WO2024098451A1 - Lanthanide-series perovskite ceramic-based light absorber, and use thereof and preparation method therefor - Google Patents

Lanthanide-series perovskite ceramic-based light absorber, and use thereof and preparation method therefor Download PDF

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WO2024098451A1
WO2024098451A1 PCT/CN2022/132885 CN2022132885W WO2024098451A1 WO 2024098451 A1 WO2024098451 A1 WO 2024098451A1 CN 2022132885 W CN2022132885 W CN 2022132885W WO 2024098451 A1 WO2024098451 A1 WO 2024098451A1
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ceramic
layer
doped lanthanum
barium
light absorber
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French (fr)
Chinese (zh)
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刘桂武
侯海港
刘军林
乔冠军
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微集电科技(苏州)有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G37/00—Compounds of chromium
    • C01G37/14—Chromates; Bichromates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses

Definitions

  • the present invention belongs to the field of optoelectronic technology, and in particular relates to a lanthanide perovskite ceramic-based light absorber, application of the light absorber, and a method for preparing the lanthanide perovskite ceramic-based light absorber.
  • Laser power meter also known as laser energy meter, is a measuring instrument dedicated to measuring laser energy.
  • thermopile laser power meters are mainly used for measuring high-power lasers.
  • the testing principle of this equipment is mainly to use the light absorber in its probe to absorb the light energy of the incident laser and convert the light energy into heat energy.
  • a temperature gradient field is formed in the center and both ends of the edge of the light absorber, and the thermoelectric material in the probe generates a temperature difference electromotive force, the magnitude of which depends on the magnitude of the heat energy converted by the laser. Therefore, the light absorber in the probe is the core component of the thermopile laser power meter.
  • the light absorption performance, laser damage resistance and thermal shock resistance of the light absorber will directly determine the response intensity during the measurement process of the laser energy meter, as well as the spectral width and power range of the measurable laser.
  • the light absorbing materials (including thin films and blocks) in thermopile laser power meter probes mainly include metal nanomaterials (such as gold black, silver black, iron black, etc.), carbon materials, sulfides, carbides, nitrides, optical glass, etc.
  • the light absorbing materials in a high-temperature oxygen-rich environment are mostly metal oxides and their composite oxide materials.
  • This solution of applying lanthanum manganate material to a light absorber has the advantages of simple preparation and low cost, but the light absorber prepared by this solution still has problems such as the light absorption coating being easily damaged and failing by laser, the coating being easily peeled off, and poor thermal shock resistance.
  • thermopile laser power meters In the design of thermopile laser power meters, the absorption spectrum range and light absorption rate of the light absorber are the primary performance parameters to be considered.
  • the material's weather resistance such as laser damage resistance, high temperature resistance, and thermal shock resistance, are key indicators that restrict the product's use effect and service life.
  • most of the various solutions provided by the existing technology cannot achieve a balance among the above performances at the same time. Finding a better solution and overcoming the above performance defects has become a technical problem that needs to be solved urgently by those skilled in the art.
  • the present invention provides a lanthanum manganate ceramic-based light absorber, the application of the light absorber, and a method for preparing the lanthanum manganate ceramic-based light absorber.
  • a lanthanum perovskite ceramic-based light absorber which adopts a multi-layer "sandwich" structure. According to the function, this type of multi-layer lanthanum manganate ceramic-based light absorber can be divided into: a ceramic matrix, a laser damage-resistant film, and a nano-transition layer located between the laser damage-resistant film and the ceramic matrix.
  • the ceramic matrix includes seven structural layers stacked in a preset order.
  • Each structural layer includes a porous calcium-doped lanthanum chromate ceramic layer located in the middle layer; a porous high-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the calcium-doped lanthanum chromate ceramic layer; a porous medium-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the high-barium-doped lanthanum manganate ceramic layer; and a dense low-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the medium-barium-doped lanthanum manganate ceramic layer.
  • the calcium-doped lanthanum chromate ceramic layer, the high-barium-doped lanthanum manganate ceramic layer, and the medium-barium-doped lanthanum manganate ceramic layer are porous structures.
  • the pore size in each structural layer in the ceramic matrix is distributed in a gradient decreasing state from the middle to the two sides; the thickness of each structural layer in the ceramic matrix is 0.05-0.2mm, and the total thickness is 0.5-1mm.
  • the anti-laser damage film is located on the outer surface of the calcium-doped lanthanum manganate ceramic layer in the ceramic matrix.
  • the anti-laser damage film material is alumina ceramic; the thickness of the anti-laser damage film is 50-200nm.
  • the nano transition layer is generated by high-temperature heat treatment of the ceramic matrix and the adjacent structural layers in the anti-laser damage film, and is located at the interface between the two.
  • the chemical composition of calcium-doped lanthanum chromate is: La 1- ⁇ Ca ⁇ CrO 3 , wherein ⁇ , which represents the Ca doping amount, is 0.3 to 0.7.
  • the chemical composition of low-barium-doped lanthanum manganate is: La 0.5 Ba x MnO 3 , wherein x, which represents the Ba doping amount, is 0.1 to 0.3.
  • the chemical composition of medium-barium-doped lanthanum manganate is: La 0.5 Ba y MnO 3 , wherein y, which represents the Ba doping amount, is 0.4 to 0.5.
  • the chemical composition of high-barium-doped lanthanum manganate is: La 0.5 Ba z MnO 3 , wherein z, which represents the Ba doping amount, is 0.6 to 0.7.
  • the nanometer transition layer is prepared by subjecting a ceramic substrate coated with a laser damage resistant film to a constant temperature heat treatment at a temperature of 500 to 1000° C. for 5 to 30 minutes.
  • the present invention also includes an application of the lanthanide perovskite ceramic substrate as described above, specifically: using the lanthanide perovskite ceramic substrate as a light energy absorption material in a probe of a laser energy meter to absorb ultraviolet, visible, near-infrared, mid-to-far infrared light in the 0.2-20 ⁇ m band.
  • the present invention also includes a wide-spectrum laser energy meter, in which the probe used in the laser energy meter adopts the lanthanide perovskite ceramic base as mentioned above.
  • the present invention also includes a method for preparing a lanthanide perovskite ceramic-based light absorber, which is used to prepare the lanthanide perovskite ceramic-based light absorber as described above. Specifically, the preparation method includes the following steps:
  • Lanthanum oxide, chromium oxide and calcium carbonate are mixed according to the stoichiometric ratio of La 1- ⁇ Ca ⁇ CrO 3 , solid-phase sintered, and then ball-milled and sieved to obtain calcium-doped lanthanum chromate powder; wherein ⁇ is 0.3 to 0.7.
  • (2) lanthanum oxide, manganese oxide and barium carbonate are mixed according to a preset stoichiometric ratio of La 0.5 Ba x MnO 3 , solid phase sintered, and then ball milled and sieved to obtain low-barium doped lanthanum manganate powder; wherein x is 0.1 to 0.3.
  • lanthanum oxide, manganese oxide and barium carbonate are mixed according to a preset stoichiometric ratio of La 0.5 Ba z MnO 3 , solid phase sintered, and then ball milled and sieved to obtain high-barium doped lanthanum manganate powder; wherein z is 0.6 to 0.7.
  • the four ceramic raw material powders prepared in the above step were respectively mixed with the polyvinyl alcohol solution and passed through a 200-mesh sieve to obtain four different granulated powders.
  • the pressed green body is subjected to high-temperature sintering in an argon environment to obtain a ceramic matrix with a dense surface, a porous middle, and a pore size that decreases gradually from the middle to both sides.
  • any coating process is adopted to form a uniform coating with a thickness of 50-200 nm on the surface of the calcium-doped lanthanum chromate ceramic layer on one side of the ceramic substrate.
  • the obtained uniform coating is the required anti-laser damage film.
  • the ceramic substrate containing the anti-laser damage film prepared in the above step is sent into an air furnace and heat-treated at a temperature of 500-1000°C for 5-30 minutes to form a specific nano transition layer at the interface of the anti-laser damage film and the ceramic substrate. Finally, the product is naturally cooled to room temperature to obtain the desired lanthanide perovskite ceramic-based light absorber.
  • the sintering temperature of the raw materials of each powder during solid phase sintering is 1000-1200°C, and the insulation time is 2-5h; the ball milling speed during ball milling is 300r/min, the ball-to-material weight ratio is 3:1, and the ball milling time is 24-48h.
  • the concentration of the polyvinyl alcohol solution used in the granulated powder is 5-10%, and the weight ratio of the polyvinyl alcohol solution to the ceramic powder is 1:(10-12.5).
  • the hot pressing mold is set to a pressure of 10-15 MPa and a holding time of 5-10 min.
  • the argon pressure is set to 10-20 kPa
  • the sintering temperature is 1400-1500°C
  • the sintering time is 2-4 h.
  • the selectable coating processes include vacuum evaporation, pulsed laser deposition, atomic layer deposition and magnetron sputtering technology.
  • the light absorber designed by the present invention uses a lanthanide perovskite-based ceramic material with a seven-layer structure as a ceramic matrix capable of absorbing light energy.
  • the ceramic matrix can effectively absorb various light components in the 0.2-20 ⁇ m band, and the light absorption rate in the working band exceeds 80%.
  • the special pore gradient distribution state in the ceramic matrix makes the product have super high temperature resistance and thermal shock resistance.
  • the present invention adopts dense calcium-doped lanthanum manganate ceramic as the outermost layer of the base material in the membrane-based structure, and plates a dense Al 2 O 3 film on its surface, so that the produced light absorber has both excellent wide-spectrum light absorption performance and high-temperature resistance.
  • the coating thickness of the dense Al 2 O 3 film in the present invention is 50-200nm, so that the anti-laser damage performance of the base material can be significantly improved on the basis of maintaining high transmittance.
  • the basic invention scheme selects materials for the surface layer of the ceramic substrate and the anti-laser damage film.
  • the invention also forms an ultra-thin nano transition layer at the interface between the two through a specific heat treatment temperature.
  • the produced nano transition layer significantly improves the high-temperature thermal shock resistance of the light absorber.
  • the present invention also provides a method for preparing the light absorber product of the above design.
  • the method is simple to operate, suitable for large-scale industrial production, has a high product yield, and can effectively reduce the production cost of the product.
  • FIG. 1 is a schematic diagram of various structures of a ceramic matrix and its pore distribution state in a light absorber provided in Example 1 of the present invention.
  • FIG. 2 is a scanning electron microscope photograph of the first ceramic structure layer sintered by calcium-doped lanthanum chromate in Example 1 of the present invention.
  • FIG. 3 is a scanning electron microscope photograph of the second ceramic structure layer sintered from high-barium-doped lanthanum manganate in Example 1 of the present invention.
  • FIG. 4 is a scanning electron microscope photograph of the third ceramic structure layer sintered by lanthanum manganate doped with barium in Example 1 of the present invention.
  • FIG. 5 is a scanning electron microscope photograph of the fourth ceramic structure layer sintered from low-barium-doped lanthanum manganate in Example 1 of the present invention.
  • FIG6 is a flow chart of a method for preparing a lanthanide perovskite ceramic-based light absorber provided in Example 2 of the present invention.
  • FIG. 7 shows the absorption spectra of different structural layer materials in the sample of the test example in the 0-2.5 ⁇ m band.
  • FIG. 8 shows the absorption spectra of different structural layer materials in the sample of the test example in the 2.5-20 ⁇ m band.
  • the present embodiment provides a lanthanum perovskite ceramic-based light absorber, as shown in FIG1 , which adopts a multi-layer "sandwich" structure.
  • this type of multi-layer lanthanum manganate ceramic-based light absorber can be divided into: a ceramic matrix, a laser damage-resistant film, and a nano-transition layer located between the laser damage-resistant film and the ceramic matrix.
  • the ceramic matrix includes seven structural layers stacked in sequence according to a preset order.
  • It includes a porous calcium-doped lanthanum chromate ceramic layer located in the middle layer; a porous high-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the calcium-doped lanthanum chromate ceramic layer; a porous medium-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the high-barium-doped lanthanum manganate ceramic layer; and a dense low-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the medium-barium-doped lanthanum manganate ceramic layer.
  • the thickness of each structural layer in the ceramic matrix is 0.05-0.2mm, and the total thickness is 0.5-1mm.
  • the anti-laser damage film in this embodiment is located on the outer surface of the calcium-doped lanthanum manganate ceramic layer on either side of the ceramic matrix.
  • the anti-laser damage film material is alumina ceramic; the thickness of the anti-laser damage film is 50-200nm.
  • the nano transition layer is generated by high-temperature heat treatment of the adjacent structural layers in the ceramic matrix and the anti-laser damage film, and is located at the interface between the two.
  • the nano transition layer is obtained by a ceramic matrix coated with an anti-laser damage film and subjected to a constant temperature heat treatment at a temperature of 500 to 1000°C for 5 to 30 minutes.
  • the chemical composition of calcium-doped lanthanum chromate is: La 1- ⁇ Ca ⁇ CrO 3 , wherein ⁇ representing the Ca doping amount is 0.3 to 0.7.
  • the chemical composition of low-barium-doped lanthanum manganate is: La 0.5 Ba x MnO 3 , wherein x representing the Ba doping amount is 0.1 to 0.3.
  • the chemical composition of medium-barium-doped lanthanum manganate is: La 0.5 Ba y MnO 3 , wherein y representing the Ba doping amount is 0.4 to 0.5.
  • the chemical composition of high-barium-doped lanthanum manganate is: La 0.5 Ba z MnO 3 , wherein z representing the Ba doping amount is 0.6 to 0.7.
  • the calcium-doped lanthanum chromate ceramic layer, the high-barium-doped lanthanum manganate ceramic layer, and the medium-barium-doped lanthanum manganate ceramic layer are porous structures, while the outermost low-barium-doped lanthanum manganate ceramic layer is dense.
  • the pore size in each structural layer in the ceramic matrix is distributed in a gradient decreasing state from the middle to the two sides.
  • the middlemost layer is a first ceramic body with larger pores sintered by calcium-doped lanthanum chromate; a partial scanning electron microscope photo of the first ceramic body is shown in Figure 2. Outside the first ceramic body, a second ceramic body with medium-sized pores sintered by high-barium-doped lanthanum manganate is coated; a partial scanning electron microscope photo of the second ceramic body is shown in Figure 3. Outside the second ceramic body, a third ceramic body with smaller pores sintered by medium-barium-doped lanthanum manganate is coated. A partial scanning electron microscope photo of the third ceramic body is shown in Figure 4. Figures 2-4 are all microscopic images with the same small magnification.
  • the laser is incident from one side of the anti-laser damage film and penetrates the anti-laser damage film material.
  • the ceramic matrix acts as the energy absorption body, efficiently absorbs the light energy contained in the laser and converts its own internal energy.
  • the ceramic matrix used in this embodiment is made of lanthanide perovskite ceramic-based materials.
  • this embodiment uses the optimized addition of different dopants to change the material properties, and produces a special ceramic matrix with a "gradient" reduction in pores from the inside to the outside of the structure.
  • the materials of each structural layer are highly similar, the thermal expansion coefficients of each interface material are similar, and the compatibility between the layers is good, which can eliminate the sudden changes in the thermal expansion coefficient and thermal conductivity of the interfaces of each layer of the substrate.
  • the increase in porosity can reduce the elastic modulus of the material, and the thermal residual stress can be released through the holes during the cooling process.
  • a complete sintered body with obvious differences in layer structure properties is formed in the scheme of this embodiment, and the structural strength of the ceramic matrix is high, thereby improving the thermal shock resistance of the material in extreme high temperature environments.
  • the special ceramic matrix used in this embodiment also has a relatively wide absorption spectrum.
  • the light absorber made of the ceramic matrix material has a relatively high absorption efficiency for light within the wavelength range of 0.2 to 20 ⁇ m.
  • the anti-laser damage film material of the light absorber in this embodiment adopts aluminum oxide coating, which has a high laser damage resistance and can produce a good anti-light radiation damage effect on the internal ceramic matrix. Even under the high-intensity irradiation conditions of nano-laser, it can still maintain a strong anti-damage threshold and improve the service life of the light absorber.
  • Another feature of aluminum oxide coating is that it has a high light transmittance, so it can ensure that the light absorber has a high light absorption rate.
  • this embodiment also forms a thin nano transition layer on the interface between the two by high-temperature heat treatment.
  • the nano transition layer is made by subjecting the ceramic matrix coated with the anti-laser damage film to a constant temperature heat treatment at 500 to 1000°C for 5 to 30 minutes. It is mainly generated by a series of complex physical and chemical reactions of two different structural layer materials, aluminum oxide and low-barium-doped lanthanum manganate, under high temperature.
  • the nano transition layer can generate positive gains in enhancing the interface effects of different structural layers, improving the conductivity of light and the conversion rate of light energy. This will improve the high temperature resistance and thermal shock resistance as well as the thermal conductivity of the light absorber.
  • the light absorber provided in this embodiment has a wide absorption spectrum, a very high absorption rate of light components in the absorption spectrum, can withstand high operating temperatures, and has strong resistance to light damage and thermal shock, this type of lanthanide perovskite ceramic-based light absorber can be used as a light energy absorption material in the probe of a laser energy meter to absorb ultraviolet, visible, near-infrared, mid-to-far infrared light in the higher spectrum range of the 0.2-20 ⁇ m band.
  • This embodiment provides a method for preparing a lanthanide perovskite ceramic-based light absorber, which is used to prepare the lanthanide perovskite ceramic-based light absorber in Example 1. Specifically, the preparation method includes the following steps:
  • Lanthanum oxide, chromium oxide and calcium carbonate are mixed according to the stoichiometric ratio of La 1- ⁇ Ca ⁇ CrO 3 , solid-phase sintered, and then ball-milled and sieved to obtain calcium-doped lanthanum chromate powder; wherein ⁇ is 0.3 to 0.7.
  • (2) lanthanum oxide, manganese oxide and barium carbonate are mixed according to a preset stoichiometric ratio of La 0.5 Ba x MnO 3 , solid phase sintered, and then ball milled and sieved to obtain low-barium doped lanthanum manganate powder; wherein x is 0.1 to 0.3.
  • lanthanum oxide, manganese oxide and barium carbonate are mixed according to a preset stoichiometric ratio of La 0.5 Ba z MnO 3 , solid phase sintered, and then ball milled and sieved to obtain high-barium doped lanthanum manganate powder; wherein z is 0.6 to 0.7.
  • the sintering temperature of the raw materials of each powder during solid phase sintering is 1000-1200°C, and the insulation time is 2-5h; the ball milling speed during ball milling is 300r/min, the ball-to-material weight ratio is 3:1, and the ball milling time is 24-48h.
  • the four ceramic raw material powders prepared in the above step were respectively mixed with the polyvinyl alcohol solution and passed through a 200-mesh sieve to obtain four different granulated powders.
  • this embodiment adds a polyvinyl alcohol solution to the ball-milled ceramic powder.
  • the purpose of the polyvinyl alcohol solution is to improve the molding effect of the over-fine ceramic powder in the pressing stage. Based on this goal, this embodiment selects a polyvinyl alcohol solution with a lower concentration, and the concentration of the polyvinyl alcohol solution is 5-10%.
  • the amount of polyvinyl alcohol solution is also relatively small. Specifically, in this embodiment, the weight ratio of the polyvinyl alcohol solution to the ceramic powder is 1: (10-12.5).
  • the shape and size of the hot pressing mold can be reasonably selected according to the structural parameters of the ceramic matrix to be produced.
  • the pressure during the pressing process is set to 10-15 MPa, and the holding time is 5-10 minutes.
  • the pressed green body is subjected to high-temperature sintering in an argon environment to obtain a ceramic matrix with a dense surface, a porous middle, and a pore size that decreases gradually from the middle to both sides.
  • the pressure of the argon atmosphere is set to 10-20 kPa
  • the sintering temperature is 1400-1500° C.
  • the sintering time is 2-4 hours.
  • any coating process is adopted to form a uniform coating with a thickness of 50-200 nm on the surface of the calcium-doped lanthanum chromate ceramic layer on one side of the ceramic substrate.
  • the obtained uniform coating is the required anti-laser damage film.
  • the Al 2 O 3 coating is coated on the surface of the dense lanthanum manganate ceramic layer in the ceramic matrix, and the base surface of the coating is uniform and has good compatibility and adhesion with the coating material.
  • the coating process that can be selected includes any one of vacuum evaporation, pulsed laser deposition, atomic layer deposition and magnetron sputtering technology.
  • the ceramic substrate containing the anti-laser damage film prepared in the above step is sent into an air furnace and heat-treated at a temperature of 500-1000°C for 5-30 minutes to form a specific nano transition layer at the interface of the anti-laser damage film and the ceramic substrate. Finally, the product is naturally cooled to room temperature to obtain the desired lanthanide perovskite ceramic-based light absorber.
  • this example also uses the above preparation method with different process parameters to test the sample production of lanthanide perovskite ceramic-based light absorbers.
  • the specific preparation cases are as follows:
  • Lanthanum oxide, manganese oxide, barium carbonate, calcium carbonate and chromium oxide powders were mixed in the stoichiometric ratio of La 0.5 Ba 0.1 MnO 3 , La 0.5 Ba 0.4 MnO 3 , La 0.5 Ba 0.6 MnO 3 and La 0.7 Ca 0.3 CrO 3 , respectively, and then solid phase sintered.
  • the sintering temperature was 1000°C
  • the heating rate was 5°C/min
  • the holding time was 5h.
  • the sintered product was ball milled at a speed of 300 rpm for 24h and sieved; finally, three barium-doped lanthanum manganate powders with different doping rates and calcium-doped lanthanum chromate powders were obtained.
  • the above four powders were mixed evenly with polyvinyl alcohol solution and passed through a 200 mesh sieve to obtain granulated powder.
  • the concentration of the polyvinyl alcohol solution was 5%, and the weight ratio of the polyvinyl alcohol solution to the ceramic powder was 1:12.
  • the granulated powder was evenly spread on the first and seventh layers in the order of La 0.5 Ba 0.1 MnO 3 , the second and sixth layers of La 0.5 Ba 0.4 MnO 3 , the third and fifth layers of La 0.5 Ba 0.6 MnO 3 , and the fourth layer of La 0.7 Ca 0.3 CrO 3.
  • the green body was obtained by placing the green body in a hot pressing mold and maintaining the pressure at 10 MPa for 10 minutes.
  • the green body was sintered for 4 hours at 1400°C and 20 kPa atmosphere pressure in an argon environment to obtain a ceramic matrix with a dense surface and porous middle.
  • the first and seventh layers in the sintered product are 0.05 mm thick, dense La 0.5 Ba 0.1 MnO 3 .
  • the second and sixth layers are 0.05 mm thick, relatively small-pore La 0.5 Ba 0.4 MnO 3 .
  • the third and fifth layers are 0.05 mm thick, medium-pore La 0.5 Ba 0.6 MnO 3 .
  • the fourth layer is 0.2 mm thick, relatively large-pore La 0.7 Ca 0.3 CrO 3 .
  • a 200nm thick Al 2 O 3 film was deposited on the surface of the ceramic substrate using vacuum evaporation technology.
  • the above-mentioned film-based structure was placed in an air furnace, heat-treated at a temperature of 500° C. for 30 minutes, and then taken out and naturally cooled to obtain the desired lanthanide perovskite ceramic-based light absorber.
  • Lanthanum oxide, manganese oxide, barium carbonate, calcium carbonate and chromium oxide powders were mixed in the stoichiometric ratio of La 0.5 Ba 0.2 MnO 3 , La 0.5 Ba 0.5 MnO 3 , La 0.5 Ba 0.7 MnO 3 and La 0.6 Ca 0.4 CrO 3 , respectively, and then solid phase sintered.
  • the sintering temperature was 1100°C
  • the heating rate was 5°C/min
  • the holding time was 3h.
  • three barium-doped lanthanum manganate powders with different doping rates and calcium-doped lanthanum chromate powders were obtained through sieving.
  • the above four powders were mixed evenly with the polyvinyl alcohol solution and passed through a 200-mesh sieve to obtain granulated powders.
  • the concentration of the polyvinyl alcohol solution was 6%
  • the weight ratio of the polyvinyl alcohol solution to the ceramic powder was 1:11.1.
  • the granulated powders were evenly spread on the surface of the ceramic powder in the following order: the first and seventh layers were La 0.5 Ba 0.2 MnO 3 , the second and sixth layers were La 0.5 Ba 0.5 MnO 3 , the third and fifth layers were La 0.5 Ba 0.7 MnO 3 , and the fourth layer was La 0.6 Ca 0.4 CrO 3.
  • the green body was obtained by placing the green body in a hot pressing mold and maintaining the pressure at 11Mpa for 9 minutes. Finally, the green body was sintered for 3 hours at 1450°C and 15kPa in an argon environment to obtain a ceramic matrix with a dense surface and porous middle.
  • the first and seventh layers in the sintered product are 0.05 mm thick, dense La 0.5 Ba 0.2 MnO 3 .
  • the second and sixth layers are 0.05 mm thick, relatively small-pore La 0.5 Ba 0.5 MnO 3 .
  • the third and fifth layers are 0.1 mm thick, medium-pore La 0.5 Ba 0.7 MnO 3 .
  • the fourth layer is 0.2 mm thick, relatively large-pore La 0.6 Ca 0.4 CrO 3 .
  • the Al 2 O 3 film with a thickness of 150 nm was deposited on the surface of the porous gradient ceramic by pulsed laser deposition technology.
  • the above-mentioned film-based structure is placed in an air furnace and subjected to constant temperature heat treatment at 600° C. for 25 minutes; after being taken out and naturally cooled, the desired lanthanide perovskite ceramic-based light absorber is obtained.
  • Lanthanum oxide, manganese oxide, barium carbonate, calcium carbonate and chromium oxide powders were mixed in the stoichiometric ratio of La 0.5 Ba 0.3 MnO 3 , La 0.5 Ba 0.4 MnO 3 , La 0.5 Ba 0.6 MnO 3 and La 0.5 Ca 0.5 CrO 3 , respectively, and then solid phase sintered.
  • the sintering temperature was 1050°C
  • the heating rate was 5°C/min
  • the holding time was 4h.
  • the powders were ball milled at a speed of 300r/min for 36h and sieved to obtain three different doping rates of barium-doped lanthanum manganate and calcium-doped lanthanum chromate powders.
  • the above four powders were mixed evenly with polyvinyl alcohol solution and passed through a 200-mesh sieve to obtain granulated powders.
  • the concentration of the polyvinyl alcohol solution was 8%, and the weight ratio of the polyvinyl alcohol solution to the ceramic powder was 1:12.5.
  • the granulated powders were evenly spread on a plate in the order of La 0.5 Ba 0.3 MnO 3 for the first and seventh layers, La 0.5 Ba 0.4 MnO 3 for the second and sixth layers, La 0.5 Ba 0.6 MnO 3 for the third and fifth layers, and La 0.5 Ca 0.5 CrO 3 for the fourth layer.
  • the green body was obtained by placing the green body in a hot pressing mold and maintaining the pressure at 14 MPa for 7 minutes.
  • the green body was sintered for 2 hours at 1500°C and 10 kPa in an argon environment to obtain a ceramic matrix with a dense surface and porous middle.
  • the first and seventh layers in the sintered product are 0.1 mm thick, dense La 0.5 Ba 0.3 MnO 3 .
  • the second and sixth layers are 0.1 mm thick, relatively small-pore La 0.5 Ba 0.4 MnO 3 .
  • the third and fifth layers are 0.1 mm thick, medium-pore La 0.5 Ba 0.6 MnO 3 .
  • the fourth layer is 0.2 mm thick, relatively large-pore La 0.5 Ca 0.5 CrO 3 .
  • Atomic layer deposition technology was used to deposit a 50nm thick Al 2 O 3 film on the surface of the pore gradient ceramic.
  • the above-mentioned film-based structure is placed in an air furnace and subjected to constant temperature heat treatment for 5 minutes at a temperature of 1000° C.; after being taken out and naturally cooled, the desired lanthanide perovskite ceramic-based light absorber is obtained.
  • Lanthanum oxide, manganese oxide, barium carbonate, calcium carbonate and chromium oxide powders were mixed in the stoichiometric ratio of La 0.5 Ba 0.3 MnO 3 , La 0.5 Ba 0.5 MnO 3 , La 0.5 Ba 0.7 MnO 3 and La 0.3 Ca 07 CrO 3 , respectively, and then solid phase sintered.
  • the sintering temperature was 1050°C
  • the heating rate was 5°C/min
  • the holding time was 4h.
  • calcium-doped lanthanum chromate powder and three barium-doped lanthanum manganate powders with different doping rates were obtained.
  • the above four powders were mixed with polyvinyl alcohol solution respectively and passed through a 200 mesh sieve to obtain granulated powders.
  • the concentration of the polyvinyl alcohol solution was 10%, and the weight ratio of the polyvinyl alcohol solution to the ceramic powder was 1:10.
  • the granulated powders were evenly spread on the surface of the ceramic powder in the following order: the first and seventh layers were La 0.5 Ba 0.3 MnO 3 , the second and sixth layers were La 0.5 Ba 0.5 MnO 3 , the third and fifth layers were La 0.5 Ba 0.7 MnO 3 , and the fourth layer was La 0.3 Ca 0.7 CrO 3 .
  • the green body was obtained by placing the green body in a hot pressing mold and maintaining the pressure at 15Mpa for 5 minutes. Finally, the green body was sintered for 2 hours at 1500°C and 10kPa in an argon environment to obtain a ceramic matrix with a dense surface and porous middle.
  • the first and seventh layers in the sintered product are 0.1 mm thick, dense La 0.5 Ba 0.3 MnO 3 .
  • the second and sixth layers are 0.1 mm thick, relatively small-pore La 0.5 Ba 0.5 MnO 3 .
  • the third and fifth layers are 0.2 mm thick, medium-pore La 0.5 Ba 0.7 MnO 3 .
  • the fourth layer is 0.2 mm thick, relatively large-pore La 0.3 Ca 0.7 CrO 3 .
  • a 50nm thick Al 2 O 3 film was deposited on the surface of the porous gradient ceramic by magnetron sputtering technology.
  • the above-mentioned film-based structure is placed in an air furnace and heat-treated at a temperature of 1000° C. for 5 minutes; after being taken out and naturally cooled, the desired lanthanide perovskite ceramic-based light absorber is obtained.
  • this embodiment also performs performance tests on each sample prepared in each test example.
  • the test items include: high temperature resistance, thermal shock resistance, and light absorption rate of materials in different bands.
  • the performance test results of the samples in each test example are as follows:
  • the main component that absorbs light components in the light absorber is the ceramic matrix.
  • This embodiment tests and statistics the absorption properties of ceramic bodies with different components and structures in the ceramic matrix, and draws the following absorption spectrum. Among them, the absorption spectrum of each material in the 0-2.5 micron band is shown in Figure 7, and the absorption spectrum in the 2.5-20 micron band (working band) is shown in Figure 8. From the analysis of the data in the figure, it can be seen that: the light absorption rate of each layer of material in the light absorber in this embodiment within the working band is maintained at a relatively high level, which can produce a good light absorption effect.
  • the absorption rate of the light absorber of this embodiment in the 2.5-14 micron band is maintained at an extremely high level, with an average absorption rate of more than 80%, and the absorption rate in the 14-20 micron band fluctuates, but it is still within an acceptable range.
  • the thermal shock resistance of the light absorber was tested by the following air cooling method.
  • the light absorber was placed in a muffle furnace at 1200°C and kept for 15 minutes, then quickly taken out of the muffle furnace and cooled to room temperature in air.
  • the above experimental process was repeated 30 times.
  • the 1-on-1 test method includes a laser irradiation sample collected at least 10 different sampling points of the optical absorber with different laser energy densities.
  • the plotting of the optical absorber's anti-laser loss performance diagram depends on the energy density, and then the data is linearly extrapolated to find the position where the damage probability is 0%, that is, the laser damage performance.
  • Statistical analysis is performed during data processing to reduce the error introduced by sample surface defects in damage threshold measurement.
  • This embodiment provides a wide-spectrum laser energy meter, in which the probe of the laser energy meter adopts the lanthanide perovskite ceramic-based light absorber prepared by the preparation method of Example 2. Therefore, the laser energy meter has a wide absorption spectrum and a high light absorption rate. At the same time, it also has strong light damage resistance and thermal shock resistance. The service life of the product is significantly improved.

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Abstract

A lanthanide-series perovskite ceramic-based light absorber, and the use of the light absorber and a preparation method therefor in the photo-electronic technical field. In the light absorber, a multi-layer "sandwich" structure is used, and comprises: a ceramic matrix, a nano transition layer and a laser-damage-resistant thin film, wherein the ceramic matrix comprises seven layers which are symmetrical up and down, and the seven layers sequentially comprise a porous calcium-doped lanthanum chromate ceramic layer, a porous high-barium-doped lanthanum manganate ceramic layer and a porous medium-barium-doped lanthanum manganate ceramic layer from inside to outside, and a compact low-barium-doped lanthanum manganate ceramic layer. The sizes of pores in each structural layer of the ceramic matrix are distributed in a gradient decreasing mode from the middle to the two sides. The laser-damage-resistant thin film on the surface of the ceramic matrix is aluminum oxide. The nano transition layer is generated by subjecting the laser-damage-resistant thin film and an adjacent structural layer in the ceramic matrix to a high-temperature heat treatment. The present invention solves the problem of various properties such as the absorption spectrum, absorptivity, heat resistance, shock resistance and laser damage resistance of an existing light absorber not being balanced.

Description

一种镧系钙钛矿陶瓷基光吸收体及其应用与制备方法A lanthanide perovskite ceramic-based light absorber and its application and preparation method 技术领域Technical Field
本发明属于光电技术领域，具体涉及一种镧系钙钛矿陶瓷基光吸收体，该光吸收体的应用，以及镧系钙钛矿陶瓷基光吸收体的制备方法。The present invention belongs to the field of optoelectronic technology, and in particular relates to a lanthanide perovskite ceramic-based light absorber, application of the light absorber, and a method for preparing the lanthanide perovskite ceramic-based light absorber.
背景技术Background technique
激光功率计，又名激光能量计；是一种专用于测量激光能量的测量仪器。在现有技术中，对于大功率激光的测量，多以热电堆型激光功率计为主。这种设备的测试原理主要是利用其探头中光吸收体吸收入射激光的光能，并将光能转化成热能。光吸收体中央和边缘两端形成温度梯度场，探头中热电材料由此产生温差电动势，电动势的大小取决于激光转化的热能的大小。因此，探头中的光吸收体是热电堆型激光功率计的核心部件。光吸收体的光吸收性能、耐激光损伤性能和抗热震性能将直接决定激光能量计测量过程中的响应强度，以及可测量的激光的光谱宽度和功率范围。Laser power meter, also known as laser energy meter, is a measuring instrument dedicated to measuring laser energy. In the prior art, thermopile laser power meters are mainly used for measuring high-power lasers. The testing principle of this equipment is mainly to use the light absorber in its probe to absorb the light energy of the incident laser and convert the light energy into heat energy. A temperature gradient field is formed in the center and both ends of the edge of the light absorber, and the thermoelectric material in the probe generates a temperature difference electromotive force, the magnitude of which depends on the magnitude of the heat energy converted by the laser. Therefore, the light absorber in the probe is the core component of the thermopile laser power meter. The light absorption performance, laser damage resistance and thermal shock resistance of the light absorber will directly determine the response intensity during the measurement process of the laser energy meter, as well as the spectral width and power range of the measurable laser.
目前，热电堆型激光功率计探头中的光吸收材料(包括薄膜和块体)，主要包括金属纳米材料(如金黑、银黑、铁黑等)、碳材料、硫化物、碳化物、氮化物、光学玻璃等。其中，在高温富氧环境下光吸收材料多为金属氧化物及其复合氧化物材料。例如，文献《Lu Y,et al.High thermal radiation of Ca-doped lanthanum chromite,RSC Advances,2015,5:30667.》公开的方案中，技术人员通过固相反应法制备了钙掺杂铬酸镧系列陶瓷，La 0.5Ca 0.5CrO 3的光吸收性能最佳，其太阳能吸收率达到95％。文献《(Ca,Fe)共掺铈酸镧陶瓷的近红外吸收性能,硅酸盐学报，2016，44:387–391.贺智勇等》公开的技术方案中，技术人员通过高温固相烧结工艺制备钙铁共掺的铈酸镧系列红外吸收陶瓷，当Ca引入量x为0.1、Fe引入量y为0.15时，样品近红外吸收性能较优，在750～2500nm波段的平均吸收率为88.7％。然而，这些材料的吸收波长范围较窄(大多处于0.2～2.5μm)，且在高温富氧环境(≥1000℃)中容易失效，材料的耐候性较差。 At present, the light absorbing materials (including thin films and blocks) in thermopile laser power meter probes mainly include metal nanomaterials (such as gold black, silver black, iron black, etc.), carbon materials, sulfides, carbides, nitrides, optical glass, etc. Among them, the light absorbing materials in a high-temperature oxygen-rich environment are mostly metal oxides and their composite oxide materials. For example, in the solution disclosed in the document "Lu Y, et al. High thermal radiation of Ca-doped lanthanum chromite, RSC Advances, 2015, 5: 30667.", technicians prepared calcium-doped lanthanum chromite series ceramics by solid-phase reaction method, and La 0.5 Ca 0.5 CrO 3 had the best light absorption performance, and its solar energy absorption rate reached 95%. In the technical solution disclosed in the document "Near-infrared absorption performance of (Ca,Fe) co-doped lanthanum ceria ceramics, Journal of the Chinese Ceramic Society, 2016, 44:387-391. He Zhiyong et al.", technicians prepared calcium-iron co-doped lanthanum ceria series infrared absorption ceramics through high-temperature solid-phase sintering process. When the amount of Ca introduced x is 0.1 and the amount of Fe introduced y is 0.15, the sample has excellent near-infrared absorption performance, and the average absorption rate in the 750-2500nm band is 88.7%. However, the absorption wavelength range of these materials is narrow (mostly in the range of 0.2-2.5μm), and they are prone to failure in high-temperature oxygen-rich environments (≥1000℃), and the weather resistance of the materials is poor.
此外，文献《Zhang PX,et al.LaCaMnO 3thin film laser energy/power meter,Optics&Laser Technology,2004,36:341–343.》公开了一种采用脉冲激光沉积法将La 1-xCa xMnO 3(0.05≤x≤0.33)沉积在LaAlO 3衬底上，制备得到La 1-xCa xMnO 3薄膜作为激光功率计和能量计的光吸收层的技术方案。这种将锰酸镧材料应用到光吸收体的方案具有制备简易成本低的优势，但是该方案制备的光吸收体仍然会存在光吸收涂层易受激光损伤失效，涂 层易剥落，抗热震性能差等问题。 In addition, the document "Zhang PX, et al. LaCaMnO 3 thin film laser energy/power meter, Optics & Laser Technology, 2004, 36: 341-343." discloses a technical solution for preparing La 1-x Ca x MnO 3 thin film as a light absorption layer of a laser power meter and energy meter by depositing La 1-x Ca x MnO 3 (0.05≤x≤0.33) on a LaAlO 3 substrate using a pulsed laser deposition method. This solution of applying lanthanum manganate material to a light absorber has the advantages of simple preparation and low cost, but the light absorber prepared by this solution still has problems such as the light absorption coating being easily damaged and failing by laser, the coating being easily peeled off, and poor thermal shock resistance.
进一步地，文献《Afifah N,et al.Enhancement of photoresponse to ultraviolet region by coupling perovskite LaMnO 3with TiO 2nanoparticles,International Symposium on Current Progress in Functional Materials,2017,188:012060.》公开了一种采用溶胶-凝胶法制备的不同LaMnO 3/TiO 2摩尔比的LaMnO 3/TiO 2纳米复合材料，该材料用作光吸收体时可以有效提高材料在紫外光区的吸收率。但是该材料为纳米粉末材料，无法应用于高温环境，如高激光测量等使用场景。 Furthermore, the document "Afifah N, et al. Enhancement of photoresponse to ultraviolet region by coupling perovskite LaMnO 3 with TiO 2 nanoparticles, International Symposium on Current Progress in Functional Materials, 2017, 188: 012060." discloses a LaMnO 3 /TiO 2 nanocomposite material with different LaMnO 3 /TiO 2 molar ratios prepared by a sol-gel method, which can effectively improve the absorption rate of the material in the ultraviolet region when used as a light absorber. However, the material is a nanopowder material and cannot be used in high-temperature environments, such as high-laser measurement and other usage scenarios.
在热电堆型激光功率计的方案设计中，光吸收体的吸收光谱范围和光吸收率是首要考虑的性能参数。而材料的耐激光损伤性能、耐高温和抗热震性等耐候性能则是制约产品使用效果和使用寿命的关键指标。但是，现有技术提供的各类方案大都无法同时在以上性能中取得平衡。寻找一种更优的方案，同时克服上述性能缺陷成为本领域技术人员亟待解决的技术问题。In the design of thermopile laser power meters, the absorption spectrum range and light absorption rate of the light absorber are the primary performance parameters to be considered. The material's weather resistance, such as laser damage resistance, high temperature resistance, and thermal shock resistance, are key indicators that restrict the product's use effect and service life. However, most of the various solutions provided by the existing technology cannot achieve a balance among the above performances at the same time. Finding a better solution and overcoming the above performance defects has become a technical problem that needs to be solved urgently by those skilled in the art.
发明内容Summary of the invention
为了解决现有光吸收体无法在吸收光谱、吸收率、耐热抗震和耐激光损伤等性能上达到均衡的问题；本发明提供一种锰酸镧陶瓷基光吸收体，该光吸收体的应用，以及锰酸镧陶瓷基光吸收体的制备方法。In order to solve the problem that existing light absorbers cannot achieve a balance in absorption spectrum, absorption rate, heat resistance, shock resistance and laser damage resistance; the present invention provides a lanthanum manganate ceramic-based light absorber, the application of the light absorber, and a method for preparing the lanthanum manganate ceramic-based light absorber.
本发明采用以下技术方案实现：The present invention is implemented by the following technical solutions:
一种镧系钙钛矿陶瓷基光吸收体，该光吸收体采用了多层的“夹心”结构。按照功能划分，该型多层的锰酸镧陶瓷基光吸收体可分为：陶瓷基体、抗激光损伤薄膜，以及位于抗激光损伤薄膜和陶瓷基体之间的纳米过渡层。A lanthanum perovskite ceramic-based light absorber, which adopts a multi-layer "sandwich" structure. According to the function, this type of multi-layer lanthanum manganate ceramic-based light absorber can be divided into: a ceramic matrix, a laser damage-resistant film, and a nano-transition layer located between the laser damage-resistant film and the ceramic matrix.
其中，陶瓷基体包括七个按照预设顺序依次叠层分布的结构层。各结构层包括位于中间层的多孔的钙掺杂铬酸镧陶瓷层；位于钙掺杂铬酸镧陶瓷层上下两侧的多孔的高钡掺杂锰酸镧陶瓷层；位于高钡掺杂锰酸镧陶瓷层上下两侧的多孔的中钡掺杂锰酸镧陶瓷层；以及位于中钡掺杂锰酸镧陶瓷层上下两侧的致密的低钡掺杂锰酸镧陶瓷层。在陶瓷基体中，钙掺杂铬酸镧陶瓷层、高钡掺杂锰酸镧陶瓷层、中钡掺杂锰酸镧陶瓷层呈多孔结构。陶瓷基体中各结构层中的孔隙尺寸从中间向两侧呈梯度递减的分布状态；陶瓷基体中各结构层的厚度为0.05-0.2mm，总厚度为0.5-1mm。The ceramic matrix includes seven structural layers stacked in a preset order. Each structural layer includes a porous calcium-doped lanthanum chromate ceramic layer located in the middle layer; a porous high-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the calcium-doped lanthanum chromate ceramic layer; a porous medium-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the high-barium-doped lanthanum manganate ceramic layer; and a dense low-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the medium-barium-doped lanthanum manganate ceramic layer. In the ceramic matrix, the calcium-doped lanthanum chromate ceramic layer, the high-barium-doped lanthanum manganate ceramic layer, and the medium-barium-doped lanthanum manganate ceramic layer are porous structures. The pore size in each structural layer in the ceramic matrix is distributed in a gradient decreasing state from the middle to the two sides; the thickness of each structural layer in the ceramic matrix is 0.05-0.2mm, and the total thickness is 0.5-1mm.
抗激光损伤薄膜位于陶瓷基体中钙掺杂锰酸镧陶瓷层的外表面，抗激光损伤薄膜材料为氧化铝陶瓷；抗激光损伤薄膜的厚度为50-200nm。纳米过渡层由陶瓷基体和抗激光损伤薄膜中的相邻结构层经高温热处理后生成，并位于二者的界面处。The anti-laser damage film is located on the outer surface of the calcium-doped lanthanum manganate ceramic layer in the ceramic matrix. The anti-laser damage film material is alumina ceramic; the thickness of the anti-laser damage film is 50-200nm. The nano transition layer is generated by high-temperature heat treatment of the ceramic matrix and the adjacent structural layers in the anti-laser damage film, and is located at the interface between the two.
作为本发明进一步的改进，钙掺杂铬酸镧的化学组成为：La 1-αCa αCrO 3，其中，表征Ca掺杂量的α为0.3～0.7。低钡掺杂锰酸镧的化学组成为：La 0.5Ba xMnO 3，其中，表征Ba掺杂量的x为0.1～0.3。中钡掺杂锰酸镧的化学组成为：La 0.5Ba yMnO 3，其中，表征Ba掺杂量的y为0.4～0.5。高钡掺杂锰酸镧的化学组成为：La 0.5Ba zMnO 3，其中，表征Ba的掺杂量z为0.6～0.7。 As a further improvement of the present invention, the chemical composition of calcium-doped lanthanum chromate is: La 1-α Ca α CrO 3 , wherein α, which represents the Ca doping amount, is 0.3 to 0.7. The chemical composition of low-barium-doped lanthanum manganate is: La 0.5 Ba x MnO 3 , wherein x, which represents the Ba doping amount, is 0.1 to 0.3. The chemical composition of medium-barium-doped lanthanum manganate is: La 0.5 Ba y MnO 3 , wherein y, which represents the Ba doping amount, is 0.4 to 0.5. The chemical composition of high-barium-doped lanthanum manganate is: La 0.5 Ba z MnO 3 , wherein z, which represents the Ba doping amount, is 0.6 to 0.7.
作为本发明进一步的改进，纳米过渡层由镀制有抗激光损伤薄膜的陶瓷基体经500～1000℃的温度恒温热处理5～30min后制得。As a further improvement of the present invention, the nanometer transition layer is prepared by subjecting a ceramic substrate coated with a laser damage resistant film to a constant temperature heat treatment at a temperature of 500 to 1000° C. for 5 to 30 minutes.
本发明还包括一种如前述的镧系钙钛矿陶瓷基的应用，具体为：将镧系钙钛矿陶瓷基作为激光能量计的探头中的光能吸收材料，用于吸收0.2～20μm波段内的紫外、可见以及近红外和中远红外光。The present invention also includes an application of the lanthanide perovskite ceramic substrate as described above, specifically: using the lanthanide perovskite ceramic substrate as a light energy absorption material in a probe of a laser energy meter to absorb ultraviolet, visible, near-infrared, mid-to-far infrared light in the 0.2-20 μm band.
本发明还包括一种宽光谱的激光能量计，该激光能量计使用的探头中采用了如前述的镧系钙钛矿陶瓷基。The present invention also includes a wide-spectrum laser energy meter, in which the probe used in the laser energy meter adopts the lanthanide perovskite ceramic base as mentioned above.
本发明还包括一种镧系钙钛矿陶瓷基光吸收体的制备方法，该制备方法用于制备如前述的镧系钙钛矿陶瓷基光吸收体。具体地，制备方法包括如下步骤：The present invention also includes a method for preparing a lanthanide perovskite ceramic-based light absorber, which is used to prepare the lanthanide perovskite ceramic-based light absorber as described above. Specifically, the preparation method includes the following steps:
一、陶瓷粉体制备：1. Preparation of ceramic powder:
(1)将氧化镧、氧化铬和碳酸钙按照La 1-αCa αCrO 3的化学计量比混料后，固相烧结，再经球磨、过筛得到钙掺杂铬酸镧粉体；其中，α为0.3～0.7。 (1) Lanthanum oxide, chromium oxide and calcium carbonate are mixed according to the stoichiometric ratio of La 1-α Ca α CrO 3 , solid-phase sintered, and then ball-milled and sieved to obtain calcium-doped lanthanum chromate powder; wherein α is 0.3 to 0.7.
(2)将氧化镧、氧化锰和碳酸钡按照La 0.5Ba xMnO 3的预设化学计量比混料后，固相烧结，再经球磨、过筛得到低钡掺杂锰酸镧粉体；其中，x为0.1～0.3。 (2) lanthanum oxide, manganese oxide and barium carbonate are mixed according to a preset stoichiometric ratio of La 0.5 Ba x MnO 3 , solid phase sintered, and then ball milled and sieved to obtain low-barium doped lanthanum manganate powder; wherein x is 0.1 to 0.3.
(3)将氧化镧、氧化锰和碳酸钡按照La 0.5Ba yMnO 3的预设化学计量比混料后，固相烧结，再经球磨、过筛得到中钡掺杂锰酸镧粉体；其中，y为0.4～0.5。 (3) After mixing lanthanum oxide, manganese oxide and barium carbonate according to a preset stoichiometric ratio of La 0.5 Ba y MnO 3 , solid phase sintering is performed, and then ball milling and sieving are performed to obtain medium-barium-doped lanthanum manganate powder; wherein y is 0.4 to 0.5.
(4)将氧化镧、氧化锰和碳酸钡按照La 0.5Ba zMnO 3的预设化学计量比混料后，固相烧结，再经球磨、过筛得到高钡掺杂锰酸镧粉体；其中，z为0.6～0.7。 (4) lanthanum oxide, manganese oxide and barium carbonate are mixed according to a preset stoichiometric ratio of La 0.5 Ba z MnO 3 , solid phase sintered, and then ball milled and sieved to obtain high-barium doped lanthanum manganate powder; wherein z is 0.6 to 0.7.
二、陶瓷基体制备：2. Ceramic matrix preparation:
(1)将上步骤制备出的四种陶瓷原料粉体分别与聚乙烯醇溶液混合均匀，过200目筛，得到四种不同的造粒粉末。(1) The four ceramic raw material powders prepared in the above step were respectively mixed with the polyvinyl alcohol solution and passed through a 200-mesh sieve to obtain four different granulated powders.
(2)根据拟生产的陶瓷基体的结构参数，将四种不同的造粒粉末按照所需的用量和预设顺序均匀平铺与热压模具中，并在预设模压条件下压制成生坯。(2) According to the structural parameters of the ceramic matrix to be produced, four different granulated powders are evenly spread in a hot pressing mold in the required amount and preset order, and pressed into a green body under preset molding conditions.
(3)在氩气环境下对压制出的生坯进行高温烧结；得到表层致密、中间多孔，且孔隙尺寸呈从中间向两侧梯度递减分布的陶瓷基体。(3) The pressed green body is subjected to high-temperature sintering in an argon environment to obtain a ceramic matrix with a dense surface, a porous middle, and a pore size that decreases gradually from the middle to both sides.
三、抗激光损伤薄膜镀制：3. Anti-laser damage thin film coating:
以Al 2O 3为镀层材料，采用任意一种镀膜工艺，在陶瓷基体其中一侧的钙掺杂铬酸镧陶瓷层表面生成厚度为50-200nm的均匀镀层，得到的均匀镀层即为所需的抗激光损伤薄膜。 With Al 2 O 3 as the coating material, any coating process is adopted to form a uniform coating with a thickness of 50-200 nm on the surface of the calcium-doped lanthanum chromate ceramic layer on one side of the ceramic substrate. The obtained uniform coating is the required anti-laser damage film.
四、纳米过渡层生成：4. Nano transition layer generation:
将上步骤制得的包含抗激光损伤薄膜的陶瓷基体送入到空气炉中，在500～1000℃的温度条件下，保温热处理5～30min，以在抗激光损伤薄膜和陶瓷基体的界面处形成特定的纳米过渡层，最后将产品自然冷却至室温，得到所需的镧系钙钛矿陶瓷基光吸收体。The ceramic substrate containing the anti-laser damage film prepared in the above step is sent into an air furnace and heat-treated at a temperature of 500-1000°C for 5-30 minutes to form a specific nano transition layer at the interface of the anti-laser damage film and the ceramic substrate. Finally, the product is naturally cooled to room temperature to obtain the desired lanthanide perovskite ceramic-based light absorber.
作为本发明进一步的改进，在陶瓷粉体制备过程中，各粉体的原料在固相烧结时的烧结温度为1000～1200℃，保温时间为2～5h；球磨粉碎时的球磨速度为300r/min，球料重量比3:1，球磨时间为24～48h。As a further improvement of the present invention, in the process of preparing ceramic powders, the sintering temperature of the raw materials of each powder during solid phase sintering is 1000-1200°C, and the insulation time is 2-5h; the ball milling speed during ball milling is 300r/min, the ball-to-material weight ratio is 3:1, and the ball milling time is 24-48h.
作为本发明进一步的改进，在陶瓷基体制备过程中，造粒粉末中使用的聚乙烯醇溶液的浓度为5～10％，聚乙烯醇溶液的重量与陶瓷粉末的重量比为1:(10～12.5)。As a further improvement of the present invention, in the process of preparing the ceramic matrix, the concentration of the polyvinyl alcohol solution used in the granulated powder is 5-10%, and the weight ratio of the polyvinyl alcohol solution to the ceramic powder is 1:(10-12.5).
作为本发明进一步的改进，在陶瓷基体制备过程中，生坯压制步骤中，采用
Figure PCTCN2022132885-appb-000001
的热压模具，压力设置为10～15MPa，保压时间为5～10min。生坯烧结过程中，氩气的压力设置为10～20kPa，烧结温度为1400～1500℃，烧结时间为2～4h。 As a further improvement of the present invention, in the process of preparing the ceramic matrix, in the green body pressing step,
Figure PCTCN2022132885-appb-000001
The hot pressing mold is set to a pressure of 10-15 MPa and a holding time of 5-10 min. During the green body sintering process, the argon pressure is set to 10-20 kPa, the sintering temperature is 1400-1500°C, and the sintering time is 2-4 h.
作为本发明进一步的改进，抗激光损伤薄膜镀制过程中，可选择的镀膜工艺包括真空蒸镀、脉冲激光沉积、原子层沉积和磁控溅射技术。As a further improvement of the present invention, in the process of coating the laser damage resistant thin film, the selectable coating processes include vacuum evaporation, pulsed laser deposition, atomic layer deposition and magnetron sputtering technology.
本发明提供的技术方案，具有如下有益效果：The technical solution provided by the present invention has the following beneficial effects:
本发明设计出的光吸收体采用具有七层结构的镧系钙钛矿基陶瓷材料作为能够吸收光能的陶瓷基体，该陶瓷基体可以有效吸收0.2～20μm波段内的各种各种光成分，在工作波段内的光吸收率超80％。陶瓷基体中特殊的孔隙梯度分布状态使得该产品具有超强的耐高温和抗热震性能。The light absorber designed by the present invention uses a lanthanide perovskite-based ceramic material with a seven-layer structure as a ceramic matrix capable of absorbing light energy. The ceramic matrix can effectively absorb various light components in the 0.2-20 μm band, and the light absorption rate in the working band exceeds 80%. The special pore gradient distribution state in the ceramic matrix makes the product have super high temperature resistance and thermal shock resistance.
本发明采用致密的钙掺杂锰酸镧陶瓷作为膜基结构中基体材料的最外层，并在其表面镀制了致密的Al 2O 3薄膜，这使得生产的光吸收体同时兼具有优良的宽光谱光吸收性能和耐高温特性。本发明中致密Al 2O 3薄膜的镀层厚度为50～200nm，因而可以在保持高透过率的基础上，显著提高基体材料的抗激光损伤性能。 The present invention adopts dense calcium-doped lanthanum manganate ceramic as the outermost layer of the base material in the membrane-based structure, and plates a dense Al 2 O 3 film on its surface, so that the produced light absorber has both excellent wide-spectrum light absorption performance and high-temperature resistance. The coating thickness of the dense Al 2 O 3 film in the present invention is 50-200nm, so that the anti-laser damage performance of the base material can be significantly improved on the basis of maintaining high transmittance.
特别地，基本发明方案对陶瓷基体表层和抗激光损伤薄膜的材料选择，本发明还通过特定的热处理温度在二者的界面处形成一层超薄的纳米过渡层，生产的纳米过渡层使得该光吸收体的抗高温热震性得到明显提升。In particular, the basic invention scheme selects materials for the surface layer of the ceramic substrate and the anti-laser damage film. The invention also forms an ultra-thin nano transition layer at the interface between the two through a specific heat treatment temperature. The produced nano transition layer significantly improves the high-temperature thermal shock resistance of the light absorber.
本发明还提供了一种制备以上设计的光吸收体产品的制备方法，该制备方法操作简单， 适于进行大规模工业化生产，产品良率高，可以有效降低产品的生产成本。The present invention also provides a method for preparing the light absorber product of the above design. The method is simple to operate, suitable for large-scale industrial production, has a high product yield, and can effectively reduce the production cost of the product.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明实施例1提供的光吸收体中陶瓷基体的各结构及其孔隙分布状态的示意图。FIG. 1 is a schematic diagram of various structures of a ceramic matrix and its pore distribution state in a light absorber provided in Example 1 of the present invention.
图2为本发明实施例1中由钙掺杂铬酸镧烧结而成的第一陶瓷体结构层的扫描电镜照片。FIG. 2 is a scanning electron microscope photograph of the first ceramic structure layer sintered by calcium-doped lanthanum chromate in Example 1 of the present invention.
图3为本发明实施例1中由高钡掺杂锰酸镧烧结而成的第二陶瓷体结构层的扫描电镜照片。FIG. 3 is a scanning electron microscope photograph of the second ceramic structure layer sintered from high-barium-doped lanthanum manganate in Example 1 of the present invention.
图4为本发明实施例1中由中钡掺杂锰酸镧烧结而成的第三陶瓷体结构层的扫描电镜照片。FIG. 4 is a scanning electron microscope photograph of the third ceramic structure layer sintered by lanthanum manganate doped with barium in Example 1 of the present invention.
图5为本发明实施例1中由低钡掺杂锰酸镧烧结而成的第四陶瓷体结构层的扫描电镜照片。FIG. 5 is a scanning electron microscope photograph of the fourth ceramic structure layer sintered from low-barium-doped lanthanum manganate in Example 1 of the present invention.
图6为本发明实施例2中提供的一种镧系钙钛矿陶瓷基光吸收体的制备方法的流程图。FIG6 is a flow chart of a method for preparing a lanthanide perovskite ceramic-based light absorber provided in Example 2 of the present invention.
图7为测试例中样本中的不同结构层材料在0-2.5微米波段内的吸收光谱。FIG. 7 shows the absorption spectra of different structural layer materials in the sample of the test example in the 0-2.5 μm band.
图8为测试例中样本中的不同结构层材料在2.5-20微米波段内的吸收光谱。FIG. 8 shows the absorption spectra of different structural layer materials in the sample of the test example in the 2.5-20 μm band.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步地详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.
实施例1Example 1
本实施例提供一种镧系钙钛矿陶瓷基光吸收体，如图1所示，该光吸收体采用了多层的“夹心”结构。按照功能划分，该型多层的锰酸镧陶瓷基光吸收体可分为：陶瓷基体、抗激光损伤薄膜，以及位于抗激光损伤薄膜和陶瓷基体之间的纳米过渡层。其中，陶瓷基体包括七个按照预设顺序依次叠层分布的结构层。包括位于中间层的多孔的钙掺杂铬酸镧陶瓷层；位于钙掺杂铬酸镧陶瓷层上下两侧的多孔的高钡掺杂锰酸镧陶瓷层；位于高钡掺杂锰酸镧陶瓷层上下两侧的多孔的中钡掺杂锰酸镧陶瓷层；以及位于中钡掺杂锰酸镧陶瓷层上下两侧的致密的低钡掺杂锰酸镧陶瓷层。陶瓷基体中各结构层的厚度为0.05-0.2mm，总厚度为0.5-1mm。The present embodiment provides a lanthanum perovskite ceramic-based light absorber, as shown in FIG1 , which adopts a multi-layer "sandwich" structure. According to the functional classification, this type of multi-layer lanthanum manganate ceramic-based light absorber can be divided into: a ceramic matrix, a laser damage-resistant film, and a nano-transition layer located between the laser damage-resistant film and the ceramic matrix. Among them, the ceramic matrix includes seven structural layers stacked in sequence according to a preset order. It includes a porous calcium-doped lanthanum chromate ceramic layer located in the middle layer; a porous high-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the calcium-doped lanthanum chromate ceramic layer; a porous medium-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the high-barium-doped lanthanum manganate ceramic layer; and a dense low-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the medium-barium-doped lanthanum manganate ceramic layer. The thickness of each structural layer in the ceramic matrix is 0.05-0.2mm, and the total thickness is 0.5-1mm.
考虑到陶瓷基体的各结构层是对称分布的，上下两面无方向性。本实施例中的抗激光损伤薄膜位于陶瓷基体任意一侧的钙掺杂锰酸镧陶瓷层的外表面。抗激光损伤薄膜材料为氧化铝陶瓷；抗激光损伤薄膜的厚度为50-200nm。纳米过渡层由陶瓷基体和抗激光损伤薄膜中的相邻结构层经高温热处理后生成，并位于二者的界面处。特别地，本实施例中纳米过渡层 由镀制有抗激光损伤薄膜的陶瓷基体经500～1000℃的温度恒温热处理5～30min后制得。Considering that the structural layers of the ceramic matrix are symmetrically distributed, the upper and lower surfaces have no directionality. The anti-laser damage film in this embodiment is located on the outer surface of the calcium-doped lanthanum manganate ceramic layer on either side of the ceramic matrix. The anti-laser damage film material is alumina ceramic; the thickness of the anti-laser damage film is 50-200nm. The nano transition layer is generated by high-temperature heat treatment of the adjacent structural layers in the ceramic matrix and the anti-laser damage film, and is located at the interface between the two. In particular, in this embodiment, the nano transition layer is obtained by a ceramic matrix coated with an anti-laser damage film and subjected to a constant temperature heat treatment at a temperature of 500 to 1000°C for 5 to 30 minutes.
具体地，在本实施例中，为了达到所需的陶瓷属性。钙掺杂铬酸镧的化学组成为：La 1-αCa αCrO 3，其中，表征Ca掺杂量的α为0.3～0.7。低钡掺杂锰酸镧的化学组成为：La 0.5Ba xMnO 3，其中，表征Ba掺杂量的x为0.1～0.3。中钡掺杂锰酸镧的化学组成为：La 0.5Ba yMnO 3，其中，表征Ba掺杂量的y为0.4～0.5。高钡掺杂锰酸镧的化学组成为：La 0.5Ba zMnO 3，其中，表征Ba的掺杂量z为0.6～0.7。 Specifically, in this embodiment, in order to achieve the desired ceramic properties. The chemical composition of calcium-doped lanthanum chromate is: La 1-α Ca α CrO 3 , wherein α representing the Ca doping amount is 0.3 to 0.7. The chemical composition of low-barium-doped lanthanum manganate is: La 0.5 Ba x MnO 3 , wherein x representing the Ba doping amount is 0.1 to 0.3. The chemical composition of medium-barium-doped lanthanum manganate is: La 0.5 Ba y MnO 3 , wherein y representing the Ba doping amount is 0.4 to 0.5. The chemical composition of high-barium-doped lanthanum manganate is: La 0.5 Ba z MnO 3 , wherein z representing the Ba doping amount is 0.6 to 0.7.
在陶瓷基体中，钙掺杂铬酸镧陶瓷层、高钡掺杂锰酸镧陶瓷层、中钡掺杂锰酸镧陶瓷层呈多孔结构；而最外侧的低钡掺杂锰酸镧陶瓷层则呈致密状态。陶瓷基体中各结构层中的孔隙尺寸从中间向两侧呈梯度递减的分布状态。In the ceramic matrix, the calcium-doped lanthanum chromate ceramic layer, the high-barium-doped lanthanum manganate ceramic layer, and the medium-barium-doped lanthanum manganate ceramic layer are porous structures, while the outermost low-barium-doped lanthanum manganate ceramic layer is dense. The pore size in each structural layer in the ceramic matrix is distributed in a gradient decreasing state from the middle to the two sides.
在这种特殊多层夹心结构中，位于最中间层的是由钙掺杂铬酸镧烧结而成的具有较大孔隙的第一陶瓷体；第一陶瓷体的局部扫描电镜照片如图2所示。而在第一陶瓷体之外，则包覆有由高钡掺杂锰酸镧烧结而成的包含中等尺寸孔隙的第二陶瓷体；第二陶瓷体的局部扫描电镜照片如图3所示。在第二陶瓷体之外，则包覆有由中钡掺杂锰酸镧烧结而成的具有较小孔隙的第三陶瓷体。第三陶瓷体的局部扫描电镜照片如图4所示。图2-4均为同一放大倍数小的显微图像，从图中可以明显看出，第一陶瓷体、第二陶瓷体和第三陶瓷体中的主要晶相的结构以及其中包含的孔隙的尺寸均依次缩小。而在第三陶瓷体之外，还包覆有由低钡掺杂锰酸镧烧结而成的致密的第四陶瓷体。第四陶瓷体的扫描电镜照片如图5所示，从图5中可以看出，第四陶瓷体是致密的结构，其中几乎不包含孔隙。In this special multilayer sandwich structure, the middlemost layer is a first ceramic body with larger pores sintered by calcium-doped lanthanum chromate; a partial scanning electron microscope photo of the first ceramic body is shown in Figure 2. Outside the first ceramic body, a second ceramic body with medium-sized pores sintered by high-barium-doped lanthanum manganate is coated; a partial scanning electron microscope photo of the second ceramic body is shown in Figure 3. Outside the second ceramic body, a third ceramic body with smaller pores sintered by medium-barium-doped lanthanum manganate is coated. A partial scanning electron microscope photo of the third ceramic body is shown in Figure 4. Figures 2-4 are all microscopic images with the same small magnification. It can be clearly seen from the figures that the structure of the main crystal phases in the first ceramic body, the second ceramic body and the third ceramic body and the size of the pores contained therein are successively reduced. Outside the third ceramic body, a dense fourth ceramic body sintered by low-barium-doped lanthanum manganate is also coated. The scanning electron microscope photo of the fourth ceramic body is shown in Figure 5. It can be seen from Figure 5 that the fourth ceramic body is a dense structure with almost no pores.
在本实施例提供的镧系钙钛矿陶瓷基光吸收体中，激光从抗激光损伤薄膜一侧入射，并穿透抗激光损伤薄膜材料，最终由陶瓷基体作为能量吸收主体，对激光中包含的光能进行高效吸收并转化自身的内能。In the lanthanide perovskite ceramic-based light absorber provided in this embodiment, the laser is incident from one side of the anti-laser damage film and penetrates the anti-laser damage film material. Finally, the ceramic matrix acts as the energy absorption body, efficiently absorbs the light energy contained in the laser and converts its own internal energy.
其中，本实施例采用的陶瓷基体由镧系钙钛矿陶瓷基材料制备而成。特别地，为了提高陶瓷基体的各项特性，本实施例利用不同掺杂物的优化添加对材料特性的改变，生产出了一种从内到外结构中孔隙“梯度”缩小的特殊陶瓷基体。The ceramic matrix used in this embodiment is made of lanthanide perovskite ceramic-based materials. In particular, in order to improve the various properties of the ceramic matrix, this embodiment uses the optimized addition of different dopants to change the material properties, and produces a special ceramic matrix with a "gradient" reduction in pores from the inside to the outside of the structure.
首先，由于本实施例中陶瓷基体的七种不同结构层均采用以镧系钙钛矿陶瓷为主的材料，因此各结构层的材料相似性高，各界面材料的热膨胀系数相似，且各层之间相容性好，可以消除基材各层界面的热膨胀系数和热导率的突变。其次，由于材料中特殊的孔隙分布，孔隙率的增加可以降低材料的弹性模量，同时在冷却过程中热残余应力可以通过孔洞释放。此外，本实施的方案中形成了一种具有明显的层结构属性差异的完整烧结体，陶瓷基体的结构强度高，从而提高了材料在极端高温环境下的抗热震性能。First, since the seven different structural layers of the ceramic matrix in this embodiment are all made of materials based on lanthanide perovskite ceramics, the materials of each structural layer are highly similar, the thermal expansion coefficients of each interface material are similar, and the compatibility between the layers is good, which can eliminate the sudden changes in the thermal expansion coefficient and thermal conductivity of the interfaces of each layer of the substrate. Secondly, due to the special pore distribution in the material, the increase in porosity can reduce the elastic modulus of the material, and the thermal residual stress can be released through the holes during the cooling process. In addition, a complete sintered body with obvious differences in layer structure properties is formed in the scheme of this embodiment, and the structural strength of the ceramic matrix is high, thereby improving the thermal shock resistance of the material in extreme high temperature environments.
本实施例采用的这种特殊的陶瓷基体还具有较宽的吸收光谱，在实际测试过程中，该陶瓷基体材料制成的光吸收体对0.2～20μm波长范围内的光线，均具有较高的吸收效率。The special ceramic matrix used in this embodiment also has a relatively wide absorption spectrum. In actual testing, the light absorber made of the ceramic matrix material has a relatively high absorption efficiency for light within the wavelength range of 0.2 to 20 μm.
本实施例的光吸收体的抗激光损伤薄膜材料采用了氧化铝镀膜，这种材料具有较高的耐激光损伤特性，可以对内部的陶瓷基体产生良好的抗光辐射损伤效果。即使在纳米激光的高强度辐照条件下，依然可以保持较强的抗损伤阈值，提高光吸收体的使用寿命。氧化铝镀膜的另外一个特点是具有较高的光线透过率，因此可以保证光吸收体具有较高的光线吸收率。The anti-laser damage film material of the light absorber in this embodiment adopts aluminum oxide coating, which has a high laser damage resistance and can produce a good anti-light radiation damage effect on the internal ceramic matrix. Even under the high-intensity irradiation conditions of nano-laser, it can still maintain a strong anti-damage threshold and improve the service life of the light absorber. Another feature of aluminum oxide coating is that it has a high light transmittance, so it can ensure that the light absorber has a high light absorption rate.
基于本案抗激光损伤薄膜和陶瓷基体材料的特性，本实施例还在二者的界面上通过高温热处理的方式形成一层薄薄的纳米过渡层。具体地，纳米过渡层由镀制有抗激光损伤薄膜的陶瓷基体经500～1000℃的温度恒温热处理5～30min后制得。主要是氧化铝和低钡掺杂锰酸镧两种不同的结构层材料在高温作用下发生一系列复杂的理化反应后生成的，纳米过渡层可在增强不同结构层的界面效果、提高光线的传导率和光能的转化率等方面产生正向增益。进而提升光吸收体的耐高温抗热震性能以及热导率。Based on the characteristics of the anti-laser damage film and the ceramic matrix material in this case, this embodiment also forms a thin nano transition layer on the interface between the two by high-temperature heat treatment. Specifically, the nano transition layer is made by subjecting the ceramic matrix coated with the anti-laser damage film to a constant temperature heat treatment at 500 to 1000°C for 5 to 30 minutes. It is mainly generated by a series of complex physical and chemical reactions of two different structural layer materials, aluminum oxide and low-barium-doped lanthanum manganate, under high temperature. The nano transition layer can generate positive gains in enhancing the interface effects of different structural layers, improving the conductivity of light and the conversion rate of light energy. This will improve the high temperature resistance and thermal shock resistance as well as the thermal conductivity of the light absorber.
由于本实施例提供的光吸收体具有吸收光谱较宽，对吸收光谱内的光线成分的吸收率极高；可以耐受较高的工作温度；产品的耐光损伤和抗热震性较强等特点。该型镧系钙钛矿陶瓷基光吸收体可以作为激光能量计的探头中的光能吸收材料，用于吸收0.2～20μm波段内较高光普范围内的紫外、可见以及近红外和中远红外光。Since the light absorber provided in this embodiment has a wide absorption spectrum, a very high absorption rate of light components in the absorption spectrum, can withstand high operating temperatures, and has strong resistance to light damage and thermal shock, this type of lanthanide perovskite ceramic-based light absorber can be used as a light energy absorption material in the probe of a laser energy meter to absorb ultraviolet, visible, near-infrared, mid-to-far infrared light in the higher spectrum range of the 0.2-20 μm band.
实施例2Example 2
本实施例提供一种镧系钙钛矿陶瓷基光吸收体的制备方法，该制备方法用于制备实施例1中的镧系钙钛矿陶瓷基光吸收体。具体地，制备方法包括如下步骤：This embodiment provides a method for preparing a lanthanide perovskite ceramic-based light absorber, which is used to prepare the lanthanide perovskite ceramic-based light absorber in Example 1. Specifically, the preparation method includes the following steps:
一、陶瓷粉体制备：1. Preparation of ceramic powder:
(1)将氧化镧、氧化铬和碳酸钙按照La 1-αCa αCrO 3的化学计量比混料后，固相烧结，再经球磨、过筛得到钙掺杂铬酸镧粉体；其中，α为0.3～0.7。 (1) Lanthanum oxide, chromium oxide and calcium carbonate are mixed according to the stoichiometric ratio of La 1-α Ca α CrO 3 , solid-phase sintered, and then ball-milled and sieved to obtain calcium-doped lanthanum chromate powder; wherein α is 0.3 to 0.7.
(2)将氧化镧、氧化锰和碳酸钡按照La 0.5Ba xMnO 3的预设化学计量比混料后，固相烧结，再经球磨、过筛得到低钡掺杂锰酸镧粉体；其中，x为0.1～0.3。 (2) lanthanum oxide, manganese oxide and barium carbonate are mixed according to a preset stoichiometric ratio of La 0.5 Ba x MnO 3 , solid phase sintered, and then ball milled and sieved to obtain low-barium doped lanthanum manganate powder; wherein x is 0.1 to 0.3.
(3)将氧化镧、氧化锰和碳酸钡按照La 0.5Ba yMnO 3的预设化学计量比混料后，固相烧结，再经球磨、过筛得到中钡掺杂锰酸镧粉体；其中，y为0.4～0.5。 (3) After mixing lanthanum oxide, manganese oxide and barium carbonate according to a preset stoichiometric ratio of La 0.5 Ba y MnO 3 , solid phase sintering is performed, and then ball milling and sieving are performed to obtain medium-barium-doped lanthanum manganate powder; wherein y is 0.4 to 0.5.
(4)将氧化镧、氧化锰和碳酸钡按照La 0.5Ba zMnO 3的预设化学计量比混料后，固相烧结，再经球磨、过筛得到高钡掺杂锰酸镧粉体；其中，z为0.6～0.7。 (4) lanthanum oxide, manganese oxide and barium carbonate are mixed according to a preset stoichiometric ratio of La 0.5 Ba z MnO 3 , solid phase sintered, and then ball milled and sieved to obtain high-barium doped lanthanum manganate powder; wherein z is 0.6 to 0.7.
具体地，在陶瓷粉体制备过程中，各粉体的原料在固相烧结时的烧结温度为1000～1200℃，保温时间为2～5h；球磨粉碎时的球磨速度为300r/min，球料重量比3:1，球磨时间为24～48h。Specifically, in the process of preparing ceramic powders, the sintering temperature of the raw materials of each powder during solid phase sintering is 1000-1200°C, and the insulation time is 2-5h; the ball milling speed during ball milling is 300r/min, the ball-to-material weight ratio is 3:1, and the ball milling time is 24-48h.
二、陶瓷基体制备：2. Ceramic matrix preparation:
(1)将上步骤制备出的四种陶瓷原料粉体分别与聚乙烯醇溶液混合均匀，过200目筛，得到四种不同的造粒粉末。(1) The four ceramic raw material powders prepared in the above step were respectively mixed with the polyvinyl alcohol solution and passed through a 200-mesh sieve to obtain four different granulated powders.
造粒时，本实施例在球磨出的陶瓷粉体中加入了聚乙烯醇溶液。聚乙烯醇溶液的目的是改善过细陶瓷粉体在压制阶段的成型效果。基于这一目标，本实施例选择了较低浓度的聚乙烯醇溶液，聚乙烯醇溶液的浓度为5～10％。聚乙烯醇溶液的用量也相对较少，具体地，本实施例中聚乙烯醇溶液的重量与陶瓷粉末的重量比为1:(10～12.5)。During granulation, this embodiment adds a polyvinyl alcohol solution to the ball-milled ceramic powder. The purpose of the polyvinyl alcohol solution is to improve the molding effect of the over-fine ceramic powder in the pressing stage. Based on this goal, this embodiment selects a polyvinyl alcohol solution with a lower concentration, and the concentration of the polyvinyl alcohol solution is 5-10%. The amount of polyvinyl alcohol solution is also relatively small. Specifically, in this embodiment, the weight ratio of the polyvinyl alcohol solution to the ceramic powder is 1: (10-12.5).
(2)根据拟生产的陶瓷基体的结构参数，将四种不同的造粒粉末按照所需的用量和预设顺序均匀平铺与热压模具中，并在预设模压条件下压制成生坯。(2) According to the structural parameters of the ceramic matrix to be produced, four different granulated powders are evenly spread in a hot pressing mold in the required amount and preset order, and pressed into a green body under preset molding conditions.
生坯压制步骤中，热压模具的形状和尺寸可以根据拟生产的陶瓷基体的结构参数进行合理选择。例如在本实施例中，采用
Figure PCTCN2022132885-appb-000002
的圆形热压模具。压制过程中的压力设置为10～15MPa，保压时间为5～10min。 In the green body pressing step, the shape and size of the hot pressing mold can be reasonably selected according to the structural parameters of the ceramic matrix to be produced.
Figure PCTCN2022132885-appb-000002
The pressure during the pressing process is set to 10-15 MPa, and the holding time is 5-10 minutes.
(3)在氩气环境下对压制出的生坯进行高温烧结；得到表层致密、中间多孔，且孔隙尺寸呈从中间向两侧梯度递减分布的陶瓷基体。(3) The pressed green body is subjected to high-temperature sintering in an argon environment to obtain a ceramic matrix with a dense surface, a porous middle, and a pore size that decreases gradually from the middle to both sides.
生坯烧结过程中，氩气气氛的压力设置为10～20kPa，烧结温度为1400～1500℃，烧结时间为2～4h。During the green body sintering process, the pressure of the argon atmosphere is set to 10-20 kPa, the sintering temperature is 1400-1500° C., and the sintering time is 2-4 hours.
三、抗激光损伤薄膜镀制：3. Anti-laser damage thin film coating:
以Al 2O 3为镀层材料，采用任意一种镀膜工艺，在陶瓷基体其中一侧的钙掺杂铬酸镧陶瓷层表面生成厚度为50-200nm的均匀镀层，得到的均匀镀层即为所需的抗激光损伤薄膜。 With Al 2 O 3 as the coating material, any coating process is adopted to form a uniform coating with a thickness of 50-200 nm on the surface of the calcium-doped lanthanum chromate ceramic layer on one side of the ceramic substrate. The obtained uniform coating is the required anti-laser damage film.
本实施例本实施例中的Al 2O 3镀层镀在陶瓷基体中致密的锰酸镧陶瓷层表面，镀膜的基面均匀且和镀层材料相容性和附着力好。在抗激光损伤薄膜镀制过程中，可选择的镀膜工艺包括真空蒸镀、脉冲激光沉积、原子层沉积和磁控溅射技术中任意一种。 This embodiment In this embodiment, the Al 2 O 3 coating is coated on the surface of the dense lanthanum manganate ceramic layer in the ceramic matrix, and the base surface of the coating is uniform and has good compatibility and adhesion with the coating material. In the process of coating the laser damage resistant film, the coating process that can be selected includes any one of vacuum evaporation, pulsed laser deposition, atomic layer deposition and magnetron sputtering technology.
四、纳米过渡层生成：4. Nano transition layer generation:
将上步骤制得的包含抗激光损伤薄膜的陶瓷基体送入到空气炉中，在500～1000℃的温度条件下，保温热处理5～30min，以在抗激光损伤薄膜和陶瓷基体的界面处形成特定的纳米过渡层，最后将产品自然冷却至室温，得到所需的镧系钙钛矿陶瓷基光吸收体。The ceramic substrate containing the anti-laser damage film prepared in the above step is sent into an air furnace and heat-treated at a temperature of 500-1000°C for 5-30 minutes to form a specific nano transition layer at the interface of the anti-laser damage film and the ceramic substrate. Finally, the product is naturally cooled to room temperature to obtain the desired lanthanide perovskite ceramic-based light absorber.
为了验证本实施例提供的制备方法的有效性，以及不同工艺参数条件下产品的性能差异，本实施例还采用不同工艺参数的上述制备方法对镧系钙钛矿陶瓷基光吸收体进行样品试制。具体的制备案例如下：In order to verify the effectiveness of the preparation method provided in this example, and the performance differences of the products under different process parameters, this example also uses the above preparation method with different process parameters to test the sample production of lanthanide perovskite ceramic-based light absorbers. The specific preparation cases are as follows:
测试例1Test Example 1
(1)固相法合成宽光谱高吸收的镧系钙钛矿陶瓷粉体：(1) Solid-phase synthesis of lanthanide perovskite ceramic powders with wide spectrum and high absorption:
将氧化镧、氧化锰、碳酸钡、碳酸钙、氧化铬粉末分别按La 0.5Ba 0.1MnO 3、La 0.5Ba 0.4MnO 3、La 0.5Ba 0.6MnO 3和La 0.7Ca 0.3CrO 3的化学计量比进行混料后固相烧结。烧结温度为1000℃，升温速度为5℃/min，保温时间为5h。烧结产物以300转/min的速度球磨24h、过筛；最后得到三种不同掺杂率的钡掺杂锰酸镧，以及钙掺杂铬酸镧粉末。 Lanthanum oxide, manganese oxide, barium carbonate, calcium carbonate and chromium oxide powders were mixed in the stoichiometric ratio of La 0.5 Ba 0.1 MnO 3 , La 0.5 Ba 0.4 MnO 3 , La 0.5 Ba 0.6 MnO 3 and La 0.7 Ca 0.3 CrO 3 , respectively, and then solid phase sintered. The sintering temperature was 1000℃, the heating rate was 5℃/min, and the holding time was 5h. The sintered product was ball milled at a speed of 300 rpm for 24h and sieved; finally, three barium-doped lanthanum manganate powders with different doping rates and calcium-doped lanthanum chromate powders were obtained.
(2)制备孔隙梯度七层结构镧系钙钛矿陶瓷基片：(2) Preparation of pore gradient seven-layer structure lanthanide perovskite ceramic substrate:
首先，将上述四种粉末与聚乙烯醇溶液混合均匀，过200目筛，得到造粒后的粉末。其中，聚乙烯醇溶液的浓度为5％，聚乙烯醇溶液与陶瓷粉末的重量比为1:12。然后，将造粒后的粉末按照第一和第七层为La 0.5Ba 0.1MnO 3，第二和第六层为La 0.5Ba 0.4MnO 3，第三和五层为La 0.5Ba 0.6MnO 3，第四层为La 0.7Ca 0.3CrO 3的顺序依次均匀平铺于
Figure PCTCN2022132885-appb-000003
的热压模具中，并在10Mpa的模压下保压10min得到生坯。最后，在氩气环境下于1400℃高温，以及20kPa气氛压力，烧结4h；得到表层致密、中间多孔的陶瓷基体。 First, the above four powders were mixed evenly with polyvinyl alcohol solution and passed through a 200 mesh sieve to obtain granulated powder. The concentration of the polyvinyl alcohol solution was 5%, and the weight ratio of the polyvinyl alcohol solution to the ceramic powder was 1:12. Then, the granulated powder was evenly spread on the first and seventh layers in the order of La 0.5 Ba 0.1 MnO 3 , the second and sixth layers of La 0.5 Ba 0.4 MnO 3 , the third and fifth layers of La 0.5 Ba 0.6 MnO 3 , and the fourth layer of La 0.7 Ca 0.3 CrO 3.
Figure PCTCN2022132885-appb-000003
The green body was obtained by placing the green body in a hot pressing mold and maintaining the pressure at 10 MPa for 10 minutes. Finally, the green body was sintered for 4 hours at 1400°C and 20 kPa atmosphere pressure in an argon environment to obtain a ceramic matrix with a dense surface and porous middle.
其中，烧结产物中的第一和第七层为厚0.05mm、致密的La 0.5Ba 0.1MnO 3。第二和第六层为厚0.05mm、较小孔的La 0.5Ba 0.4MnO 3。第三和第五层为厚0.05mm、中孔的La 0.5Ba 0.6MnO 3。第四层为厚0.2mm、较大孔的La 0.7Ca 0.3CrO 3。 The first and seventh layers in the sintered product are 0.05 mm thick, dense La 0.5 Ba 0.1 MnO 3 . The second and sixth layers are 0.05 mm thick, relatively small-pore La 0.5 Ba 0.4 MnO 3 . The third and fifth layers are 0.05 mm thick, medium-pore La 0.5 Ba 0.6 MnO 3 . The fourth layer is 0.2 mm thick, relatively large-pore La 0.7 Ca 0.3 CrO 3 .
(3)镀制致密Al 2O 3膜： (3) Plating of dense Al 2 O 3 film:
采用真空蒸镀技术在陶瓷基体表面镀制200nm厚的Al 2O 3膜。 A 200nm thick Al 2 O 3 film was deposited on the surface of the ceramic substrate using vacuum evaporation technology.
(4)在空气炉中热处理：(4) Heat treatment in an air furnace:
将上述膜基结构置于空气炉中，以500℃的温度热处理30min，取出自然冷却后得到所需镧系钙钛矿陶瓷基光吸收体。The above-mentioned film-based structure was placed in an air furnace, heat-treated at a temperature of 500° C. for 30 minutes, and then taken out and naturally cooled to obtain the desired lanthanide perovskite ceramic-based light absorber.
测试例2Test Example 2
(1)固相法合成宽光谱高吸收的镧系钙钛矿陶瓷粉体：(1) Solid-phase synthesis of lanthanide perovskite ceramic powders with wide spectrum and high absorption:
将氧化镧、氧化锰、碳酸钡、碳酸钙、氧化铬粉末分别按La 0.5Ba 0.2MnO 3、La 0.5Ba 0.5MnO 3、La 0.5Ba 0.7MnO 3和La 0.6Ca 0.4CrO 3的化学计量比进行混料后固相烧结。烧结温度为1100℃，升温速度为5℃/min，保温时间为3h。再经300r/min的速度球磨48h、过筛分别得到三种不同掺杂率的钡掺杂锰酸镧，以及钙掺杂铬酸镧粉末。 Lanthanum oxide, manganese oxide, barium carbonate, calcium carbonate and chromium oxide powders were mixed in the stoichiometric ratio of La 0.5 Ba 0.2 MnO 3 , La 0.5 Ba 0.5 MnO 3 , La 0.5 Ba 0.7 MnO 3 and La 0.6 Ca 0.4 CrO 3 , respectively, and then solid phase sintered. The sintering temperature was 1100℃, the heating rate was 5℃/min, and the holding time was 3h. After ball milling at a speed of 300r/min for 48h, three barium-doped lanthanum manganate powders with different doping rates and calcium-doped lanthanum chromate powders were obtained through sieving.
(2)制备孔隙梯度七层结构镧系钙钛矿陶瓷基片：(2) Preparation of pore gradient seven-layer structure lanthanide perovskite ceramic substrate:
首先，将上述四种粉末与聚乙烯醇溶液混合均匀，过200目筛，得到造粒后的粉末。其中，聚乙烯醇溶液的浓度为6％，聚乙烯醇溶液与陶瓷粉末的重量比为1:11.1。然后，将造粒后的粉末按照第一和第七层为La 0.5Ba 0.2MnO 3，第二和第六层为La 0.5Ba 0.5MnO 3，第三和五 层为La 0.5Ba 0.7MnO 3，第四层为La 0.6Ca 0.4CrO 3的顺序依次均匀平铺于
Figure PCTCN2022132885-appb-000004
的热压模具中，并在11Mpa的模压下保压9min得到生坯。最后，在氩气环境下于1450℃高温以及15kPa气氛压力为烧结3h，即得到表层致密中间多孔的陶瓷基体。 First, the above four powders were mixed evenly with the polyvinyl alcohol solution and passed through a 200-mesh sieve to obtain granulated powders. The concentration of the polyvinyl alcohol solution was 6%, and the weight ratio of the polyvinyl alcohol solution to the ceramic powder was 1:11.1. Then, the granulated powders were evenly spread on the surface of the ceramic powder in the following order: the first and seventh layers were La 0.5 Ba 0.2 MnO 3 , the second and sixth layers were La 0.5 Ba 0.5 MnO 3 , the third and fifth layers were La 0.5 Ba 0.7 MnO 3 , and the fourth layer was La 0.6 Ca 0.4 CrO 3.
Figure PCTCN2022132885-appb-000004
The green body was obtained by placing the green body in a hot pressing mold and maintaining the pressure at 11Mpa for 9 minutes. Finally, the green body was sintered for 3 hours at 1450℃ and 15kPa in an argon environment to obtain a ceramic matrix with a dense surface and porous middle.
其中，烧结产物中的第一和第七层为厚0.05mm、致密的La 0.5Ba 0.2MnO 3。第二和第六层为厚0.05mm、较小孔的La 0.5Ba 0.5MnO 3。第三和第五层为厚0.1mm、中孔的La 0.5Ba 0.7MnO 3。第四层为厚0.2mm、较大孔的La 0.6Ca 0.4CrO 3。 The first and seventh layers in the sintered product are 0.05 mm thick, dense La 0.5 Ba 0.2 MnO 3 . The second and sixth layers are 0.05 mm thick, relatively small-pore La 0.5 Ba 0.5 MnO 3 . The third and fifth layers are 0.1 mm thick, medium-pore La 0.5 Ba 0.7 MnO 3 . The fourth layer is 0.2 mm thick, relatively large-pore La 0.6 Ca 0.4 CrO 3 .
(3)镀制致密Al 2O 3膜： (3) Plating of dense Al 2 O 3 film:
采用脉冲激光沉积技术在孔隙梯度陶瓷表面镀制150nm厚的Al 2O 3膜。 The Al 2 O 3 film with a thickness of 150 nm was deposited on the surface of the porous gradient ceramic by pulsed laser deposition technology.
(4)在空气炉中热处理：(4) Heat treatment in an air furnace:
将上述膜基结构置于空气炉中，在600℃的温度下恒温热处理25min；取出自然冷却后得到所需镧系钙钛矿陶瓷基光吸收体。The above-mentioned film-based structure is placed in an air furnace and subjected to constant temperature heat treatment at 600° C. for 25 minutes; after being taken out and naturally cooled, the desired lanthanide perovskite ceramic-based light absorber is obtained.
测试例3Test Example 3
(1)固相法合成宽光谱高吸收的镧系钙钛矿陶瓷粉体：(1) Solid-phase synthesis of lanthanide perovskite ceramic powders with wide spectrum and high absorption:
将氧化镧、氧化锰、碳酸钡、碳酸钙、氧化铬粉末分别按La 0.5Ba 0.3MnO 3、La 0.5Ba 0.4MnO 3、La 0.5Ba 0.6MnO 3和La 0.5Ca 0.5CrO 3的化学计量比进行混料后固相烧结。烧结温度为1050℃，升温速度为5℃/min，保温时间为4h。再经以300r/min的速度球磨36h、过筛分别得到三种不同掺杂率的钡掺杂锰酸镧，以及钙掺杂铬酸镧粉末。 Lanthanum oxide, manganese oxide, barium carbonate, calcium carbonate and chromium oxide powders were mixed in the stoichiometric ratio of La 0.5 Ba 0.3 MnO 3 , La 0.5 Ba 0.4 MnO 3 , La 0.5 Ba 0.6 MnO 3 and La 0.5 Ca 0.5 CrO 3 , respectively, and then solid phase sintered. The sintering temperature was 1050℃, the heating rate was 5℃/min, and the holding time was 4h. Then, the powders were ball milled at a speed of 300r/min for 36h and sieved to obtain three different doping rates of barium-doped lanthanum manganate and calcium-doped lanthanum chromate powders.
(2)制备孔隙梯度七层结构镧系钙钛矿陶瓷基片：(2) Preparation of pore gradient seven-layer structure lanthanide perovskite ceramic substrate:
首先，将上述四种粉末与聚乙烯醇溶液混合均匀，过200目筛，得到造粒后的粉末。其中，聚乙烯醇溶液的浓度为8％，聚乙烯醇溶液与陶瓷粉末的重量比为1:12.5；然后，将造粒后的粉末按照第一和第七层为La 0.5Ba 0.3MnO 3，第二和第六层为La 0.5Ba 0.4MnO 3，第三和五层为La 0.5Ba 0.6MnO 3，第四层为La 0.5Ca 0.5CrO 3的顺序依次均匀平铺于
Figure PCTCN2022132885-appb-000005
的热压模具中，并在14Mpa的模压下保压7min得到生坯。最后，在氩气环境下于1500℃高温以及10kPa的气压条件下为烧结2h，即得到表层致密中间多孔的陶瓷基体。 First, the above four powders were mixed evenly with polyvinyl alcohol solution and passed through a 200-mesh sieve to obtain granulated powders. The concentration of the polyvinyl alcohol solution was 8%, and the weight ratio of the polyvinyl alcohol solution to the ceramic powder was 1:12.5. Then, the granulated powders were evenly spread on a plate in the order of La 0.5 Ba 0.3 MnO 3 for the first and seventh layers, La 0.5 Ba 0.4 MnO 3 for the second and sixth layers, La 0.5 Ba 0.6 MnO 3 for the third and fifth layers, and La 0.5 Ca 0.5 CrO 3 for the fourth layer.
Figure PCTCN2022132885-appb-000005
The green body was obtained by placing the green body in a hot pressing mold and maintaining the pressure at 14 MPa for 7 minutes. Finally, the green body was sintered for 2 hours at 1500°C and 10 kPa in an argon environment to obtain a ceramic matrix with a dense surface and porous middle.
其中，烧结产物中的第一和第七层为厚0.1mm、致密的La 0.5Ba 0.3MnO 3。第二和第六层为厚0.1mm、较小孔的La 0.5Ba 0.4MnO 3。第三和第五层为厚0.1mm、中孔的La 0.5Ba 0.6MnO 3。第四层为厚0.2mm、较大孔的La 0.5Ca 0.5CrO 3。 The first and seventh layers in the sintered product are 0.1 mm thick, dense La 0.5 Ba 0.3 MnO 3 . The second and sixth layers are 0.1 mm thick, relatively small-pore La 0.5 Ba 0.4 MnO 3 . The third and fifth layers are 0.1 mm thick, medium-pore La 0.5 Ba 0.6 MnO 3 . The fourth layer is 0.2 mm thick, relatively large-pore La 0.5 Ca 0.5 CrO 3 .
(3)镀制致密Al 2O 3膜： (3) Plating of dense Al 2 O 3 film:
采用原子层沉积技术在孔隙梯度陶瓷表面镀制50nm厚的Al 2O 3膜。 Atomic layer deposition technology was used to deposit a 50nm thick Al 2 O 3 film on the surface of the pore gradient ceramic.
(4)在空气炉中热处理：(4) Heat treatment in an air furnace:
将上述膜基结构置于空气炉中，在1000℃的温度条件下，恒温热处理5min；取出自然冷却后得到所需镧系钙钛矿陶瓷基光吸收体。The above-mentioned film-based structure is placed in an air furnace and subjected to constant temperature heat treatment for 5 minutes at a temperature of 1000° C.; after being taken out and naturally cooled, the desired lanthanide perovskite ceramic-based light absorber is obtained.
测试例4Test Example 4
(1)固相法合成宽光谱高吸收的镧系钙钛矿陶瓷粉体：(1) Solid-phase synthesis of lanthanide perovskite ceramic powders with wide spectrum and high absorption:
将氧化镧、氧化锰、碳酸钡、碳酸钙、氧化铬粉末分别按La 0.5Ba 0.3MnO 3、La 0.5Ba 0.5MnO 3、La 0.5Ba 0.7MnO 3和La 0.3Ca 07CrO 3的化学计量比进行混料后固相烧结。烧结温度为1050℃，升温速度为5℃/min，保温时间为4h。再经以300r/min的速度球磨48h、过筛；分别得到钙掺杂铬酸镧粉末，以及三种不同掺杂率的钡掺杂锰酸镧粉末。 Lanthanum oxide, manganese oxide, barium carbonate, calcium carbonate and chromium oxide powders were mixed in the stoichiometric ratio of La 0.5 Ba 0.3 MnO 3 , La 0.5 Ba 0.5 MnO 3 , La 0.5 Ba 0.7 MnO 3 and La 0.3 Ca 07 CrO 3 , respectively, and then solid phase sintered. The sintering temperature was 1050℃, the heating rate was 5℃/min, and the holding time was 4h. After ball milling at a speed of 300r/min for 48h and sieving, calcium-doped lanthanum chromate powder and three barium-doped lanthanum manganate powders with different doping rates were obtained.
(2)制备孔隙梯度七层结构镧系钙钛矿陶瓷基片：(2) Preparation of pore gradient seven-layer structure lanthanide perovskite ceramic substrate:
首先，将上述四种粉末分别与聚乙烯醇溶液混合均匀，过200目筛，得到造粒后的粉末。其中，聚乙烯醇溶液的浓度为10％，聚乙烯醇溶液与陶瓷粉末的重量比为1:10。然后，将造粒后的粉末按照第一和第七层为La 0.5Ba 0.3MnO 3，第二和第六层为La 0.5Ba 0.5MnO 3，第三和五层为La 0.5Ba 0.7MnO 3，第四层为La 0.3Ca 0.7CrO 3的顺序，依次均匀平铺于
Figure PCTCN2022132885-appb-000006
的热压模具中，并在15Mpa的模压下保压5min得到生坯。最后，在氩气环境下于1500℃高温以及10kPa的气氛压力条件下烧结2h，即得到表层致密中间多孔的陶瓷基体。 First, the above four powders were mixed with polyvinyl alcohol solution respectively and passed through a 200 mesh sieve to obtain granulated powders. The concentration of the polyvinyl alcohol solution was 10%, and the weight ratio of the polyvinyl alcohol solution to the ceramic powder was 1:10. Then, the granulated powders were evenly spread on the surface of the ceramic powder in the following order: the first and seventh layers were La 0.5 Ba 0.3 MnO 3 , the second and sixth layers were La 0.5 Ba 0.5 MnO 3 , the third and fifth layers were La 0.5 Ba 0.7 MnO 3 , and the fourth layer was La 0.3 Ca 0.7 CrO 3 .
Figure PCTCN2022132885-appb-000006
The green body was obtained by placing the green body in a hot pressing mold and maintaining the pressure at 15Mpa for 5 minutes. Finally, the green body was sintered for 2 hours at 1500℃ and 10kPa in an argon environment to obtain a ceramic matrix with a dense surface and porous middle.
其中，烧结产物中的第一和第七层为厚0.1mm、致密的La 0.5Ba 0.3MnO 3。第二和第六层为厚0.1mm、较小孔的La 0.5Ba 0.5MnO 3。第三和第五层为厚0.2mm、中孔的La 0.5Ba 0.7MnO 3。第四层为厚0.2mm、较大孔的La 0.3Ca 0.7CrO 3。 The first and seventh layers in the sintered product are 0.1 mm thick, dense La 0.5 Ba 0.3 MnO 3 . The second and sixth layers are 0.1 mm thick, relatively small-pore La 0.5 Ba 0.5 MnO 3 . The third and fifth layers are 0.2 mm thick, medium-pore La 0.5 Ba 0.7 MnO 3 . The fourth layer is 0.2 mm thick, relatively large-pore La 0.3 Ca 0.7 CrO 3 .
(3)镀制致密Al 2O 3膜： (3) Plating of dense Al 2 O 3 film:
采用磁控溅射技术在孔隙梯度陶瓷表面镀制50nm厚的Al 2O 3膜。 A 50nm thick Al 2 O 3 film was deposited on the surface of the porous gradient ceramic by magnetron sputtering technology.
(4)在空气炉中热处理：(4) Heat treatment in an air furnace:
将上述膜基结构置于空气炉中，在1000℃的温度条件下保温热处理5min；取出自然冷却后，得到所需镧系钙钛矿陶瓷基光吸收体。The above-mentioned film-based structure is placed in an air furnace and heat-treated at a temperature of 1000° C. for 5 minutes; after being taken out and naturally cooled, the desired lanthanide perovskite ceramic-based light absorber is obtained.
性能测试：Performance Testing:
1、陶瓷基体各结构层的局部微观结构1. Local microstructure of each structural layer of the ceramic matrix
在以上各测试例制备出的样品中，具有孔隙梯度的七层结构镧系钙钛矿基陶瓷中各个结构层的电镜照片均如附图2-5所示。不同样品中，对应陶瓷层中孔隙的大小和密度差异不大，且整体均呈明显的七层结构。In the samples prepared in the above test examples, the electron microscope photos of each structural layer in the seven-layer structure lanthanide perovskite-based ceramic with pore gradient are shown in Figures 2 to 5. In different samples, the size and density of the pores in the corresponding ceramic layers are not much different, and the overall seven-layer structure is obvious.
2、光吸收体的性能测试2. Performance test of light absorber
为了验证本实施例提供的各个光吸收体的产品性能，本实施例还对各测试例中制备出各 个样品进行性能测试，测试项目包括：耐高温性能、抗热震性能，以及在不同波段内材料的光吸收率。各测试例中样品的性能测试结果如下：In order to verify the product performance of each light absorber provided in this embodiment, this embodiment also performs performance tests on each sample prepared in each test example. The test items include: high temperature resistance, thermal shock resistance, and light absorption rate of materials in different bands. The performance test results of the samples in each test example are as follows:
(1)吸收光谱(1) Absorption spectrum
考虑到光吸收体中对光成分起到吸收作用的主要是陶瓷基体。本实施例对陶瓷基体中不同组分和结构的陶瓷体的吸收性能进行测试和统计，并绘制出如下吸收光谱。其中，各材料在0-2.5微米波段内的吸收光谱如图7所示，而在2.5-20微米波段(工作波段)内吸收光谱如图8所示，分析图中数据可知：本实施例中光吸收体中各层材料在工作波段范围内的光吸收率均维持在较高水平，可以产生良好的光吸收效果。其中，本实施例的光吸收体在2.5-14微米波段内的吸收率均维持在极高水平，平均吸收率达80％以上，而在14-20微米波段内吸收率存在波动，但仍在可接受范围内。Considering that the main component that absorbs light components in the light absorber is the ceramic matrix. This embodiment tests and statistics the absorption properties of ceramic bodies with different components and structures in the ceramic matrix, and draws the following absorption spectrum. Among them, the absorption spectrum of each material in the 0-2.5 micron band is shown in Figure 7, and the absorption spectrum in the 2.5-20 micron band (working band) is shown in Figure 8. From the analysis of the data in the figure, it can be seen that: the light absorption rate of each layer of material in the light absorber in this embodiment within the working band is maintained at a relatively high level, which can produce a good light absorption effect. Among them, the absorption rate of the light absorber of this embodiment in the 2.5-14 micron band is maintained at an extremely high level, with an average absorption rate of more than 80%, and the absorption rate in the 14-20 micron band fluctuates, but it is still within an acceptable range.
(2)耐高温抗热震测试(2) High temperature resistance and thermal shock resistance test
光吸收体的抗热震性通过以下空冷方法进行测试。将光吸收体置于1200℃的马弗炉中并保持15分钟，然后迅速从马弗炉中取出并在空气中冷却至室温。上述实验过程重复30次。The thermal shock resistance of the light absorber was tested by the following air cooling method. The light absorber was placed in a muffle furnace at 1200°C and kept for 15 minutes, then quickly taken out of the muffle furnace and cooled to room temperature in air. The above experimental process was repeated 30 times.
(3)抗激光损失性能(3) Anti-laser loss performance
通过1-on-1测试方法，包括在具有不同激光能量密度的光吸收体的至少10个不同采样点上采集的一个激光辐射样本。光吸收体抗激光损失性能图的绘制取决于能量密度，然后将数据线性外推以找到损伤概率为0％的位置，即是激光损伤性能。在数据处理过程中进行统计分析，从而减小样品表面缺陷在损伤阈值测量中引入的误差。The 1-on-1 test method includes a laser irradiation sample collected at least 10 different sampling points of the optical absorber with different laser energy densities. The plotting of the optical absorber's anti-laser loss performance diagram depends on the energy density, and then the data is linearly extrapolated to find the position where the damage probability is 0%, that is, the laser damage performance. Statistical analysis is performed during data processing to reduce the error introduced by sample surface defects in damage threshold measurement.
表1：各测试例样品的性能测试结果统计表Table 1: Statistics of performance test results of each test case sample
Figure PCTCN2022132885-appb-000007
Figure PCTCN2022132885-appb-000007
实施例3Example 3
本实施例提供一种宽光谱的激光能量计，该激光能量计的的探头中采用了如实施例2的制备方法制备出的镧系钙钛矿陶瓷基光吸收体。因此，该激光能量计有较宽的吸收光谱，光吸收率高。同时还有较强的耐光损伤性能和抗热震性能。产品的使用寿命得到明显提升。This embodiment provides a wide-spectrum laser energy meter, in which the probe of the laser energy meter adopts the lanthanide perovskite ceramic-based light absorber prepared by the preparation method of Example 2. Therefore, the laser energy meter has a wide absorption spectrum and a high light absorption rate. At the same time, it also has strong light damage resistance and thermal shock resistance. The service life of the product is significantly improved.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims (10)

  1. 一种镧系钙钛矿陶瓷基光吸收体，其特征在于，其包括：A lanthanide perovskite ceramic-based light absorber, characterized in that it comprises:
    陶瓷基体，其包括七个按照预设顺序依次叠层分布的结构层；各结构层包括位于中间层的钙掺杂铬酸镧陶瓷层；位于所述钙掺杂铬酸镧陶瓷层上下两侧的高钡掺杂锰酸镧陶瓷层；位于所述高钡掺杂锰酸镧陶瓷层上下两侧的中钡掺杂锰酸镧陶瓷层；以及位于所述中钡掺杂锰酸镧陶瓷层上下两侧的致密的低钡掺杂锰酸镧陶瓷层；其中，钙掺杂铬酸镧陶瓷层、高钡掺杂锰酸镧陶瓷层、中钡掺杂锰酸镧陶瓷层呈多孔结构，所述陶瓷基体中各结构层中的孔隙尺寸从中间向两侧呈梯度递减的分布状态；所述陶瓷基体中各结构层的厚度为0.05-0.2mm，总厚度为0.5-1mm；A ceramic matrix, comprising seven structural layers stacked in sequence according to a preset order; each structural layer comprises a calcium-doped lanthanum chromate ceramic layer located in the middle layer; a high-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the calcium-doped lanthanum chromate ceramic layer; a medium-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the high-barium-doped lanthanum manganate ceramic layer; and a dense low-barium-doped lanthanum manganate ceramic layer located on the upper and lower sides of the medium-barium-doped lanthanum manganate ceramic layer; wherein the calcium-doped lanthanum chromate ceramic layer, the high-barium-doped lanthanum manganate ceramic layer, and the medium-barium-doped lanthanum manganate ceramic layer are porous structures, and the pore size in each structural layer in the ceramic matrix is distributed in a gradient decreasing state from the middle to the two sides; the thickness of each structural layer in the ceramic matrix is 0.05-0.2 mm, and the total thickness is 0.5-1 mm;
    抗激光损伤薄膜，其位于所述陶瓷基体中钙掺杂锰酸镧陶瓷层的外表面；所述抗激光损伤薄膜材料为氧化铝陶瓷；所述抗激光损伤薄膜的厚度为50-200nm；以及A laser damage resistant film, which is located on the outer surface of the calcium-doped lanthanum manganate ceramic layer in the ceramic matrix; the laser damage resistant film material is alumina ceramic; the laser damage resistant film has a thickness of 50-200 nm; and
    纳米过渡层，其由陶瓷基体和抗激光损伤薄膜中的相邻结构层经高温热处理后生成，并位于二者的界面处。The nano transition layer is generated by high-temperature heat treatment of the ceramic matrix and the adjacent structural layer in the laser damage resistant film, and is located at the interface between the two.
  2. 如权利要求1所述的镧系钙钛矿陶瓷基光吸收体，其特征在于：所述钙掺杂铬酸镧的化学组成为：La 1-αCa αCrO 3，其中，表征Ca掺杂量的α为0.3～0.7；所述低钡掺杂锰酸镧的化学组成为：La 0.5Ba xMnO 3，其中，表征Ba掺杂量的x为0.1～0.3；所述中钡掺杂锰酸镧的化学组成为：La 0.5Ba yMnO 3，其中，表征Ba掺杂量的y为0.4～0.5；所述高钡掺杂锰酸镧的化学组成为：La 0.5Ba zMnO 3，其中，表征Ba的掺杂量z为0.6～0.7。 The lanthanum perovskite ceramic-based light absorber according to claim 1 is characterized in that: the chemical composition of the calcium-doped lanthanum chromate is: La 1-α Ca α CrO 3 , wherein α representing the Ca doping amount is 0.3-0.7; the chemical composition of the low-barium-doped lanthanum manganate is: La 0.5 Ba x MnO 3 , wherein x representing the Ba doping amount is 0.1-0.3; the chemical composition of the medium-barium-doped lanthanum manganate is: La 0.5 Ba y MnO 3 , wherein y representing the Ba doping amount is 0.4-0.5; the chemical composition of the high-barium-doped lanthanum manganate is: La 0.5 Ba z MnO 3 , wherein z representing the Ba doping amount is 0.6-0.7.
  3. 如权利要求1所述的镧系钙钛矿陶瓷基光吸收体，其特征在于：所述纳米过渡层由镀制有抗激光损伤薄膜的陶瓷基体经500～1000℃的温度恒温热处理5～30min后制得。The lanthanide perovskite ceramic-based light absorber according to claim 1 is characterized in that the nano-transition layer is prepared by subjecting a ceramic substrate coated with an anti-laser damage film to a constant temperature heat treatment at a temperature of 500 to 1000° C. for 5 to 30 minutes.
  4. 一种如权利要求1-3任意一项所述的镧系钙钛矿陶瓷基光吸收体的应用，其特征在于：将所述镧系钙钛矿陶瓷基作为激光能量计的探头中的光能吸收材料，用于吸收0.2～20μm波段内的紫外、可见以及近红外和中远红外光。An application of a lanthanide perovskite ceramic-based light absorber as described in any one of claims 1 to 3, characterized in that the lanthanide perovskite ceramic-based light absorber is used as a light energy absorption material in a probe of a laser energy meter to absorb ultraviolet, visible, near-infrared, mid-to-far-infrared light in the 0.2 to 20 μm band.
  5. 一种宽光谱的激光能量计，其特征在于：其使用的探头中采用了如权利要求1-3中任意一项所述的镧系钙钛矿陶瓷基。A wide spectrum laser energy meter, characterized in that the probe used therein adopts the lanthanide perovskite ceramic matrix as described in any one of claims 1 to 3.
  6. 一种镧系钙钛矿陶瓷基光吸收体的制备方法，其特征在于：其用于制备如权利要求1-3中任意一项所述的镧系钙钛矿陶瓷基光吸收体；所述制备方法包括如下步骤：A method for preparing a lanthanide perovskite ceramic-based light absorber, characterized in that it is used to prepare the lanthanide perovskite ceramic-based light absorber as claimed in any one of claims 1 to 3; the preparation method comprises the following steps:
    一、陶瓷粉体制备：1. Preparation of ceramic powder:
    (1)将氧化镧、氧化铬和碳酸钙按照La 1-αCa αCrO 3的化学计量比混料后，固相烧结， 再经球磨、过筛得到钙掺杂铬酸镧粉体；其中，α为0.3～0.7； (1) lanthanum oxide, chromium oxide and calcium carbonate are mixed according to the stoichiometric ratio of La 1-α Ca α CrO 3 , solid-phase sintered, and then ball-milled and sieved to obtain calcium-doped lanthanum chromate powder; wherein α is 0.3 to 0.7;
    (2)将氧化镧、氧化锰和碳酸钡按照La 0.5Ba xMnO 3的预设化学计量比混料后，固相烧结，再经球磨、过筛得到低钡掺杂锰酸镧粉体；其中，x为0.1～0.3； (2) mixing lanthanum oxide, manganese oxide and barium carbonate according to a preset stoichiometric ratio of La 0.5 Ba x MnO 3 , solid phase sintering, and then ball milling and sieving to obtain low-barium doped lanthanum manganate powder; wherein x is 0.1 to 0.3;
    (3)将氧化镧、氧化锰和碳酸钡按照La 0.5Ba yMnO 3的预设化学计量比混料后，固相烧结，再经球磨、过筛得到中钡掺杂锰酸镧粉体；其中，y为0.4～0.5； (3) mixing lanthanum oxide, manganese oxide and barium carbonate according to a preset stoichiometric ratio of La 0.5 Ba y MnO 3 , solid phase sintering, and then ball milling and sieving to obtain medium-barium-doped lanthanum manganate powder; wherein y is 0.4 to 0.5;
    (4)将氧化镧、氧化锰和碳酸钡按照La 0.5Ba zMnO 3的预设化学计量比混料后，固相烧结，再经球磨、过筛得到高钡掺杂锰酸镧粉体；其中，z为0.6～0.7； (4) mixing lanthanum oxide, manganese oxide and barium carbonate according to a preset stoichiometric ratio of La 0.5 Ba z MnO 3 , solid phase sintering, and then ball milling and sieving to obtain high-barium doped lanthanum manganate powder; wherein z is 0.6 to 0.7;
    二、陶瓷基体制备：2. Ceramic matrix preparation:
    (1)将上步骤制备出的四种陶瓷原料粉体分别与聚乙烯醇溶液混合均匀，过200目筛，得到四种不同的造粒粉末；(1) The four ceramic raw material powders prepared in the above step are respectively mixed with the polyvinyl alcohol solution and passed through a 200-mesh sieve to obtain four different granulated powders;
    (2)根据拟生产的陶瓷基体的结构参数，将四种不同的造粒粉末按照所需的用量和预设顺序均匀平铺与热压模具中，并在预设模压条件下压制成生坯；(2) according to the structural parameters of the ceramic matrix to be produced, four different granulated powders are evenly spread in a hot pressing mold in the required amount and in a preset order, and pressed into a green body under preset molding conditions;
    (3)在氩气环境下对压制出的生坯进行高温烧结；得到表层致密、中间多孔，且孔隙尺寸呈从中间向两侧梯度递减分布的陶瓷基体；(3) sintering the pressed green body at high temperature in an argon environment to obtain a ceramic matrix with a dense surface layer, porous middle, and pore size gradually decreasing from the middle to both sides;
    三、抗激光损伤薄膜镀制：3. Anti-laser damage thin film coating:
    以Al 2O 3为镀层材料，采用任意一种镀膜工艺，在所述陶瓷基体其中一侧的钙掺杂铬酸镧陶瓷层表面生成厚度为50-200nm的均匀镀层，得到的均匀镀层即为所需的抗激光损伤薄膜； Using Al 2 O 3 as the coating material and adopting any coating process, a uniform coating with a thickness of 50-200 nm is formed on the surface of the calcium-doped lanthanum chromate ceramic layer on one side of the ceramic substrate, and the obtained uniform coating is the desired anti-laser damage film;
    四、纳米过渡层生成：4. Nano transition layer generation:
    将上步骤制得的包含抗激光损伤薄膜的陶瓷基体送入到空气炉中，在500～1000℃的温度条件下，保温热处理5～30min，以在抗激光损伤薄膜和陶瓷基体的界面处形成特定的纳米过渡层；将产品自然冷却至室温，得到所需的镧系钙钛矿陶瓷基光吸收体。The ceramic substrate containing the anti-laser damage film prepared in the above step is sent into an air furnace and heat-treated at a temperature of 500-1000°C for 5-30 minutes to form a specific nano transition layer at the interface of the anti-laser damage film and the ceramic substrate; the product is naturally cooled to room temperature to obtain the desired lanthanide perovskite ceramic-based light absorber.
  7. 如权利要求6所述的镧系钙钛矿陶瓷基光吸收体的制备方法，其特征在于：在陶瓷粉体制备过程中，各粉体的原料在固相烧结时的烧结温度为1000～1200℃，保温时间为2～5h；球磨粉碎时的球磨速度为300r/min，球料重量比3:1，球磨时间为24～48h。The method for preparing a lanthanide perovskite ceramic-based light absorber as described in claim 6 is characterized in that: in the process of preparing ceramic powders, the sintering temperature of the raw materials of each powder during solid-phase sintering is 1000-1200°C, and the insulation time is 2-5h; the ball milling speed during ball milling is 300r/min, the ball-to-material weight ratio is 3:1, and the ball milling time is 24-48h.
  8. 如权利要求6所述的镧系钙钛矿陶瓷基光吸收体的制备方法，其特征在于：在陶瓷基体制备过程中，造粒粉末中使用的聚乙烯醇溶液的浓度为5～10％，聚乙烯醇溶液的重量与陶瓷粉末的重量比为1:(10～12.5)。The method for preparing a lanthanide perovskite ceramic-based light absorber as described in claim 6 is characterized in that: during the preparation of the ceramic matrix, the concentration of the polyvinyl alcohol solution used in the granulated powder is 5-10%, and the weight ratio of the polyvinyl alcohol solution to the ceramic powder is 1: (10-12.5).
  9. 如权利要求6所述的镧系钙钛矿陶瓷基光吸收体的制备方法，其特征在于：在陶瓷基体制备过程中，生坯压制步骤中，采用
    Figure PCTCN2022132885-appb-100001
    的热压模具，压力设置为10～15MPa，保压 时间为5～10min；生坯烧结过程中，氩气的压力设置为10～20kPa，烧结温度为1400～1500℃，烧结时间为2～4h。     The method for preparing a lanthanide perovskite ceramic-based light absorber according to claim 6, characterized in that: in the process of preparing the ceramic matrix, in the green body pressing step,
    Figure PCTCN2022132885-appb-100001
    The hot pressing mold has a pressure set to 10-15MPa and a holding time of 5-10min. During the green body sintering process, the argon pressure is set to 10-20kPa, the sintering temperature is 1400-1500°C, and the sintering time is 2-4h.
  10. 如权利要求6所述的镧系钙钛矿陶瓷基光吸收体的制备方法，其特征在于：抗激光损伤薄膜镀制过程中，可选择的镀膜工艺包括真空蒸镀、脉冲激光沉积、原子层沉积和磁控溅射技术。The method for preparing a lanthanide perovskite ceramic-based light absorber as described in claim 6 is characterized in that: during the coating process of the laser damage-resistant thin film, the selectable coating processes include vacuum evaporation, pulsed laser deposition, atomic layer deposition and magnetron sputtering technology.
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