Rare earth ion-doped functional nanocrystalline glass and method for producing the same

Abstract

W 3+ Lu4Zr3O doped with rare earth ions 12 The present invention provides functional nanocrystalline glass and a simple, low-cost method for manufacturing the same, which allows for controllable nanocrystal size. [Solution] The glass components consist of SiO2: 57-59, Al2O3: 12-16, ZnO: 14-18, Li2O: 6-8, ZrO2: 3-5, Lu2O3: 2-3, and Er2O3: 0.05-0.2 in molar percentage, with the total of the glass components being 100. This invention uses combination design and heat treatment process control to create a glass with Er 3+ Lu4Zr3O doped with rare earth ions 12 We have achieved the controllable manufacturing of functional nanocrystals, and these functional nanocrystalline glasses have potential applications in low-temperature optical temperature measurement.

Description

Technical Field

[0001] The present invention relates to the field of glass, and specifically to functional nanocrystalline glass doped with Er 3+ rare earth ions and a method for manufacturing the same. 12

Background Art

[0002] Oxides composed of RE2O3-MO2 (RE = La-Lu; M = Ti, Zr, Hf) have many unique properties. This type of oxide may have a defective fluorite structure, a pyrochlore structure or a δ-phase rhombohedral structure, and its specific structure depends on the chemical composition of the oxide and the shown order-disorder transition. For example, transitions from pyrochlore to defective fluorite, from rhombohedral δ-phase to defective fluorite, and from β-phase (hexagonal) to defective fluorite, all of which strongly depend on temperature and annealing time. The chemical formula of the oxide in these systems is generally represented by [AB]2O 8-x , for example, A2B2O7 pyrochlore, A4B3O 12 δ-phase, A2BO5 β-phase. Here, A and B are trivalent and tetravalent cations, respectively. In many cases, this type of oxide has good physical and chemical properties, particularly low thermal conductivity and high solubility of rare earth ions. Due to these properties, oxides such as those described above are expected to be applied to heat insulation coating layers, nuclear waste solidifying materials, hosts for luminescent rare earth ions, pigments, etc.

[0003] In recent years, extensive research has been conducted on the optical properties of δ-phase RE4Zr3O 12 crystals. For example, ultraviolet emission of Y4Zr3O 12 :Gd 3+ , red latent fingerprint emission of Y4Zr3O 12 :Eu 3+ , etc. Many of these materials are synthesized by sol-gel method, high-temperature sintering, sintering method, coprecipitation method, mechanical activation method, solution combustion method, etc. However, in glass, δ-phase RE4Zr3O 12 cannot be directly synthesized. Therefore, δ-phase RE4Zr3O 12There is a need to provide new materials and methods for precipitation.

Summary of the Invention

Problems to be Solved by the Invention

[0004] The object of the present invention is to provide functional nanocrystalline glass in which Lu4Zr3O is doped with rare earth ions Er, and a method for producing the same. The manufacturing process is simple, the size of the nanocrystals can be controlled, and the cost is low. 3+ in which Lu4Zr3O is doped with rare earth ions 12 The solution adopted by the present invention to solve the above technical problems is as follows.

[0005] The solution adopted by the present invention to solve the above technical problems is as follows. Er 3+ Functional nanocrystalline glass in which Lu4Zr3O is doped with rare earth ions 12 The glass contains a glass matrix and nanocrystals composed of Lu4Zr3O and Er rare earth ions in the glass matrix. 12 and Er 3+ including nanocrystals composed of rare earth ions.

[0006] Preferably, the glass components include, in mol%, SiO2: 57 - 59, Al2O3: 12 - 16, ZnO: 14 - 18, Li2O: 6 - 8, ZrO2: 3 - 5, Lu2O3: 2 - 3, Er2O3: 0.05 - 0.2, and the total of the glass components is 100.

[0007] Preferably, the size of the nanocrystals is 5 - 10 nm.

[0008] Preferably, the glass further contains 0.1 - 0.3 mol% of Sb2O3.

[0009] The method for producing the Lu4Zr3O 12 functional nanocrystalline glass is Weigh all raw materials according to the composition, mix them uniformly, put them into a crucible, melt at 1600 °C to 1650 °C for 1 - 3 hours, then pour into a mold and rapidly cool; anneal the rapidly cooled glass at 600 - 650 °C for 2 - 4 hours, and cool to room temperature to obtain a precast glass; heat-treat the precast glass at 700 - 800 °C for 5 - 7 hours to obtain the 12 functional nanocrystalline glass. The process includes these steps.

[0010] The 12 functional nanocrystalline glass can be used as a low-temperature optical temperature measurement material.

[0011] Preferably, the low-temperature range is from -263 °C to 25 °C.

[0012] Compared with the prior art, the present invention has the following effects. Based on the design and optimization of the glass composition, the present invention adopts a melting and rapid cooling - heat treatment method to produce Er 3+ doped Lu4Zr3O 12 . The manufacturing process is simple, and the composition and size of the nanocrystals can be easily adjusted and controlled. By compounding Lu4Zr3O 12 nanocrystals with glass, the excellent stability of the glass substrate is effectively utilized to improve the stability of Lu4Zr3O 12 nanocrystals and prevent aggregation. Furthermore, such a composite material of nanocrystals and glass has the potential for application in low-temperature optical temperature measurement.

Brief Description of the Drawings

[0013] [Figure 1] It is a diagram showing the XRD of the Lu4Zr3O12 functional nanocrystalline glass obtained under heat treatment at different temperatures of the precast glass AP in Example 1. [Figure 2] It is a transmission electron microscope diagram of the functional nanocrystalline glass obtained at 760 °C in Figure 1. (a) is a bright-field image, (b) is an enlarged image, and (c) is a HR-TEM image. [Figure 3]Figure 1 shows the EDS spectral results of a functional nanocrystalline glass obtained at 760°C. (a) Two-field images of the sample, (b) distribution of Lu, (c) Zr, (d) Er, (e) Si, (f) Zn, (g) Al, and (h) O. [Figure 4] (a) is a figure showing the normalized emission spectrum of the functional nanocrystalline glass obtained at 760°C in Figure 1, (b) is a figure showing the emission intensity ratio between the 2H11 / 2→4I15 / 2 and 4S3 / 2→4I15 / 2 transition emission, and (c) is a figure showing the curves of relative sensitivity (SR) and absolute sensitivity SA. [Modes for carrying out the invention]

[0014] The present invention will be described in detail below with reference to the drawings and embodiments, but the content of the present invention is not limited to the embodiments described below.

[0015] <Example 1> This embodiment is Er 3+ Lu4Zr3O doped with rare earth ions 12 A functional nanocrystalline glass is provided. The glass comprises a glass matrix and Lu4Zr3O 12 and Er 3+ The glass contains nanocrystals composed of rare earth ions. The glass components consist of 58 mol% SiO2, 13 mol% Al2O3, 15 mol% ZnO, 7 mol% Li2O, 4 mol% ZrO2, 2.9 mol% Lu2O3, and 0.1 mol% Er2O3, and the glass further contains 0.2 mol% Sb2O3.

[0016] Based on the aforementioned composition, the raw materials were weighed according to the aforementioned composition, mixed uniformly, placed in a crucible, melted at 1630°C for 2 hours, poured into a brass mold and rapidly cooled, the rapidly cooled glass was quickly transferred to a strengthening furnace, annealed at 630°C for 3 hours, and then the power was turned off and the furnace was cooled to room temperature to obtain precast glass (hereinafter referred to as AP). The AP glass was heat-treated at 700°C, 720°C, 740°C and 760°C for 6 hours to obtain the aforementioned Lu4Zr3O 12 We obtained functional nanocrystalline glass.

[0017] As shown in Figure 1, a broad diffraction halo (Figure 1) is observed in the AP sample, indicating that the AP sample is mainly amorphous and does not contain any detectable nanocrystalline phases. Heat treatment at 700°C reveals a weak diffraction peak around 30°. As the heat treatment temperature increases, this peak gradually strengthens, and simultaneously, other diffraction peaks with large diffraction angles appear (Figure 1). These diffraction peaks are Lu4Zr3O 12 The diffraction peaks are consistent with those of the crystal (PDF#77-738, space group R

[16] ), and Lu4Zr3O is present in the heat-treated glass. 12 This indicates that nanocrystals of the crystal are precipitated.

[0018] As shown in Figure 2, after heat treatment, numerous dark spots (10-25 nm) can be observed in the sample, and these dark spots are distributed almost uniformly within the sample (Figure 2a). In the magnified image shown in Figure 2b, it can be seen that these dark spots are composed of multiple small nanocrystals (5-10 nm), have clear lattice patterns, and indicate aggregation of small nanocrystals. The HR-TEM image (Figure 2c) shows that the spacing between the crystal planes of these small nanocrystals is approximately 2.97 μm, and Lu4Zr3O 12 This matches the distance between crystal planes (=2.9763 μm, PDF#77-738). XRD patterns and HR-TEM images show that Lu4Zr3O is released from the glass after heat treatment. 12 It has been proven that nanocrystals were precipitated. Furthermore, after heat treatment, Lu4Zr3O was released from the glass. 12 To prove that nanocrystals were precipitated, EDS mapping was performed on samples treated at 760°C for 6 hours, and the results are shown in Figure 3. The elemental distribution in the region shown in Figure 3a shows that Lu (Figure 3b) and Zr (Figure 3c) are concentrated in these nanocrystals, and the analysis results from XRD and TEM are in agreement. The concentration of Er2O3 in the glass is relatively low, and the contrast in Figure 3d is also relatively weak, but the distribution of Er (Figure 3d) is almost identical to the distribution of Lu and Zr, and Er 3+ Ion is Lu4Zr3O 12This indicates doping within the nanocrystals. Other elements such as Si (Figure 3e), Zn (Figure 3f), Al (Figure 3g), and O (Figure 3h) are distributed almost uniformly in the sample. During the heat treatment process, Er 3+ Ion is Lu4Zr3O 12 Doped into nanocrystals, Er 3+ The local environment and optical properties of ions can be altered. 3+ Lu4Zr3O was doped. 12 To evaluate the potential applications of nanocrystalline microcrystalline glass in low-temperature optical temperature measurement, the emission spectra that change with temperature were measured for samples heat-treated at 760°C for 6 hours (shown in Figure 4). Figure 4a shows the normalized emission spectra recorded under 10-296K conditions (Figure 4a shows the spectra from 10K, 20K, 40K, 60K, 80K, 100K, 120K, 140K, 160K, 180K, 200K, 225K, 250K, 275K, and 296K, starting from the bottom around 525nm). Absolute temperature sensitivity S A It increases with increasing temperature, reaching a maximum value at 465K, and relative temperature sensitivity S R S decreased with increasing temperature (Figure 4c). A is 0.3%K -1 S R is 1.03%K -1 As a result of the above, Er 3+ Lu4Zr3O was doped. 12 Microcrystalline glass containing nanocrystals has been found to have potential applications in low-temperature optical temperature measurement.

[0019] <Example 2> This example is substantially identical to Example 1, except that the glass components, in mol% terms, consist of 57 mol% SiO2, 16 mol% Al2O3, 18 mol% ZnO, 6 mol% Li2O, 3 mol% ZrO2, 2 mol% Lu2O3, 0.2 mol% Er2O3, and also contain 0.1 mol% Sb2O3. The AP glass was heat-treated at 760°C for 6 hours. A is 0.25%K -1 S R is 1.13%K-1 That was the case.

[0020] <Example 3> This example is substantially identical to Example 1, except that the glass components, in mol% terms, consist of 59 mol% SiO2, 12 mol% Al2O3, 14 mol% ZnO, 8 mol% Li2O, 5 mol% ZrO2, 3 mol% Lu2O3, 0.05 mol% Er2O3, and also contain 0.3 mol% Sb2O3. The AP glass was heat-treated at 760°C for 6 hours. A is 0.28%K -1 S R is 1.20%K -1 That was the case. Although preferred specific embodiments of the present invention have been described in detail above, a person skilled in the art can make many modifications and changes based on the concept of the present invention without performing any creative work. Therefore, any technical solutions obtained by a person skilled in the art through logical analysis, reasoning, or limited experimentation based on the concept of the present invention and the prior art should fall within the scope of protection defined in the claims of the present invention.

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