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CN-121974562-A - Rare earth doped optical glass ink, additive manufacturing method thereof and optical glass

CN121974562ACN 121974562 ACN121974562 ACN 121974562ACN-121974562-A

Abstract

The invention discloses rare earth doped multi-component optical glass ink, an additive manufacturing method thereof and optical glass. The ink is prepared from raw materials such as metal salt containing rare earth metal salt, precursor compound, deionized water, photo-curing monomer, photoinitiator and the like by a sol-gel process, so that in-situ uniform doping of rare earth ions on a molecular level is realized. The ink can be molded into gel blanks with complex structures through a photocuring 3D printing technology, and then the gel blanks are dried, sintered and annealed to finally obtain the high-performance rare earth doped multi-component optical glass. The method breaks through the limitations of the traditional high-temperature melting method and the existing second phase doping additive manufacturing technology, realizes the organic combination of the device with the complex structure and the molecular level uniform doping and low-temperature preparation, and has wide application prospect in the fields of micro lasers, integrated optical devices and the like.

Inventors

  • LI BEINING
  • HU LILI
  • YU CHUNLEI
  • CHEN SHUBIN
  • WANG XIN

Assignees

  • 中国科学院上海光学精密机械研究所

Dates

Publication Date
20260505
Application Date
20260120

Claims (17)

  1. 1. A rare earth doped multi-component optical glass ink is characterized in that the visible light range transmittance of the ink The ink is prepared from raw materials including a precursor compound, metal salt, deionized water, a photo-curing monomer and a photoinitiator by a method comprising the following steps: S1, selecting metal salt, deionized water, a photo-curing monomer, a photo-initiator and a precursor compound according to the mass ratio of (10-70): (30-100): (1-20): (0.1-1): 100 respectively; s2, regulating the pH value of the deionized water to 2-6 by using a pH regulator to obtain hydrolysate; s3, adding the precursor compound into the hydrolysate, and stirring until the precursor compound fully reacts to obtain transparent sol; S4, adding the metal salt into the transparent sol, and fully stirring, dissolving and chelating to obtain transparent doped sol; And S5, mixing the photo-curing monomer and the photoinitiator, adding the mixture into the transparent doped sol, and uniformly stirring to obtain the ink.
  2. 2. The rare earth doped multi-component optical glass ink according to claim 1, wherein said steps of In S2, the pH regulator adopts one or more of hydrochloric acid, nitric acid, acetic acid, phosphoric acid, sulfuric acid, ammonium acetate, potassium hydrogen phthalate, sodium hydrogen phosphate, monoammonium phosphate, carbonic acid and sodium bicarbonate.
  3. 3. The rare earth doped multi-component optical glass ink according to claim 1, wherein said front side The precursor compound is one or more selected from ethyl orthosilicate, methyl orthosilicate, tetrabutyl titanate, isopropyl titanate, aluminum isopropoxide, trimethyl borate, triethyl borate and trimethyl phosphate.
  4. 4. The rare earth doped multi-component optical glass ink according to claim 1, wherein said gold The salt is one or more selected from aluminum lactate, calcium lactate, aluminum acetate, erbium acetate, aluminum nitrate, erbium nitrate, ytterbium nitrate, europium nitrate, aluminum chloride, ytterbium chloride, erbium chloride, neodymium chloride and erbium iodide.
  5. 5. The rare earth doped multi-component optical glass ink according to claim 1, wherein said light The curing monomer is one or more selected from 3-acryloxypropyl trimethoxy silane, butenoic acid, acrylic acid, ethoxylated trimethylolpropane triacrylate and trimethylolpropane triacrylate.
  6. 6. The rare earth doped multi-component optical glass ink according to claim 1, wherein said light The initiator is one or more selected from TPO, TPO-L, diacylphosphine oxide 819, omnirad, 184 and Pasteur 651.
  7. 7. The rare earth doped multi-component optical glass ink according to claim 1, wherein said steps are Stirring in the steps S3-S5 is one of the following two ways: a) Stirring in an ultrasonic environment, wherein the ultrasonic frequency is 1-120 kHz, and the stirring speed is 500-2000 r/min; b) Stirring is carried out in an ultrasonic-free environment, and the stirring speed is 500-2000 r/min.
  8. 8. Use of an ink according to any one of claims 1 to 7 for augmentation by photo-curing The rare earth doped multi-component optical glass is prepared by the material manufacturing technology.
  9. 9. Manufacturing of rare earth doped multicomponent optical glass using the ink additive of any one of claims 1-7 The method is characterized by comprising the following steps: (1) After a 3D model is established and sliced by using 3D modeling software, placing the ink into a 3D printer material box for photo-curing 3D printing to obtain a gel blank; (2) Drying the gel blank to obtain a dried body; (3) The rare earth doped multi-component optical glass is obtained after the drying body is sintered and annealed, the rare earth doped multi-component optical glass is thin The highest sintering temperature of the soil doped multi-component optical glass is 700-1000 ℃.
  10. 10. A rare earth doped multi-component optical glass, which is characterized by being prepared by the method of claim 9, And the optical glass simultaneously meets the following conditions: (a) The ultraviolet-near infrared transmittance of the optical glass is more than or equal to 75%; (b) The density is more than or equal to 95 percent; (c) The total content of rare earth ions is 0.5-5.5 mol%.
  11. 11. The rare earth doped multi-component optical glass according to claim 10, wherein when co-doped Er 3+ /Yb 3+ and the total rare earth ion content is greater than 1.0 mol%, the full width at half maximum (FWHM) of the fluorescence emission peak at 1540nm is not greater than 50 nm.
  12. 12. The method for preparing rare earth doped multi-component optical glass according to claim 9, wherein the steps are In the step (1), the wavelength of the light source used for the photo-curing 3D printing is less than 500 nm.
  13. 13. The method for preparing rare earth doped multi-component optical glass according to claim 9, wherein the following steps The photo-cured 3D printing is Digital Light Processing (DLP) or Stereolithography (SLA) printing.
  14. 14. The method for preparing rare earth doped multi-component optical glass according to claim 9, wherein the steps are In the step (2), the drying process is that the temperature is raised from room temperature to 100-200 ℃ at a temperature raising rate of 0.1-5 ℃ per minute, the temperature is kept for 6 hours at 30 ℃, and then the temperature is kept for 6 hours every 10 ℃ raising time.
  15. 15. The method for preparing rare earth doped multi-component optical glass according to claim 9, wherein the steps are In step (3), the inorganic content of the dried body after sintering at a temperature of more than 700 ℃ is more than 50wt%.
  16. 16. The method for preparing rare earth doped multi-component optical glass according to claim 9, wherein the steps are In the step (3), the sintering process is that the temperature is raised to 150-200 ℃ at the rate of 0.1-5 ℃ per minute for 6-10 hours, then raised to 400-600 ℃ at the rate of 0.1-5 ℃ per minute and kept for 2-10 hours, and then raised to 700-1000 ℃ at the rate of 0.1-5 ℃ per minute and kept for 1-6 hours.
  17. 17. The method for preparing rare earth doped multi-component optical glass according to claim 9, wherein the steps are In the step (3), the annealing process is that the temperature is raised to 600-800 ℃ from room temperature at 2-10 ℃ per minute under the air condition, and the temperature is kept for 10-30 hours.

Description

Rare earth doped optical glass ink, additive manufacturing method thereof and optical glass Technical Field The invention relates to the technical field of inorganic optical material preparation, in particular to rare earth doped multi-component optical glass ink, an additive manufacturing method thereof and optical glass prepared by the method. Background The rare earth doped optical glass is a core material of photonic devices such as a laser, an optical fiber amplifier, an optical sensor and the like. At present, although bulk glass and optical fibers can be prepared by a high-temperature melting method, three inherent defects exist, namely, the high temperature causes rare earth ions to be agglomerated to form clusters to trigger a concentration quenching effect, so that concentration doping is low, the mold forming is difficult to manufacture a device with a complex structure such as a three-dimensional integrated microwave waveguide, an internal cavity and the like, and the process has high energy consumption and rare earth is easy to volatilize at high temperature. To break through the structural limitations, additive manufacturing techniques have been introduced into the field of glass manufacturing. Among them, the prior art is mainly divided into two paths, one is a nanoparticle-based ink system, for example, the chinese patent literature (CN 118754424 a) is to physically mix glass powder with photosensitive resin, and sinter the mixture at high temperature after photo-curing and molding. However, the vitrification process in this approach still relies on high temperature (> 1300 ℃) reactions, limiting its use in precision optics. Secondly, the sol-gel photo-curing technology shows unique advantages, such as the scheme disclosed in China patent document (CN 116874182A) that siloxane oligomer is formed by hydrolyzing alkoxy silane, DLP printing is carried out by matching photosensitive resin, and then the nano-pore aluminosilicate glass is obtained through drying and sintering. The method utilizes sol-gel reaction to construct a silica network at molecular scale, and the glass forming temperature is obviously reduced. However, this technique employs a "first-formed-then-dip" secondary rare earth doping process, i.e., a mesoporous glass body is first prepared, and then a rare earth salt solution is introduced into the mesoporous channels by dipping. The physical adsorption mode causes weak binding force between rare earth ions and a glass network, and the rare earth ions are easy to migrate, agglomerate or volatilize in the high-temperature treatment process, and in addition, the rare earth ions are attached to the surface of the mesoporous through physical adsorption, and are easy to separate out or migrate and agglomerate from a pore canal in the subsequent high-temperature treatment process, so that the doping uniformity is poor. The existing additive manufacturing technology can not solve the problem of molecular-level in-situ doping of rare earth ions in a glass matrix. Both the "post-dipping" mode disclosed in the chinese patent literature (CN 111018321 a) and the "physical mixing" mode disclosed in the chinese patent literature (CN 118754424A) lead to insufficient uniformity of rare earth ion dispersion, and the limitation of the system components is large, which makes it difficult to satisfy the requirements of complex structure formation and high quality optical performance. Therefore, developing an in-situ doped additive manufacturing technology which can realize uniform dispersion of rare earth ion molecular level in a sol stage and is compatible with a multi-component system becomes a key to be broken through in the field. Disclosure of Invention The invention aims to break through the bottleneck of the prior art, and provides an additive manufacturing technology which can realize the in-situ uniform doping of rare earth ion molecular level at the ink level and synchronously finish the formation of a complex three-dimensional structure, thereby fundamentally avoiding the dependence on a second phase doping path. The core of the invention is to develop rare earth doped multi-component optical glass ink special for photo-curing additive manufacturing and a 3D printing forming and sintering process matched with the rare earth doped multi-component optical glass ink. According to the scheme, through sol-gel chemistry designed at a molecular level, in-situ uniform doping of rare earth ions in a glass network precursor is realized in an ink preparation stage, so that a brand new material platform is provided for directly manufacturing an optical function device with a complex three-dimensional structure. In order to achieve the above object, the specific solution is as follows: in a first aspect, the present invention provides a rare earth doped multi-component optical glass ink. The ink is characterized by excellent comprehensive properties of high transmittance (more than or equal to 77 perc