PbF2-0.55 ErF3-1 Li2CO3-1 Y2O3]]>

[0135] The glass samples prepared from the four experimental groups were processed into fully polished glass samples with dimensions of 21mm × 21mm × 10mm, and subjected to dual-frequency excitation upconversion luminescence tests at 850nm and 1550nm. A digital photograph of the dual-frequency upconversion luminescent glass from experimental group 4-1 is shown below. Figure 11 As shown, the 850nm and 1550nm lasers emit bright green light at the intersection of the tellurium germanate microcrystalline glass. Figure 12 The fluorescence spectra of tellurium germanate glass obtained in experimental group 4-2 are those of single-frequency and double-frequency excitation upconversion luminescence at 850 nm and 1550 nm. Figure 13 The fluorescence spectra of germanium gallium tellurate glass obtained by dual-frequency excitation upconversion luminescence at 850 nm and 1550 nm are shown for four experimental groups.

[0136] The results showed that introducing Y2O3 into the glass composition could significantly improve the efficiency of dual-frequency upconversion luminescence. Compared with experimental group 4-1, the dual-frequency excitation luminescence intensity of experimental group 4-2 with 0.5% mol Y2O3 doping increased by 1.88%, the dual-frequency excitation luminescence intensity of experimental group 4-3 with 0.8% mol Y2O3 doping increased by 11.66%, and the luminescence efficiency of experimental group 4-4 with 1% mol Y2O3 doping increased by 4.88%.

[0137] In the description of this specification, references to terms such as "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example.

[0138] Although embodiments of the invention have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.

Claims

1. A kind of Er 3+ A doped dual-frequency excited upconversion luminescent glass, characterized in that, The luminescent glass comprises the following components by molar percentage: 50-80% molar TeO2, 15-25% molar ZnO, 0.3%-2% molar luminescent ions ErF3, 0.5%-10% molar cosolvent Li2CO3, 0-15% molar PbF2, 0-15% molar Bi2O3, and 0-40% molar GeO2.

2. The Er as described in claim 1 3+ A doped dual-frequency excited upconversion luminescent glass, characterized in that, The luminescent glass is Er 3+ ,Sc 3+ The co-doped dual-frequency upconversion luminescent glass, by molar percentage, comprises the following components: 50–70 mol of TeO2, 15–25 mol of ZnO, 0.3–2 mol of ErF3, 0.5–10 mol of Li2CO3, 3–15 mol of PbF2, 5–20 mol of GeO2, and 0.1–2 mol of ScF3; The preferred composition includes the following components: 50-65% moles of TeO2, 17-23% moles of ZnO, 0.4-0.8% moles of ErF3, 0.5-5% moles of Li2CO3, 4-12% moles of PbF2, 7-13% moles of GeO2, and 0.5-2% moles of ScF3; The preferred composition includes the following components: 55-61% molar TeO2, 19-21% molar ZnO, 0.5-0.6% molar ErF3, 0.5-1.5% molar Li2CO3, 6-8% molar PbF2, 9-11% molar GeO2, and 0.5-2% molar ScF3; The preferred composition includes the following components: 56-61% moles of TeO2, 20% moles of ZnO, 0.55% moles of ErF3, 1% moles of Li2CO3, 7% moles of PbF2, 10% moles of GeO2, and 0.5-2% moles of ScF3.

3. The Er as described in claim 1 3+ A doped dual-frequency excited upconversion luminescent glass, characterized in that, The luminescent glass is Er 3+ The doped bismuth telluride microcrystalline glass comprises, by molar percentage, the following components: 60–70 mol of TeO2, 15–25 mol of ZnO, 5–15 mol of Bi2O3, 0.5–2 mol of ErF3, 3–10 mol of Li2CO3, and 0.1–2 mol of CaF2; Preferably, it includes the following components: 60-70% moles of TeO2, 17-23% moles of ZnO, 6-10% moles of Bi2O3, 0.5-1% moles of ErF3, 3-8% moles of Li2CO3, and 0.1-2% moles of CaF2; Preferably, it includes the following components: 65-67% moles of TeO2, 19-21% moles of ZnO, 7-9% moles of Bi2O3, 0.6-0.7% moles of ErF3, 4-6% moles of Li2CO3, and 0.5-2% moles of CaF2; The preferred composition includes the following components: 65-67% moles of TeO2, 20% moles of ZnO, 8% moles of Bi2O3, 0.65% moles of ErF3, 5% moles of Li2CO3, and 0.5-1.5% moles of CaF2. 50–80% moles of TeO2, 15–25% moles of ZnO, 0.3%–2% moles of ErF3, 0.5%–10% moles of Li2CO3, 1–15% moles of PbF2, and 5–40% moles of GeO2.

4. The Er as described in claim 1 3+ A doped dual-frequency excited upconversion luminescent glass, characterized in that, The luminescent glass is a monochromatic dual-frequency upconversion gallium telluride germanate glass, comprising the following components by molar percentage: 50–80 mol of TeO2, 10–25 mol of ZnO, 0.5–9 mol of gallium compound, 5–20 mol of GeO2, 0.3–2 mol of ErF3, 0.5–10 mol of Li2CO3, and 3–15 mol of PbF2; wherein the gallium compound is Ga2O3 or Ga2S3. Preferably, it comprises the following components: 50-65% molar TeO2, 18-22% molar ZnO, 0.5-7% molar gallium compound, 7-13% molar GeO2, 0.3-0.8% molar ErF3, 0.5-2% molar Li2CO3, and 5-12% molar PbF2; Preferably, the composition includes the following components: 54-62% molar TeO2, 19-21% molar ZnO, 0.5-7% molar gallium compound, 9-11% molar GeO2, 0.5-0.6% molar ErF3, 0.9-1.1% molar Li2CO3, and 6-8% molar PbF2; The preferred composition includes the following components: 54-61.5% molar TeO2, 20% molar ZnO, 5-7% molar gallium compound, 10% molar GeO2, 0.55% molar ErF3, 1% molar Li2CO3, and 7% molar PbF2.

5. The Er as described in claim 1 3+ A doped dual-frequency excited upconversion luminescent glass, characterized in that, The luminescent glass is made of rare earth ion Er. 3+ Y 3+ The co-doped dual-frequency upconversion luminescent telluride germanate microcrystalline glass comprises, by molar percentage: 50–70 mol of TeO2, 15–25 mol of ZnO, 0.5–10 mol of Ga2O3, 5–20 mol of GeO2, 0.3–2 mol of ErF3, 0.5–10 mol of Li2CO3, 3–15 mol of PbF2, and 0.1–5 mol of Y2O3; The preferred composition includes the following components: 40–60 mol of TeO2, 18–22 mol of ZnO, 3–9 mol of Ga2O3, 7–13 mol of GeO2, 0.3–0.8 mol of ErF3, 0.5–2 mol of Li2CO3, 5–12 mol of PbF2, and 0.1–3 mol of Y2O3; The preferred composition includes the following components: 50-60% moles of TeO2, 19-21% moles of ZnO, 4-7% moles of Ga2O3, 8-12% moles of GeO2, 0.5-0.6% moles of ErF3, 0.8-1.3% moles of Li2CO3, 6-8% moles of PbF2, and 0.3-1.5% moles of Y2O3; The preferred composition includes the following components: 54-57% moles of TeO2, 20% moles of ZnO, 5-6% moles of Ga2O3, 10% moles of GeO2, 0.55% moles of ErF3, 1% moles of Li2CO3, 7% moles of PbF2, and 0.5-1.0% moles of Y2O3.

6. The Er as described in any one of claims 1 to 5 3+ A method for preparing doped dual-frequency excited upconversion luminescent glass, characterized in that, Weigh each raw material component according to the formula and prepare it by melt cooling.

7. The Er as described in claim 6 3+ A method for preparing doped dual-frequency excited upconversion luminescent glass, characterized in that, Includes the following steps: S1. Weigh each raw material component according to the proportion, grind and mix thoroughly to obtain a mixture; S2. Melt the mixture in step S1 in a high-temperature sintering furnace to melt the raw materials into a liquid state and homogenize the glass liquid to obtain a uniform molten glass liquid. S3. Pour the molten glass from step S2 into the mold and allow the glass to cool and solidify. S4. Anneal the cooled and shaped glass obtained in step S3. S5. Polish the glass from step S4.

8. The Er as described in claim 7 3+ A method for preparing doped dual-frequency excited upconversion luminescent glass, characterized in that: In step S1, after the raw material components are mixed and initially ground to ensure uniformity, anhydrous ethanol is added and grinding is continued to ensure that the materials are fully mixed and uniform. Then, the raw materials are heated and dried. In step S2, the melting temperature is 900-1100℃, and the temperature is held for 30-80 minutes to homogenize the glass melt. In step S3, the molten glass from step S2 is poured into a preheated graphite mold and left to stand in air for 10 to 100 seconds. In step S5, the glass is ground flat using water grinding, and then polished using CeO2 as the polishing agent.

9. The Er as described in claim 7 3+ A method for preparing doped dual-frequency excited upconversion luminescent glass, characterized in that: The annealing method in step S4 is as follows: Transfer the mold containing the molten glass from step S3 to a precision temperature-controlled muffle furnace at 280℃~320℃ and hold it at that temperature for 4 hours. Then, reduce the temperature of the precision temperature-controlled muffle furnace to room temperature at a rate of 1℃ / min; or, The graphite mold containing the glass molten metal is transferred to a precision temperature-controlled muffle furnace at 280℃~320℃ and held for 4 hours. Then, the temperature is increased to 320℃~350℃ at a rate of 1℃ / min and held for 2 hours. Finally, the temperature of the precision temperature-controlled muffle furnace is reduced to room temperature at a rate of 1℃ / min.

10. The Er as described in claim 7 3+ A method for preparing doped dual-frequency excited upconversion luminescent glass, characterized in that, It also includes step S6: S6. The cold-processed glass was subjected to a dual-frequency excitation luminescence performance test. The laser wavelengths for dual-frequency excitation were 850nm and 1550nm, respectively.

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