Rare earth ion doped high-purity quartz, its preparation method and application

Abstract

The application relates to the technical field of quartz preparation, in particular to rare earth ion doped high-purity quartz and a preparation method and application thereof. The preparation method comprises the following steps: S1, uniformly mixing organic amine, ultrapure water, high-purity silicon sol or silane or orthosilicate and a rare earth salt; S2, performing hydrothermal reaction on the mixed solution in a continuous stirring reaction kettle under the condition of 1-30 MPa pressure and 100-350 DEG C reaction temperature for 10-200 hours, and the stirring speed is 10-1000 r / min; S3, performing gravity sedimentation or centrifugal separation on the mixed solution to obtain a precipitate; and washing and drying the precipitate to obtain the rare earth ion doped high-purity quartz. In the application, the in-situ introduction of rare earth ions is realized in the quartz crystal formation process, the rare earth ions can enter the crystal lattice in the form of solid solution or interstitial in the quartz nucleation and growth process, are uniformly distributed in the particle interior, the quartz particle is prepared into a nano structure with good dispersity by adjusting the type and doping concentration of the rare earth ions, and the optical, electrical and sensing performance of the quartz material can be adjusted.

Description

Technical Field

[0001] This invention relates to the field of quartz preparation technology, and in particular to a rare earth ion-doped high-purity quartz, its preparation method, and its application. Background Technology

[0002] Quartz has enormous industrial demand and is widely used in fields such as biosensors, thin film materials, photonic crystals, and semiconductor adsorbents. Currently, the global supply of high-quality quartz raw materials remains tight. Against this backdrop, processing and purifying silicon-based materials and doping them with rare earth ions to meet application standards is of significant practical importance for alleviating resource pressure, reducing production costs, and promoting sustainable development.

[0003] Rare earth ions are characterized by their narrow spectral lines, stable wavelengths, abundant energy levels, minimal influence from the matrix, and extremely strong optical properties, making them ideal doping ions for achieving multifunctionality in quartz. The unique advantage of matching rare earth metal ions with quartz lies in their ionic radius and similarity to Si. 4+ With good matching, rare earth ions can be used to partially replace or enter the interstitial spaces of the quartz network, retaining its low thermal expansion, high transparency, and high stability. Furthermore, rare earth metal ions have minimal impact on the quartz structure, strong 4f orbital shielding, and weak interaction with the matrix. After doping, the quartz retains high light transmittance with minimal decrease in thermal and mechanical properties. It can also significantly enhance quartz functions such as laser gain, UV absorption, radiation resistance, and magnetic field sensing. By doping luminescent rare earth ions into quartz under hydrothermal conditions, the rare earth ions synergistically participate in the quartz growth process with the silicon source, being introduced during its nucleation and growth stages. This achieves lattice solid solution or interstitial doping of rare earth ions, thereby realizing its unique optical properties. Rare earth ion-doped nano-quartz has significant application potential in catalysis, nanosensors, gene delivery, and luminescent materials.

[0004] Traditional rare earth ion doping processes for amorphous silica are prepared in high-temperature and high-pressure plasma, but they still have core drawbacks, such as limited solubility, poor uniformity, high energy consumption and cost of high-temperature and high-pressure processes, products that are prone to being in a glassy and amorphous state with defects and poor stability, disordered positions and uneven diffusion of doped rare earth ions, difficulty in directly forming silica, and the need for high-temperature crystal transformation, etc., which pose significant environmental and safety risks and directly restrict product performance and large-scale application. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of the prior art by proposing a rare earth ion-doped high-purity quartz, its preparation method, and its application.

[0006] The first objective of this invention is to provide a method for preparing rare-earth ion-doped high-purity quartz, comprising the following steps: S1, uniformly mix organic amine, ultrapure water, high-purity silica sol or silane or orthosilicate and rare earth salt; S2, the mixed solution is subjected to hydrothermal reaction in a continuously stirred reactor at a reaction temperature of 100-350 ℃ and a pressure of 1-30 MPa for 10-200 hours, with a stirring speed of 10-1000 r / min; S3, the mixed solution is separated by gravity sedimentation or centrifugation to obtain a precipitate; the precipitate is washed and dried to obtain rare earth ion-doped high-purity quartz.

[0007] Further, the mixed solution comprises, by weight percentage, 10-60 parts of high-purity silica sol or silane or orthosilicate, 10-60 parts of organic amine, rare earth salt at 0.01-50 wt% relative to the mass of the silicon source, and the remainder of ultrapure water, totaling 100 parts.

[0008] Furthermore, the reaction temperature is 150–300 °C, the pressure is 4–10 MPa, the stirring speed is 50–500 r / min, and the reaction time is 10–180 hours.

[0009] Further, in step S1, the organic amine is one or more of ethylenediamine, ethanolamine, diethanolamine, triethanolamine, tri(2-ethylhexyl)amine, tri-n-octylamine, tridecylamine, and triisotridecylamine; The silane is one or more of methylsilane, ethylsilane, propane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, trimethylfluorosilane, and methyldibromosilane, and the orthosilicate is methyl orthosilicate (TMOS) or ethyl orthosilicate (TEOS).

[0010] Furthermore, rare earth salts are inorganic or organic salts of rare earth metals; wherein the rare earth metal elements are lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, or yttrium.

[0011] Furthermore, the rare earth salt is one or more of the following: nitrate, chloride, oxalate, acetate, and acetylacetone salt; Wash away residual alkali and salt with deionized water; dry the precipitate after washing at 100-200 ℃.

[0012] Furthermore, rare earth ions are introduced in situ during the nucleation and growth of quartz, allowing them to enter the quartz crystal structure in the form of lattice solid solution or interstitial space.

[0013] Furthermore, R60702 pure zirconium or Ta1 high-purity tantalum are used as materials for the continuous stirred reactor.

[0014] Compared to existing technologies where reactors often use ordinary stainless steel or polymer linings, which are prone to corrosion, heavy metal precipitation, and rare earth ion adsorption under high-temperature hydrothermal rare earth systems, resulting in uneven doping, low purity, and poor performance, thus affecting the optical and structural stability of rare earth ion-doped quartz, this invention uses R60702 pure zirconium or Ta1 high-purity tantalum as the material for a continuous stirred reactor. These materials exhibit extreme chemical inertness to rare earth ions such as lanthanum, cerium, neodymium, and holmium, and do not adsorb, complex, or chemically react with rare earth components under high-temperature hydrothermal conditions. No heavy metal impurities such as iron, chromium, nickel, and niobium are dissolved, effectively avoiding rare earth ion loss and crystal contamination. The material possesses excellent high-temperature strength, creep resistance, and hydrothermal stability, exhibiting no corrosion, leakage, or deformation under long-term operation. This ensures uniform rare earth ion-doped quartz with high purity, stable optical performance, and good batch repeatability, solving the technical bottlenecks of rare earth ion adsorption, impurity contamination, and equipment failure associated with traditional materials.

[0015] A second objective of this invention is to provide a rare-earth ion-doped high-purity quartz prepared using the above-described preparation method.

[0016] Furthermore, the mass fraction of rare earth ions is from 100 ppm to 8%.

[0017] A third objective of this invention is to provide an application of rare-earth ion-doped high-purity quartz as described above, characterized in that it is used as a dielectric material.

[0018] Compared with the prior art, the beneficial effects of the present invention include: Compared to the structural disorder and extremely high energy consumption problems caused by the traditional high-temperature melting (>1700 ℃) process for preparing silicon dioxide, this invention adopts a medium-temperature and medium-pressure hydrothermal method to directly generate quartz crystals. During the crystal growth process, rare earth ions are simultaneously doped, which avoids the problems of difficult and few quartz nucleation, severe crystal agglomeration, and irregular shape. This invention produces crystalline rather than glassy quartz, which effectively reduces production costs and improves process safety.

[0019] This invention achieves in-situ introduction of rare earth ions during the formation of quartz crystals, enabling rare earth ions to enter the crystal lattice in solid solution or interstitial form during quartz nucleation and growth, and to be uniformly distributed within the particles. This avoids the problems of rare earth ion enrichment, uneven distribution, and phase separation that exist in traditional methods that first generate silicon dioxide and then dope it with rare earth ions. At the same time, rare earth ion doping can reduce the concentration of non-bridged oxygen bonds and fill the space of the quartz network. The product can effectively reduce polarization loss when used as a dielectric material. After the product is modified with LCP, PPS, and PBT, the dielectric loss factor and dielectric constant are effectively reduced, which is far superior to existing technology products.

[0020] The organic amine of this invention can regulate the state and dispersion of rare earth ions through complexation, thereby promoting their uniform introduction during crystal formation. Both can also regulate the hydrolysis, condensation, and crystallization processes of the silicon source, transforming the system from producing amorphous silica using traditional methods to directly producing crystalline quartz. Simultaneously, it achieves synchronous doping of rare earth ions, effectively avoiding the problem of uncontrolled doping caused by additional high-temperature crystal transformation in traditional processes. By controlling the type and concentration of rare earth ions, well-dispersed nanostructured quartz particles are obtained, enabling the controllability of the optical, electrical, and sensing properties of quartz materials. Attached Figure Description

[0021] Figure 1 This is the XRD pattern of the La-doped quartz prepared in Example 1 of this invention; Figure 2 This is a SEM image of the La-doped quartz prepared in Example 1 of this invention; Figure 3 This is an EDS image of the Gd-doped quartz prepared in Example 2 of this invention; Figure 4 This is an EDS image of the Tm-doped quartz prepared in Example 3 of this invention; Figure 5 These are the UV-Vis absorption spectra of Sm-doped quartz in Example 4 of the present invention and pure quartz in Comparative Example 2. Figure 6 This is the EDS image of the Ho-doped quartz prepared in Example 5 of this invention; Figure 7 This is the XRD pattern of Ho-doped amorphous quartz prepared in Comparative Example 1. Figure 8 This is the EDS image of the Ho-doped amorphous quartz prepared in Comparative Example 1. Figure 9 This is a SEM image of the quartz prepared in Comparative Example 1. Detailed Implementation

[0022] The following are specific embodiments of the present invention, which are described in conjunction with the accompanying drawings to further illustrate the technical solutions of the present invention. However, the present invention is not limited to these embodiments.

[0023] Example 1 Place 48.46 g of ethylenediamine into a beaker, and add 1.95 g of rare earth salt La(NO3)3 while stirring. In a 6H₂O mixture, stir at room temperature for 30–60 min until the solid is completely dissolved, yielding a transparent, light yellow complex solution. Slowly add 42 g of tetraethyl orthosilicate (TEOS), and the remainder is added with ultrapure water, resulting in a total mixed solution mass of 100 g. Mix thoroughly. Then, pour this mixture into a zirconium hydrothermal reactor, heat to 220 °C, maintain a pressure of 2–3.4 MPa, and stir at 300 r / min for 150 h. After cooling, centrifuge to settle, wash twice with deionized water, dry at 100 °C, and collect.

[0024] The product after hydrothermal synthesis is high-purity quartz. After centrifugation, washing with deionized water, and drying, the resulting powder sample showed quartz diffraction peaks under XRD. Figure 1 ICP-MS analysis showed that the purity of quartz and crystalline quartz were both higher than 99.9999%.

[0025] EDS analysis of the La-doped quartz prepared in Example 1 showed a La content of 4.2% (wt%). The rare earth element La was synchronously distributed with the silicon-oxygen support, exhibiting uniform doping and highly overlapping mapping, confirming that the preparation method of this invention can achieve uniform composite doping of rare earth elements and silicon-oxygen supports. (Mapping only shows elemental distribution, not the microstructure of individual particles; the rounded outline of the agglomerates is the overall shape formed by the aggregation and stacking of a large number of nanoparticles, not the shape of a single particle itself.)

[0026] Microscopic morphological observation shows that, Figure 2 The main particles of the sample have a nearly round appearance, most of the particles are independently distributed, only a small number of particles are slightly adhered, there is no large-scale agglomeration, the overall particle size distribution range is narrow, the particle size uniformity is good, and the particle size is about 10 μm.

[0027] In Example 1 of this invention, rare earth La-doped quartz was used to modify LCP, PPS, and PBT, and the dielectric constant (D) at 10 GHz was improved. k ) and dielectric loss factor (D f As shown in Table 1 below, the dielectric constant (D) of the material is significantly reduced. k ) and dielectric loss factor (D f ).

[0028] LCP system D k Decreased to 2.4-2.6, D f Reduced to 0.0011-0.002; PPS system D k Decreased to 2.5–2.9, D f <0.005; PBT system D k Decreased to 2.7–3.0, D f<0.019. Rare-earth La-doped quartz suppresses interfacial polarization and molecular chain movement, improving the high-frequency stability and thermal stability of dielectric properties over a wide temperature range ( 30℃~150℃) within D k / D f With low fluctuations, it can be applied to the manufacturing of 5G / 6G millimeter-wave communication, radio frequency modules and high-speed connectors. The dielectric material has low loss and high stability.

[0029] Table 1

[0030] Example 2 46.15 g of ethanolamine was placed in a beaker, and 4 g of rare earth salt Gd(NO3)3·6H2O was added with stirring. The mixture was stirred at room temperature for 30–60 min until the solid was completely dissolved, yielding a transparent, light yellow complex solution. 40 g of methyl orthosilicate was slowly added dropwise, with the remainder added as ultrapure water. The total mass of the mixed solution was 100 g, and the mixture was thoroughly mixed. This mixture was then poured into a zirconium hydrothermal reactor, heated to 220 °C, maintained at a pressure of 2–3.4 MPa, and stirred at a stirring speed of 300 r / min for 180 h. After cooling, the mixture was centrifuged to settle, washed twice with deionized water, dried at 100 °C, and collected.

[0031] The product after hydrothermal synthesis is high-purity quartz. After centrifugation, washing with deionized water and drying, the powder sample showed quartz diffraction peaks under XRD. The purity of quartz was determined by ICP-MS and chemical element analysis. The purity of crystalline quartz was higher than 99.9999%.

[0032] Figure 3 The EDS diagram shows that it contains 7.0% (wt%) Gd, and the Gd element is uniformly distributed in the silicon-oxygen aggregate phase. It has a high degree of matching with the distribution of matrix elements and excellent uniformity of rare earth Gd doping. This confirms that the preparation method of the present invention can achieve uniform composite doping of rare earth elements and silicon-oxygen carrier.

[0033] Example 3 34.61 g of triethanolamine was placed in a beaker, and 1.79 g of rare earth salt Tm(NO3)3·3H2O was added with stirring. The mixture was stirred at room temperature for 30–60 min until the solid was completely dissolved, yielding a transparent, light yellow complex solution. 30 g of tetraethyl orthosilicate was slowly added dropwise, with the remainder added as ultrapure water. The total mass of the mixed solution was 100 g, and the mixture was thoroughly mixed. This mixture was then poured into a tantalum hydrothermal reactor, heated to 220 °C, maintained at a pressure of 2–3.4 MPa, and stirred at a stirring speed of 350 r / min for 140 h. After cooling, the mixture was centrifuged to settle, washed twice with deionized water, dried at 100 °C, and collected.

[0034] The product after hydrothermal synthesis is high-purity quartz. After centrifugation, washing with deionized water and drying, the powder sample showed quartz diffraction peaks under XRD. The purity of quartz was determined by ICP-MS and chemical element analysis. The purity of crystalline quartz was higher than 99.9999%.

[0035] Figure 4 The EDS diagram shows that it contains 6.9% (wt%) of Tm, and the Tm element is uniformly distributed in the silicon-oxygen aggregate phase. It has a high degree of matching with the distribution of matrix elements and excellent uniformity of rare earth Tm doping. This confirms that the preparation method of the present invention can achieve uniform composite doping of rare earth elements and silicon-oxygen support.

[0036] Example 4 40.23 g of ethylenediamine was placed in a beaker, and 3 g of rare earth salt Sm(NO3)3·6H2O was added with stirring. The mixture was stirred at room temperature for 30–60 min until the solid was completely dissolved, yielding a transparent, light yellow complex solution. 34.87 g of tetraethyl orthosilicate was slowly added dropwise, with the remainder added as ultrapure water. The total mass of the mixed solution was 100 g, and the mixture was thoroughly mixed. This mixture was then poured into a zirconium hydrothermal reactor, heated to 220 °C, maintained at a pressure of 2–3.4 MPa, and stirred at a stirring speed of 300 r / min for 150 h. After cooling, the mixture was centrifuged to settle, washed twice with deionized water, dried at 100 °C, and collected.

[0037] The product after hydrothermal synthesis is high-purity quartz. After centrifugation, washing with deionized water and drying, the powder sample showed quartz diffraction peaks under XRD. The purity of quartz was determined by ICP-MS and chemical element analysis. The purity of crystalline quartz was higher than 99.9999%.

[0038] EDS showed that it contained 7.9% (wt%) of Sm. The Sm element was uniformly distributed in the silicon-oxygen aggregate phase, with a high degree of matching with the matrix element distribution. The uniformity of rare earth Sm doping was excellent, which confirmed that the preparation method of the present invention can achieve uniform composite doping of rare earth elements and silicon-oxygen carrier.

[0039] like Figure 5 As shown, UV-Vis absorption spectra of Sm-doped quartz (red line) in Example 4 and pure quartz (black line) in Comparative Example 2 were measured in the range of 280–800 nm. The sample in Example 4 showed Sm³⁺ in the range of 300–360 nm. +The strong and broad absorption peak of charge transfer confirms the effective doping of Sm ions; the absorption in the 400~800 nm visible light region is gradually attenuated, exhibiting strong ultraviolet absorption and high visible light transmittance. In contrast, the pure quartz in Comparative Example 2 has no characteristic absorption peaks across the entire wavelength range, only an intrinsic absorption tail caused by lattice defects and trace impurities that increases with wavelength shortening. It has no wavelength-selective absorption capability and can only be used as a light-transmitting substrate, unable to achieve ultraviolet light control function. Therefore, the Sm-doped quartz prepared in Example 4 exhibits strong absorption in the near-ultraviolet band, which can achieve selective capture and control of ultraviolet light, while retaining the excellent optical, thermal, and chemical stability properties of quartz materials, greatly expanding the high-frequency, low-loss application scenarios such as ultraviolet laser sensors, fluorescent luminescent materials, optical fiber communication, and radio frequency optical transmission.

[0040] Example 5 39.15 g of tri-n-octylamine was placed in a beaker, and 3 g of rare earth salt Ho(NO3)3·6H2O was added with stirring. The mixture was stirred at room temperature for 30–60 min until the solid was completely dissolved, yielding a transparent, light yellow complex solution. 33.95 g of methyl orthosilicate was slowly added dropwise, with the remainder added as ultrapure water. The total mass of the mixed solution was 100 g, and the mixture was thoroughly mixed. This mixture was then poured into a tantalum hydrothermal reactor, heated to 250 °C, maintained at a pressure of 2–3.4 MPa, and stirred at a stirring speed of 400 r / min for 120 h. After cooling, the mixture was centrifuged to settle, washed twice with deionized water, dried at 100 °C, and collected.

[0041] The product after hydrothermal synthesis is high-purity quartz. After centrifugation, washing with deionized water and drying, the powder sample showed quartz diffraction peaks under XRD. The purity of quartz was determined by ICP-MS and chemical element analysis. The purity of crystalline quartz was higher than 99.9999%.

[0042] Figure 6 The EDS plot shows that it contains 6.4% (wt%) Ho, such as Figure 5 The Ho element is uniformly distributed within the silicon-oxygen aggregate matrix, exhibiting a high degree of matching with the matrix element distribution. The uniformity of rare earth Ho doping is excellent, confirming that the preparation method of this invention can achieve uniform composite doping of rare earth elements and silicon-oxygen supports.

[0043] Comparative Example 1 39.15 g of tri-n-octylamine was placed in a beaker, and 3 g of rare earth salt Ho(NO3)3·6H2O was added with stirring. The mixture was stirred at room temperature for 30–60 min until the solid was completely dissolved, resulting in a transparent light yellow complex solution. 33.95 g of methyl orthosilicate was slowly added dropwise, with the remainder added as ultrapure water. The total mass of the mixed solution was 100 g. The mixture was stirred at room temperature for 120 h until homogeneous, with a stirring speed of 400 r / min. The mixture was placed in an evaporating dish and evaporated in a water bath at 100 ℃ until completely dry, yielding a solid precursor. This precursor was then transferred to a crucible and placed in a high-temperature muffle furnace. The temperature was gradually increased to 1650 ℃ and sintered at this temperature for 4 h, during which a normal atmospheric pressure environment was naturally formed without stirring. After sintering, the mixture was cooled to room temperature with the furnace. The sintered block product was then crushed and ground to obtain a powder sample. The powder sample was washed twice with deionized water, dried at 100 ℃, and collected.

[0044] XRD patterns show that the characteristic diffraction peaks of quartz are weak in intensity and broadened in shape, such as Figure 7 Unlike the clear quartz diffraction peaks of Example 5, chemical elemental analysis by ICP-MS showed that the purity of the quartz powder was only 99.5%, far lower than the 99.9999% of Example 5. EDS showed low and uneven Ho doping, with the silica-oxygen matrix exhibiting a continuous flocculent stacked agglomerate structure. Ho was only detected as a trace discrete signal at the edge of the field of view, indicating that it could hardly be uniformly incorporated into the silica-oxygen matrix. The rare earth components showed extremely poor compatibility with the silica-oxygen matrix. Figure 8 The Ho element content is only 2.1% (wt%), which is much lower than the 6.4% in Example 5.

[0045] Microscopic morphology observation of Comparative Example 1 shows that... Figure 9 The powder has a high degree of micro-agglomeration, with fine particles sintering and sticking together to form irregular agglomerates. The particles have a messy and irregular shape, a wide particle size distribution, extremely poor dispersibility, and a large difference in particle size. Compared to the comparative example, the SEM images of the sample in Example 1 of this invention show that most particles can be separated from each other, with only a small number of particles slightly adhering in certain areas. The particles have a nearly circular outer contour, and the overall size range is concentrated and the uniformity is significantly improved.

[0046] In Comparative Example 1, defects such as porosity, crystallization, and microcracks are easily generated during high-temperature sintering, leading to a decrease in the light transmittance of the powder. The traditional melting method requires heating to 1650 ℃ and holding for 4 h, which consumes more than 8 times the energy of Example 5 (250 ℃, constant temperature for 120 h). The additional crushing and grinding steps make the process cumbersome and the production cycle long. Moreover, new impurities are easily introduced during the grinding process, resulting in a yield of only 65%, far lower than the more than 98% of Example 5. This makes large-scale production difficult and costly.

[0047] Comparative Example 1 uses a traditional high-temperature melting process, which has many drawbacks such as low purity, excessive impurities, low and uneven distribution of rare earth ion doping, particle agglomeration, many crystal defects, high energy consumption, and poor stability, fully demonstrating the limitations of traditional quartz doping rare earth ion processes. In contrast, the hydrothermal synthesis process in Examples 1-5 can achieve the preparation of high-purity, high-doping, and well-dispersed rare earth ion-doped quartz powder under mild conditions, effectively solving all the pain points of traditional processes, and its comprehensive performance is far superior to that of traditional processes.

[0048] Comparative Example 2 48.46 g of ethylenediamine was placed in a beaker, and 42 g of tetraethyl orthosilicate was slowly added dropwise with stirring. The remainder was added with ultrapure water, bringing the total mass of the mixed solution to 100 g. The mixture was then thoroughly mixed. This solution was poured into a zirconium hydrothermal reactor, heated to 220 °C, maintained at a pressure of 2–3.4 MPa, and stirred at 300 r / min for 150 h. After cooling, the mixture was centrifuged to allow sedimentation, washed twice with deionized water, and dried at 100 °C for collection.

[0049] Rare earth La-doped quartz powder prepared in Example 1 and pure quartz powder without rare earth doping in Comparative Example 2 were filled with modified LCP, PPS, and PBT matrix resins in equal amounts. The dielectric constant Dk and dielectric loss Df of the composite materials were tested at 10 GHz. The test data are shown in Table 1 (after Example 1) and Table 2.

[0050] Table 2

[0051] Table 2 shows that the reduction in Dk and Df is limited in the modified system filled only with pure quartz; the highest Dk is only 3.43% and the highest Df is only 16.7%, which is much smaller than the reduction in Dk of the three types of resin composites after La-doped quartz modification in Table 1, which is 14.3%~23.1% and the reduction in Df is over 26.6%. Among them, the dielectric loss of PPS and PBT systems is reduced by more than 36.6%.

[0052] Compared to the pure quartz filler in Comparative Example 2, the La-doped modified quartz in Example 1 can significantly weaken the polarization effect of the resin matrix and simultaneously achieve optimization of low dielectric and low loss. The resulting modified resin can be used in fields such as 5G / 6G high-frequency and high-speed circuit boards and millimeter-wave communication insulating substrates.

[0053] For any points not covered above, existing technologies shall apply.

[0054] Although specific embodiments of the present invention have been described in detail by way of examples, those skilled in the art should understand that the above examples are for illustrative purposes only and are not intended to limit the scope of the invention. Those skilled in the art can make various modifications or additions to the described specific embodiments or use similar methods to replace them, without departing from the direction of the invention or exceeding the scope defined by the appended claims. Those skilled in the art should understand that any modifications, equivalent substitutions, improvements, etc., made to the above embodiments based on the technical essence of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing rare earth ion-doped high-purity quartz, characterized in that, Includes the following steps: S1, uniformly mix organic amine, ultrapure water, high-purity silica sol or silane or orthosilicate and rare earth salt; S2, the mixed solution is subjected to hydrothermal reaction in a continuously stirred reactor at a reaction temperature of 100-350 ℃ and a pressure of 1-30 MPa for 10-200 hours, with a stirring speed of 10-1000 r / min; S3, the mixed solution is separated by gravity sedimentation or centrifugation to obtain a precipitate; the precipitate is washed and dried to obtain rare earth ion-doped high-purity quartz.

2. The preparation method according to claim 1, characterized in that, The mixed solution comprises, by weight percentage, 10-60 parts of high-purity silica sol or silane or orthosilicate, 10-60 parts of organic amine, rare earth salt at 0.01-50 wt% relative to the mass of the silicon source, and the remainder of ultrapure water, totaling 100 parts.

3. The preparation method according to claim 1, characterized in that, The reaction temperature is 150–300 °C, the pressure is 4–10 MPa, the stirring speed is 50–500 r / min, and the reaction time is 10–180 hours.

4. The preparation method according to claim 1, characterized in that, In step S1, the organic amine is one or more of ethylenediamine, ethanolamine, diethanolamine, triethanolamine, tri(2-ethylhexyl)amine, tri-n-octylamine, tridecylamine, and triisotridecylamine; The silane is one or more of methylsilane, disilane, propane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, trimethylfluorosilane, and methyldibromosilane, and the orthosilicate is methyl orthosilicate or ethyl orthosilicate.

5. The preparation method according to claim 1, characterized in that, Rare earth salts are inorganic or organic salts of rare earth metals; among which the rare earth metal elements are lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, or yttrium.

6. The preparation method according to claim 1, characterized in that, Rare earth salts are one or more of nitrates, chlorides, oxalates, acetates, and acetylacetones; Wash away residual alkali and salt with deionized water; dry the precipitate after washing at 100-200 ℃.

7. The preparation method according to claim 1, characterized in that, In-situ introduction of rare earth ions is achieved during the nucleation and growth of quartz, allowing rare earth ions to enter the quartz crystal structure in the form of lattice solid solution or interstitial space.

8. A rare earth ion-doped high-purity quartz prepared by the preparation method according to any one of claims 1-7.

9. The rare earth ion-doped high-purity quartz as described in claim 8, characterized in that, The mass fraction of rare earth ions ranges from 100 ppm to 8%.

10. An application of rare earth ion-doped high-purity quartz as described in claim 8, characterized in that, Used as a dielectric material.

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