CN115353389A - Ho ion doped sesquioxide transparent ceramic and preparation method thereof - Google Patents

Ho ion doped sesquioxide transparent ceramic and preparation method thereof Download PDF

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CN115353389A
CN115353389A CN202211175496.7A CN202211175496A CN115353389A CN 115353389 A CN115353389 A CN 115353389A CN 202211175496 A CN202211175496 A CN 202211175496A CN 115353389 A CN115353389 A CN 115353389A
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王俊
徐文强
王莹
刘鹏
马杰
沈德元
唐定远
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Jiangsu Normal University
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Abstract

The invention discloses a Ho ion doped sesquioxide transparent ceramic and a preparation method thereof, which comprises the step of mixing Y 2 O 3 And a dopant containing Ho ions are represented by the formula (Ho) x Y 1‑x ) 2 O 3 Weighing, mixing to obtain mixed powder, and performing ball milling, drying, grinding, sieving and calcining on the mixed powder in sequence to obtain Ho: Y 2 O 3 Powder, wherein x is more than or equal to 0.001 and less than or equal to 0.05; placing Ho to Y 2 O 3 Molding the powder to obtain a blank; sequentially carrying out vacuum sintering and hot isostatic pressing sintering on the green bodyAnnealing and polishing to obtain Ho: Y 2 O 3 Transparent ceramics; the heating and boosting process of the hot isostatic pressing sintering comprises the steps of firstly raising the hot isostatic pressing sintering temperature to a target temperature, then boosting the pressure of a hot isostatic pressing cavity, and raising the pressure of the hot isostatic pressing cavity to a target pressure; the temperature and pressure reduction process of the hot isostatic pressing sintering comprises the steps of reducing the hot isostatic pressing sintering temperature to be below 1000 ℃, then releasing pressure of a hot isostatic pressing cavity, and reducing the pressure of the hot isostatic pressing cavity to be normal atmospheric pressure. The invention can reduce the residual porosity of the transparent ceramic and improve the linear transmittance of visible light.

Description

Ho ion doped sesquioxide transparent ceramic and preparation method thereof
Technical Field
The invention relates to Ho ion doped sesquioxide transparent ceramic and a preparation method thereof, belonging to the technical field of transparent ceramic.
Background
2 μm lasers operating at the eye-safe band have important applications in atmospheric remote sensing, medical surgery, lidar systems, and free space optical communications (FSO).
Trivalent Ho 3+ Due to which the ions are in an excited state ( 5 I 7 ) To the ground state ( 5 I 8 ) The 1.9-2.1 μm transition and the large emission cross section and the long fluorescence lifetime are widely used to realize the laser output of 2 μm band.
Y 2 O 3 As a solid laser gain medium with great potential, the high-performance crystal silicon nitride crystal has excellent physical and chemical characteristics, such as wide-range transparency (0.2-8 mu m) and high corrosion resistance, the laser has the advantages of high thermal conductivity, high laser damage threshold, low phonon energy and low thermal expansion coefficient in the aspect of laser performance.
Furthermore, in comparison with other gain media, Y is hexa-coordinated 3+ Ion to Ho with six coordination 3+ Ions have nearly perfectly matched ionic radii (0.90A), and the better compatibility of the two will result in Ho: Y 2 O 3 No deterioration in parameters affecting laser performance such as thermal conductivity, Y 2 O 3 Will be more suitable as Ho of 2 μm band 3+ Of ion lasersA gain medium.
Traditionally single crystals were used as the gain medium for solid state lasers, however due to Y 2 O 3 The melting point is extremely high (2410 ℃), the preparation of large-size single crystals with high optical quality is difficult to realize, and the uniform doping of high-concentration rare earth ions is difficult to realize in process. In recent years, ceramics have emerged as a promising laser host material, and a fabrication process different from single crystals has been made to exhibit more advantages than single crystal laser gain media, such as low fabrication cost, uniform doping of active ions at high concentration, large-size specific shape customization, excellent mechanical strength, and high thermal conductivity. By adopting the ceramic forming process and the regulation and control of the sintering system, Y can be realized at the sintering temperature (1400-1800 ℃) far lower than the melting point of the material 2 O 3 The transparency of the ceramic is improved. In addition, Y is compared with a single crystal material 2 O 3 The mechanical strength of the ceramic is higher, the preparation period is shorter, and the ceramic is more suitable for large-scale production. At Y 2 O 3 Doping a ceramic matrix with a specific concentration of Ho 3+ Ion, by adjusting the powder preparation process, the ceramic forming process, the sintering system and Ho 3+ The ion doping concentration and the specific post-treatment process can be realized in Y 2 O 3 The single crystal obtains the best laser performance output on the basis of equivalent high optical quality.
Currently, ho: Y 2 O 3 Transparent ceramics typically use vacuum sintering in combination with a hot isostatic pressing sintering process. However, if the sintering process is not properly controlled, a large amount of pores are easily generated in the ceramic, thereby affecting the material transmittance and laser performance. Accordingly, the present application provides Ho ion-doped sesquioxide transparent ceramics and a method for preparing the same.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the Ho ion doped sesquioxide transparent ceramic and the preparation method thereof, which can reduce the residual porosity of the transparent ceramic and improve the linear transmittance of visible light.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
in one aspect, the present invention provides a method for preparing a Ho ion-doped sesquioxide transparent ceramic, comprising the steps of:
will Y 2 O 3 And a dopant containing Ho ions are represented by the formula (Ho) x Y 1-x ) 2 O 3 Weighing, mixing to obtain mixed powder, and performing ball milling, drying, grinding, sieving and calcining on the mixed powder in sequence to obtain Ho: Y 2 O 3 Powder, wherein x is more than or equal to 0.001 and less than or equal to 0.05;
mixing Ho with Y 2 O 3 Molding the powder to obtain a blank;
sequentially carrying out vacuum sintering, hot isostatic pressing sintering, annealing and polishing on the biscuit to obtain the Ho: Y 2 O 3 A transparent ceramic;
the hot isostatic pressing sintering comprises a heating and pressure increasing process and a cooling and pressure reducing process;
the temperature and pressure raising process comprises the steps of raising the hot isostatic pressing sintering temperature to a target temperature, then pressurizing the hot isostatic pressing cavity, and raising the pressure of the hot isostatic pressing cavity to a target pressure;
and in the temperature and pressure reduction process, the hot isostatic pressing sintering temperature is reduced to be below 1000 ℃, then the pressure of the hot isostatic pressing cavity is reduced to be normal atmospheric pressure.
Further, during the hot isostatic pressing sintering treatment:
the target temperatures for hot isostatic pressing sintering were: 1400-1700 ℃;
the hot isostatic pressing sintering time is 0.5-6 h;
inert gases for hot isostatic pressing sintering include argon or nitrogen;
the pressure of the inert gas is: 196MPa;
the target pressure of hot isostatic pressing sintering is 50-200 MPa.
Further, during the vacuum sintering process:
the vacuum degree of the vacuum environment is less than or equal to 10-3 Pa;
the vacuum sintering temperature is 1400-1700 ℃;
the vacuum sintering time is 0.5-40 h.
Further, during the annealing treatment:
the annealing atmosphere is air atmosphere or oxygen atmosphere;
the temperature of the annealing atmosphere is 600-1300 ℃;
the annealing time is 0.5-30 h.
Further, the step of adding Y 2 O 3 And a dopant containing Ho ions are represented by the formula (Ho) x Y 1-x ) 2 O 3 The method comprises the following steps of weighing, mixing, ball-milling, drying, grinding, sieving and calcining the raw materials in sequence:
adding absolute ethyl alcohol into the mixed powder to obtain slurry with the powder content of 10-30 Vol%, and performing ball milling treatment on the slurry;
placing the slurry subjected to ball milling treatment in an oven for drying to obtain a dried material;
grinding and sieving the dried material to obtain a sieved material;
calcining the sieved material in a muffle furnace to obtain Ho: Y 2 O 3 And (3) powder.
Further, the rotation speed of the ball milling treatment is 100-250 rpm, and the ball milling treatment time is 3-48 h;
and/or the mass ratio of the grinding balls subjected to ball milling to the mixed powder is 3;
and/or the particle diameter of the sieved material is less than 104 μm;
and/or the calcining temperature is 400-1100 ℃, and the calcining time is 3-10 h.
In a second aspect, the invention provides a Ho ion doped sesquioxide transparent ceramic prepared by the preparation method of the Ho ion doped sesquioxide transparent ceramic.
Further, the Ho ion doped sesquioxide transparent ceramic is applied to a solid laser gain medium of a laser;
the fixed laser gain medium is used for a 2.1 μm laser.
Compared with the prior art, the invention has the following beneficial effects:
the temperature rise and pressure rise process of the hot isostatic pressing sintering adopts the steps of firstly raising the temperature, then pressurizing after the temperature reaches the target temperature, and the temperature reduction and pressure reduction process of the hot isostatic pressing sintering adopts the steps of firstly reducing the temperature, and then slowly releasing the pressure after the temperature is reduced to 1000 ℃.
The Ho ion doped sesquioxide transparent ceramic provided by the invention is excited by a pumping source and utilizes Ho 3+ The energy level of the ions is transited, and 2.1 mu m laser output is realized.
Drawings
FIG. 1 is a flow chart of a method of making a Ho ion-doped sesquioxide transparent ceramic of the present invention;
FIG. 2 is 0.5 at.% Ho: Y obtained in inventive example 1 2 O 3 A photograph of a sample of the ceramic;
FIG. 3 is 0.5 at.% Ho: Y obtained in inventive example 1 2 O 3 The transmission spectrum of the ceramic;
FIG. 4 is 0.5 at.% Ho: Y obtained in inventive example 1 2 O 3 The change rule of the output power of the laser of the ceramic at the wavelength of 2117 nm along with the absorption power.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The application discloses a Ho ion doped sesquioxide transparent ceramic and a preparation method thereof.
Referring to fig. 1, the preparation method of the Ho ion doped sesquioxide transparent ceramic specifically comprises the following steps:
step A, adding Y 2 O 3 And a dopant containing Ho according to the formula (Ho) x Y 1-x ) 2 O 3 Weighing and mixing to obtain mixed powder, and sequentially performing ball milling, drying, grinding, sieving and calcining to obtain Ho: Y 2 O 3 And (3) powder. Wherein x is more than or equal to 0.001 and less than or equal to 0.05.
When in application, the step A comprises the following steps:
a1 weighing the high-purity Y 2 O 3 And containing Ho 2 O 3 Placing the mixture into a ball mill and adding absolute ethyl alcohol to obtain slurry with the powder content of 10-30 Vol%.
And A2, adding grinding balls into the slurry, and finishing ball milling treatment on the slurry through a ball mill.
In practical application, the rotation speed of ball milling treatment is 100-250 rpm, and the ball milling time is 3-48 h; the mass ratio of the grinding balls to the mixed powder is 3.
And A3, drying the slurry subjected to ball milling in an oven to obtain a dried material.
And A4, grinding the dried material, and screening to obtain a screened material with the particle diameter of less than 104 mu m.
A5, placing the obtained sieved material in a muffle furnace for calcination treatment to obtain Ho: Y 2 O 3 And (3) powder.
In practical application, the calcining temperature is 400-1100 ℃, and the calcining time is 3-10 h.
Step B, adding Ho to Y 2 O 3 And molding the powder to obtain a blank.
When in use, the step B comprises the following steps:
b1 combining Ho with Y 2 O 3 And carrying out dry pressing on the powder.
In actual application, the pressure of dry pressing is 0.5-20 MPa.
B2 pairs of Ho: Y after dry pressing 2 O 3 And carrying out cold isostatic pressing on the powder to obtain a biscuit.
In practical application, the pressure of the cold isostatic pressing is 100-200 MPa.
Step C, sequentially carrying out vacuum sintering, hot isostatic pressing sintering, annealing and polishing on the biscuit to obtain the Ho: Y 2 O 3 Transparent ceramics
When in application, the biscuit is placed in a vacuum environment at 1400-1700 ℃ for sintering for 0.5-40 h, then sintered in an inert gas at 1400-1700 ℃ for hot isostatic pressing for 0.5-6 h, finally annealed in an air or oxygen atmosphere at 600-1300 ℃ for 0.5-30 h, and polished on both sides to obtain the product with Ho: Y 2 O 3 A transparent ceramic.
Wherein the vacuum degree of the vacuum environment is less than or equal to 10 -3 Pa; the target pressure for hot isostatic pressing sintering is 50-200 MPa, and the inert gas for the hot isostatic pressing sintering comprises argon or nitrogen.
The heating and pressure raising process of the traditional hot isostatic pressing sintering generally adopts the steps of firstly pressurizing and then raising the temperature, or the pressure and the temperature are increased simultaneously; the temperature and pressure reduction process of the traditional hot isostatic pressing sintering generally adopts the simultaneous reduction of temperature and pressure.
In practical application of this embodiment, the temperature and pressure raising process during the hot isostatic pressing sintering includes raising the temperature of the hot isostatic pressing sintering to a target temperature, and then pressurizing the hot isostatic pressing cavity to raise the pressure of the hot isostatic pressing cavity to a target pressure. In addition, in the cooling and pressure reduction process during hot isostatic pressing sintering, the temperature of the hot isostatic pressing sintering is firstly reduced to be below 1000 ℃, then the pressure of the hot isostatic pressing cavity is released, and the pressure of the hot isostatic pressing cavity is reduced to be normal atmospheric pressure.
The Ho ion-doped sesquioxide transparent ceramic can be obtained by the above Ho ion-doped sesquioxide transparent ceramic and the preparation method thereof, referring to fig. 2. The Ho ion doped sesquioxide transparent ceramic is applied to a solid laser gain medium of a laser. Wherein the fixed laser gain medium is used for a 2.1 μm laser.
Example 1
Selection of commercially high purity Y 2 O 3 And Ho 2 O 3 The powder is prepared from raw materials according to the chemical formula (Ho) 0.005 Y 0.995 ) 2 O 3 The raw material was weighed, wherein the amount of yttrium oxide was 100 g. And adding 120 mL of absolute ethyl alcohol and 700 g of zirconia grinding balls, and then carrying out ball milling treatment, wherein the rotating speed of the ball mill is 180 rpm, and the ball milling time is 10 h. Mixing the materials, drying in 70 deg.C oven for 36 hr, grinding, sieving, and calcining in muffle furnace at 600 deg.C for 5 hr to obtain Ho: Y 2 O 3 And (3) powder.
Placing Ho to Y 2 O 3 The powder is firstly unidirectionally pressed under the pressure of 5 MPa, and in order to further improve the compactness, the powder is subjected to unidirectional pressingCold isostatic pressing the biscuit at 200 MPa to obtain Ho: Y 2 O 3 A ceramic biscuit.
The biscuit is sintered for 5 hours under 1550 ℃ high vacuum, the vacuum degree is less than 5 multiplied by 10 -3 Pa。
Then, hot isostatic pressing sintering was performed under 180 MPa argon atmosphere. The technological parameters of hot isostatic pressing sintering are as follows: firstly, the vacuum degree of a hearth for hot isostatic pressing sintering is pumped to 1 multiplied by 10 -2 Pa below, then raising the temperature of the hearth to 1500 ℃ at a heating rate of 10 ℃/min and starting heat preservation. After the temperature is kept for 1 minute, argon is pumped into the hearth to pressurize the hearth. And after the pressure of the hearth is increased to 180 MPa, continuously preserving heat and pressure for 2 hours. After the heat preservation and pressure maintenance are finished, the temperature of the hearth is reduced to 1000 ℃ at the speed of 4 ℃/min, and the pressure of the hearth is maintained between 150 and 180 MPa by an intermittent pressure supplementing means in the period. After the temperature of the hearth is reduced to below 1000 ℃, the temperature reduction rate is adjusted to 8 ℃/min, and the pressure is reduced along with the temperature reduction and no pressure compensation is carried out. After sintering, the ceramic is subjected to air annealing in a muffle furnace at 1000 ℃ for 30 h to realize transparent Ho: Y 2 O 3 And (3) preparing the ceramic.
EXAMPLES example 2
Selection of commercially high purity Y 2 O 3 And Ho 2 O 3 The powder is prepared from raw materials according to the chemical formula (Ho) 0.04 Y 0.96 ) 2 O 3 The raw material was weighed, wherein the amount of yttrium oxide was 100 g. And adding 120 mL of absolute ethyl alcohol and 700 g of zirconia grinding balls, and then carrying out ball milling treatment, wherein the rotating speed of the ball mill is 150 rpm, and the ball milling time is 10 h. Mixing the materials uniformly, drying in an oven at 70 deg.C for about 36 hr, grinding, sieving, calcining in a muffle furnace at 600 deg.C for 5 hr to obtain Ho: Y 2 O 3 And (3) powder.
Placing Ho to Y 2 O 3 The powder is firstly pressed unidirectionally under the pressure of 5 MPa, and in order to further improve the density, the biscuit is subjected to cold isostatic pressing under the pressure of 200 MPa to obtain the product with Ho, Y 2 O 3 A ceramic biscuit.
Firstly, the biscuit is sintered for 5 hours under the high vacuum of 1450 ℃, and the vacuum degree is less than 5 multiplied by 10 -3 Pa. Then, hot isostatic pressing sintering was performed under an argon atmosphere of 196 MPa. The technological parameters of hot isostatic pressing sintering are as follows: firstly, the vacuum degree of a hearth for hot isostatic pressing sintering is pumped to 1 multiplied by 10 -2 Pa below, then raising the temperature of the hearth to 1450 ℃ at a heating rate of 10 ℃/min and starting heat preservation. After the temperature is kept for 1 minute, argon is pumped into the hearth to pressurize the hearth. And after the pressure of the hearth is increased to 196MPa, continuously preserving heat and pressure for 2 hours. After the heat preservation and pressure maintenance are finished, the temperature of the hearth is reduced to 1000 ℃ at the speed of 4 ℃/min, and the pressure of the hearth is maintained between 160 and 180 MPa by an intermittent pressure supplementing means in the period. After the temperature of the hearth is reduced to below 1000 ℃, the temperature reduction rate is adjusted to 8 ℃/min, and the pressure is reduced along with the temperature reduction and no pressure compensation is carried out. After sintering, the ceramic is subjected to air annealing in a muffle furnace at 1000 ℃ for 30 h to realize transparent Ho: Y 2 O 3 And (3) preparing the ceramic.
EXAMPLE 3
Selection of commercially high purity Y 2 O 3 And Ho 2 O 3 The powder is used as raw material. According to the chemical formula (Ho) 0.02 Y 0.98 ) 2 O 3 The raw material was weighed, wherein the amount of yttrium oxide was 100 g. And adding 120 mL of absolute ethyl alcohol and 700 g of zirconia grinding balls, and then carrying out ball milling treatment, wherein the rotating speed of the ball mill is 180 rpm, and the ball milling time is 10 h. Mixing the materials, drying in 70 deg.C oven for 36 hr, grinding, sieving, and calcining in muffle furnace at 600 deg.C for 5 hr to obtain Ho: Y 2 O 3 And (3) powder.
Placing Ho to Y 2 O 3 The powder is firstly pressed unidirectionally under the pressure of 5 MPa, and in order to further improve the density, the biscuit is subjected to cold isostatic pressing under the pressure of 200 MPa to obtain the product with Ho, Y 2 O 3 A ceramic biscuit.
Firstly, the biscuit is sintered for 1 hour under the high vacuum condition at 1700 ℃, and the vacuum degree is less than 5 multiplied by 10 -3 Pa. Then, hot isostatic pressing sintering was performed under an argon atmosphere of 196 MPa. The technological parameters of hot isostatic pressing sintering are as follows: firstly, the vacuum degree of a hearth for hot isostatic pressing sintering is pumped to 1 multiplied by 10 -2 Pa below, then raising the temperature of the hearth to 1650 ℃ at a heating rate of 10 ℃/min and startingAnd (5) preserving heat. After the temperature is kept for 1 minute, argon is pumped into the hearth to pressurize the hearth. And after the pressure of the hearth is increased to 196MPa, continuously preserving heat and pressure for 2 hours. After the heat preservation and pressure maintenance are finished, the temperature of the hearth is reduced to 1000 ℃ at the speed of 4 ℃/min, and the pressure of the hearth is maintained between 150 and 170 MPa by an intermittent pressure supplementing means in the period. After the temperature of the hearth is reduced to below 1000 ℃, the temperature reduction rate is adjusted to 8 ℃/min, and the pressure is reduced along with the reduction of the temperature and pressure compensation is not carried out. After sintering, the ceramic is subjected to air annealing in a muffle furnace at 1000 ℃ for 30 h to realize transparent Ho: Y 2 O 3 And (3) preparing the ceramic.
Example 4
Selection of commercially high purity Y 2 O 3 And Ho 2 O 3 The powder is used as raw material. According to the chemical formula (Ho) 0.0008 Y 0.9992 ) 2 O 3 The raw material was weighed, wherein the amount of yttrium oxide was 100 g. And adding 120 mL of absolute ethyl alcohol and 700 g of zirconia grinding balls, and then carrying out ball milling treatment, wherein the rotating speed of the ball mill is 160 rpm, and the ball milling time is 15 h. Mixing the materials, drying in 70 deg.C oven for 36 hr, grinding, sieving, and calcining in muffle furnace at 600 deg.C for 5 hr to obtain Ho: Y 2 O 3 And (3) powder.
Placing Ho to Y 2 O 3 The powder is firstly pressed unidirectionally under the pressure of 5 MPa, and in order to further improve the compactness, the biscuit is subjected to cold isostatic pressing under the pressure of 200 MPa to obtain Ho, Y 2 O 3 A ceramic biscuit.
Firstly, the biscuit is sintered for 5 hours under the high vacuum of 1530 ℃ and the vacuum degree is less than 5 multiplied by 10 -3 Pa. Then, hot isostatic pressing sintering was performed under an argon atmosphere of 160 MPa. The technological parameters of hot isostatic pressing sintering are as follows: firstly, the vacuum degree of a hearth for hot isostatic pressing sintering is pumped to 1 multiplied by 10 -2 Pa below, then raising the temperature of the hearth to 1520 ℃ at a heating rate of 10 ℃/min and starting heat preservation. After the temperature is kept for 1 minute, argon is started to be pumped into the hearth so as to pressurize the hearth. And after the pressure of the hearth is increased to 160 MPa, continuously preserving heat and pressure for 2 hours. After the heat preservation and pressure maintenance are finished, the temperature of the hearth is reduced to 1000 ℃ at the speed of 4 ℃/min, and the pressure of the hearth is increased by an intermittent pressure supplementing means in the periodThe pressure is maintained between 140 and 160 MPa. After the temperature of the hearth is reduced to below 1000 ℃, the temperature reduction rate is adjusted to 8 ℃/min, and the pressure is reduced along with the temperature reduction and no pressure compensation is carried out. After sintering, the ceramic is subjected to air annealing in a muffle furnace at 1000 ℃ for 30 h to realize transparent Ho: Y 2 O 3 And (3) preparing the ceramic.
Comparative example 1
Comparative example 1 differs from example 1 in the elevated temperature and pressure process of hot isostatic pressing sintering.
The temperature and pressure rise process of the hot isostatic pressing sintering of the comparative example is as follows:
pumping argon into the hearth to increase the pressure of the hearth to 30 MPa. And then raising the temperature of the hearth to 1500 ℃ at the heating rate of 10 ℃/min, starting heat preservation, raising the pressure in the hearth to 180 MPa, and continuing heat preservation and pressure maintaining for 2 hours.
Comparative example 2
Comparative example 1 differs from example 1 in the temperature and pressure reduction process of hot isostatic pressing sintering.
The cooling and pressure reduction process of the hot isostatic pressing sintering of the comparative example is as follows:
after the heat preservation and pressure maintenance are finished, the temperature of the hearth is reduced to the room temperature at the speed of 10 ℃/min, the pressure intensity is reduced along with the reduction of the temperature, and pressure compensation is not carried out in the process of temperature reduction and pressure reduction. After sintering, the ceramic was air annealed in a muffle furnace at 1000 deg.C for 30 h to obtain Ho: Y 2 O 3 A ceramic.
As can be seen from Table 1, ho: Y obtained in examples 1 to 4 2 O 3 The ceramics all have a porosity lower than 0.0004% and a linear transmittance of visible light higher than 80%, refer to fig. 3. Y Ho obtained in comparative examples 1 and 2 2 O 3 The ceramics also achieved transparentization, but Ho: Y obtained in comparative examples 1 and 2 was comparable to examples 1 to 4 2 O 3 The residual porosity of the ceramic is relatively large. Too many residual pores affect the visible light straight-line transmittance, and thus, ho: Y obtained in comparative examples 1 and 2 2 O 3 The visible light linear transmittance of the ceramic is lower than 80%.
TABLE 1 Ho ion-doped sesquioxide transparent ceramic Properties
Linear transmittance (600 nm linear light) 2.1 Mum laser output slope efficiency 2.1 μ m laser output power Residual porosity
Example 1 80.2% 55% ~50 W <0.0004%
Example 2 80% -36% ~42 W <0.0004%
Example 3 80.3% -45% ~57 W <0.0004%
Example 4 80.2% - - <0.0004%
Comparative example 1 78.6% 21% ~10 W ~0.005%
Comparative example 2 77.9% 16% ~7 W ~0.006%
In addition, in the laser experiment, ho: Y 2 O 3 The residual gas holes of the ceramic scatter the laser, which leads to increased scattering loss and prominent thermal effect, and makes it difficult to further improve the laser output power and laser output tilt efficiency.
Example 4 because the doping concentration of the Ho ions is too low, the absorption of the pump light by the material is insufficient, and high-power light extraction of 2.1 μm cannot be obtained. However, the high optical quality Ho: Y prepared in examples 1-3 2 O 3 Transparent ceramics, excited by a suitable pump source, making use of Ho 3+ And the energy level transition of the ions realizes the high-power 2.1 mu m laser output.
Referring to FIG. 4, is 0.5 at.% Ho: Y obtained in example 1 2 O 3 The output power of the ceramic laser with the wavelength of 2117 nm changes along with the change rule of the absorption power, and when the ceramic laser is applied, a pump source is a 1931 nm thulium optical fiber laser, namely, 0.5 at.% Ho: Y is obtained in the embodiment 1 under the excitation of the pump source of the thulium optical fiber 2 O 3 Ceramic utilization Ho 3+ Excited state of ion ( 5 I 7 ) To the ground state ( 5 I 8 ) The energy level transition of the laser can realize high-efficiency 2.1 mu m laser output.
In conclusion, the Ho ion doped sesquioxide transparent ceramic prepared by the invention can be used as an ideal laser gain medium in the fields of laser radar, laser ranging, atmospheric detection and the like.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, it is possible to make various improvements and modifications without departing from the technical principle of the present invention, and those improvements and modifications should be considered as the protection scope of the present invention.

Claims (8)

  1. A preparation method of the Ho ion doped sesquioxide transparent ceramic is characterized by comprising the following steps:
    will Y 2 O 3 And a dopant containing Ho ions are represented by the formula (Ho) x Y 1-x ) 2 O 3 Weighing and mixing to obtain mixed powder, and performing ball milling, drying, grinding, sieving and calcining treatment on the mixed powder in sequence to obtain Ho: Y 2 O 3 Powder, wherein x is more than or equal to 0.001 and less than or equal to 0.05;
    placing Ho to Y 2 O 3 Molding the powder to obtain a blank;
    sequentially carrying out vacuum sintering, hot isostatic pressing sintering, annealing and polishing on the biscuit to obtain the Ho: Y 2 O 3 A transparent ceramic;
    the hot isostatic pressing sintering comprises a heating and pressure increasing process and a cooling and pressure reducing process;
    the temperature and pressure raising process comprises the steps of raising the hot isostatic pressing sintering temperature to a target temperature, then pressurizing the hot isostatic pressing cavity, and raising the pressure of the hot isostatic pressing cavity to a target pressure;
    and in the temperature and pressure reduction process, the hot isostatic pressing sintering temperature is reduced to be below 1000 ℃, then the pressure of the hot isostatic pressing cavity is reduced to be normal atmospheric pressure.
  2. 2. The method of claim 1, wherein during the hot isostatic pressing sintering process:
    the target temperatures for hot isostatic pressing sintering were: 1400-1700 ℃;
    the hot isostatic pressing sintering time is as follows: 0.5-6 h;
    inert gases for hot isostatic pressing sintering include argon or nitrogen;
    the pressure of the inert gas is: 196MPa;
    the target pressure for hot isostatic pressing sintering is: 50-200 MPa.
  3. 3. The method for preparing a Ho ion-doped sesquioxide transparent ceramic according to claim 1, wherein during the vacuum sintering process:
    vacuum degree of vacuum environment is less than or equal to 10 -3 Pa；
    The vacuum sintering temperature is 1400-1700 ℃;
    the vacuum sintering time is 0.5-40 h.
  4. 4. The method for preparing a Ho ion-doped sesquioxide transparent ceramic according to claim 1, wherein during the annealing treatment:
    the annealing atmosphere is air atmosphere or oxygen atmosphere;
    the temperature of the annealing atmosphere is 600-1300 ℃;
    the annealing time is 0.5-30 h.
  5. 5. The method of claim 1, wherein the step of preparing the Ho ion-doped sesquioxide transparent ceramic is carried out by mixing Y with the mixture of the Ho ion-doped sesquioxide transparent ceramic and the mixture of the Y ion-doped sesquioxide transparent ceramic 2 O 3 And a dopant containing Ho ions are represented by the formula (Ho) x Y 1-x ) 2 O 3 The method comprises the following steps of weighing, mixing, ball-milling, drying, grinding, sieving and calcining the raw materials in sequence:
    adding absolute ethyl alcohol into the mixed powder to obtain slurry with the powder content of 10-30 Vol%, and performing ball milling treatment on the slurry;
    placing the slurry subjected to ball milling treatment in an oven for drying to obtain a dried material;
    grinding and sieving the dried material to obtain a sieved material;
    calcining the sieved material in a muffle furnace to obtain Ho: Y 2 O 3 And (3) powder.
  6. 6. The method for preparing the Ho ion doped sesquioxide transparent ceramic according to claim 5, wherein the rotation speed of the ball milling treatment is 100-250 rpm, and the ball milling treatment time is 3-48 h;
    and/or the mass ratio of the grinding balls subjected to ball milling to the mixed powder is 3;
    and/or the particle diameter of the screened material is less than 104 μm;
    and/or the calcining temperature is 400-1100 ℃, and the calcining time is 3-10 h.
  7. A Ho ion-doped sesquioxide transparent ceramic prepared by the method for preparing a Ho ion-doped sesquioxide transparent ceramic according to any one of claims 1 to 6.
  8. 8. The Ho ion-doped sesquioxide transparent ceramic of claim 7 is applied to a solid laser gain medium of a laser;
    the fixed laser gain medium is used for a 2.1 μm laser.
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WO2007065914A1 (en) * 2005-12-08 2007-06-14 Ceramtec Ag Finely crystalline al2o3 ceramic
CN102476445A (en) * 2010-11-24 2012-05-30 浙江中能防腐设备有限公司 Hot static pressure equipment for sintering polytetrafluoroethylene or modified polytetrafluoroethylene
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CN104529449A (en) * 2014-12-18 2015-04-22 徐州市江苏师范大学激光科技有限公司 Method for preparing yttrium oxide-based transparent ceramic employing two-step sintering method
CN108203300A (en) * 2018-02-07 2018-06-26 陕西科谷新材料科技有限公司 A kind of preparation method of high tenacity, high resistivity silicon carbide ceramics
CN113773081A (en) * 2021-10-22 2021-12-10 江苏师范大学 Transparent ceramic and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007065914A1 (en) * 2005-12-08 2007-06-14 Ceramtec Ag Finely crystalline al2o3 ceramic
CN102476445A (en) * 2010-11-24 2012-05-30 浙江中能防腐设备有限公司 Hot static pressure equipment for sintering polytetrafluoroethylene or modified polytetrafluoroethylene
CN103864409A (en) * 2014-01-28 2014-06-18 中国科学院上海光学精密机械研究所 Preparation method of neodymium-doped yttrium aluminum garnet transparent ceramic
CN104529449A (en) * 2014-12-18 2015-04-22 徐州市江苏师范大学激光科技有限公司 Method for preparing yttrium oxide-based transparent ceramic employing two-step sintering method
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