CN115353389B - 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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CN115353389B
CN115353389B CN202211175496.7A CN202211175496A CN115353389B CN 115353389 B CN115353389 B CN 115353389B CN 202211175496 A CN202211175496 A CN 202211175496A CN 115353389 B CN115353389 B CN 115353389B
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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 application discloses a Ho ion doped sesquioxide transparent ceramic and a preparation method thereof, comprising the following steps of 2 O 3 And a Ho ion-containing dopant are both of 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 Powder, wherein x is more than or equal to 0.001 and less than or equal to 0.05; ho: Y 2 O 3 Shaping the powder to obtain a blank; sequentially performing vacuum sintering, hot isostatic pressing sintering, annealing and polishing treatment on the green body to obtain Ho:Y 2 O 3 A transparent ceramic; the heating and boosting process of the hot isostatic pressing sintering is to firstly raise the hot isostatic pressing sintering temperature to a target temperature, then boost the pressure of the hot isostatic pressing cavity, and raise the pressure of the hot isostatic pressing cavity to the target pressure; the cooling and depressurization process of the hot isostatic pressing sintering is to firstly reduce the hot isostatic pressing sintering temperature to below 1000 ℃, then to decompress the hot isostatic pressing cavity, and to reduce the pressure of the hot isostatic pressing cavity to normal atmospheric pressure. The application can reduce the residual porosity of the transparent ceramic and improve the visible light linear transmittance.

Description

Ho ion doped sesquioxide transparent ceramic and preparation method thereof
Technical Field
The application relates to Ho ion doped sesquioxide transparent ceramic and a preparation method thereof, and belongs to the technical field of transparent ceramics.
Background
2 μm lasers operating in the eye safety band have important applications in atmospheric telemetry, medical procedures, lidar systems, and free space optical communications (FSO).
Trivalent Ho 3+ The ion is from excited state 5 I 7 ) To the ground state% 5 I 8 ) Is widely used to achieve a laser output in the 2 μm band, with a large emission cross section and a long fluorescence lifetime.
Y 2 O 3 The solid-state laser gain medium with great potential has excellent physical and chemical characteristics, such as wide transparency (0.2-8 mu m) and high corrosion resistance, and has the advantages of high heat conductivity, high laser damage threshold, low phonon energy and low thermal expansion coefficient in the aspect of laser performance.
In addition, compared with other gain media, six-coordinated Y 3+ Ho with ion and hexacoordination 3+ The ions have an almost perfect match of ion radii (0.90 a), and the better compatibility of the two will result in Ho: Y 2 O 3 Does not deteriorate in parameters affecting laser performance such as thermal conductivity, Y 2 O 3 Ho which will be more suitable as a2 μm band 3+ Gain medium of ion laser.
Traditionally single crystals have been used as gain medium for solid state lasers, however due to Y 2 O 3 The melting point is extremely high (2410 ℃), large-size single crystal preparation with high optical quality is difficult to realize, and uniform doping of rare earth ions with high concentration is not easy to realize in the process. In recent years, ceramics have emerged as a promising laser host material, and the fabrication process of the different from single crystals has led to the display of advantages over single crystal laser gain media such as low manufacturing cost, high concentration of active ions uniformly doped, large-size custom-made specific shapes, excellent mechanical strength and high thermal conductivity. By adopting the ceramic molding 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 And (3) transparentizing the ceramic. In addition, compared with single crystal material, Y 2 O 3 The ceramic has higher mechanical strength, shorter preparation period and suitability for mass production. In Y 2 O 3 Doping Ho in specific concentration into ceramic matrix 3+ Ion is prepared by adjusting the powder preparation process, the ceramic forming process, the sintering system and Ho 3+ Ion doping concentration and specific post-treatment process can be realized and carried out 2 O 3 The best laser performance output is obtained on the basis of the relatively high optical quality of the single crystal.
Currently, ho:Y 2 O 3 Transparent ceramics are generally sintered by vacuum sintering in combination with hot isostatic pressing. However, if the sintering process is controlled improperly, a large number of pores are easily generated in the ceramic, thereby affecting the material transmittance and laser performance. Therefore, the application provides a Ho ion doped sesquioxide transparent ceramic and a preparation method thereof.
Disclosure of Invention
The application 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 visible light linear transmittance.
In order to achieve the above purpose, the application is realized by adopting the following technical scheme:
in one aspect, the application provides a method for preparing a Ho ion doped sesquioxide transparent ceramic, comprising the following steps:
y is set to 2 O 3 And a Ho ion-containing dopant are both of 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 Powder, wherein x is more than or equal to 0.001 and less than or equal to 0.05;
ho: Y 2 O 3 Shaping the powder to obtain a blank;
sequentially performing vacuum sintering, hot isostatic pressing sintering, annealing and polishing treatment on the green body to obtain Ho:Y 2 O 3 A transparent ceramic;
the hot isostatic pressing sintering comprises a heating and boosting process and a cooling and depressurization process;
the heating and boosting process is to firstly raise the sintering temperature of the hot isostatic pressing to a target temperature, then boost the pressure of the hot isostatic pressing cavity and raise the pressure of the hot isostatic pressing cavity to the target pressure;
the cooling and depressurization process is to reduce the sintering temperature of the hot isostatic pressing to below 1000 ℃ and then to depressurize the hot isostatic pressing cavity, so that the pressure of the hot isostatic pressing cavity is reduced to normal atmospheric pressure.
Further, during the hot isostatic pressing sintering process:
the target temperature for hot isostatic pressing sintering is: 1400-1700 ℃;
the sintering time of the hot isostatic pressing is 0.5-6 h;
the inert gas for hot isostatic pressing sintering comprises argon or nitrogen;
the gas pressure of the inert gas is as follows: 196MPa;
the target pressure of the 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 duration of vacuum sintering 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, said will Y 2 O 3 And a Ho ion-containing dopant are both of the formula (Ho x Y 1-x ) 2 O 3 Weighing, mixing, ball milling, drying, grinding, sieving and calcining in sequence, wherein the method comprises the following steps:
absolute ethyl alcohol is added into the mixed powder to obtain slurry with the powder content of 10-30 Vol percent, and ball milling treatment is carried out 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 rotating speed of the ball milling treatment is 100-250 rpm, and the duration of the ball milling treatment is 3-48 h;
and/or the mass ratio of the grinding balls subjected to ball milling to the mixed powder is 3:1-8:1;
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 application provides a Ho ion doped sesquioxide transparent ceramic, which is 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 application has the beneficial effects that:
the temperature and pressure increasing process of the hot isostatic pressing sintering adopts the steps of firstly increasing the temperature, then pressurizing after the temperature reaches the target temperature, and the temperature and pressure reducing process of the hot isostatic pressing sintering adopts the steps of firstly reducing the temperature, and slowly releasing the pressure after the temperature is reduced to 1000 ℃, compared with the traditional hot isostatic pressing sintering, the application can improve the uniformity of the hot isostatic pressing sintering, reduce the residual porosity of the transparent ceramic product and improve the visible light linear transmittance of the transparent ceramic product.
The Ho ion doped sesquioxide transparent ceramic of the application utilizes Ho under the excitation of a pumping source 3+ The energy level transition of the ions realizes 2.1 mu m laser output.
Drawings
FIG. 1 is a flow chart of a method of preparing a Ho ion doped sesquioxide transparent ceramic of the present application;
FIG. 2 is a graph of 0.5. 0.5 at.% Ho:Y obtained in example 1 of the application 2 O 3 A sample photograph of the ceramic;
FIG. 3 is a graph of 0.5. 0.5 at.% Ho:Y obtained in example 1 of the application 2 O 3 A transmission spectrum of the ceramic;
FIG. 4 is a graph of 0.5. 0.5 at.% Ho:Y obtained in example 1 of the application 2 O 3 The laser output power of the ceramic at 2117 and nm wavelengths changes with the absorption power.
Detailed Description
The application is further described below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present application, and are not intended to limit the scope of the present application.
The application discloses Ho ion doped sesquioxide transparent ceramic and a preparation method thereof.
The preparation method of the Ho ion doped sesquioxide transparent ceramic specifically comprises the following steps with reference to FIG. 1:
step A, Y 2 O 3 And a Ho-containing dopant 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 use, the step A comprises the following steps:
a1 high purity Y after weighing 2 O 3 And contain Ho 2 O 3 Placing in a ball mill, and adding absolute ethyl alcohol to obtain slurry with powder content of 10-30 Vol%.
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 ball to the mixed powder is 3:1-8:1.
And A3, placing the slurry subjected to ball milling treatment in an oven for drying to obtain a dried material.
A4, grinding the dried material, and screening to obtain a screened material with the particle diameter smaller than 104 mu m.
A5 will obtainThe sieved material is placed in a muffle furnace for calcination treatment to obtain Ho: Y 2 O 3 And (3) powder.
In practical application, the calcination temperature is 400-1100 ℃ and the calcination time is 3-10 h.
Step B, ho: Y 2 O 3 And (5) carrying out shaping treatment on the powder to obtain the blank.
When in use, the step B comprises the following steps:
b1 is Ho:Y 2 O 3 And (5) carrying out dry pressing molding on the powder.
In practical application, the dry-pressing molding pressure is 0.5-20 MPa.
B2 Ho: Y after dry press molding 2 O 3 And (5) performing cold isostatic pressing on the powder to obtain the blank.
In practical application, the pressure of cold isostatic pressing is 100-200 MPa.
Step C, sequentially performing vacuum sintering, hot isostatic pressing sintering, annealing and polishing treatment on the green body to obtain Ho:Y 2 O 3 Transparent ceramic
When in use, the green body is placed in a vacuum environment with the temperature of 1400-1700 ℃ to sinter 0.5-40 h, then sintered in an inert gas with the temperature of 1400-1700 ℃ in a hot isostatic pressing way to sinter 0.5-6 h, finally annealed in an air or oxygen atmosphere with the temperature of 600-1300 ℃ to anneal 0.5-30 h, and then polished on both sides to obtain Ho: Y 2 O 3 Transparent ceramics.
Wherein the vacuum degree of the vacuum environment is less than or equal to 10 -3 Pa; the target pressure for the HIP is 50-200 MPa, and the inert gas used for the HIP comprises argon or nitrogen.
The traditional heating and boosting process of hot isostatic pressing sintering generally adopts the steps of pressurizing firstly and then heating, or the pressure and the temperature are increased simultaneously; the temperature and pressure drop process of traditional hot isostatic pressing sintering generally adopts the simultaneous drop of temperature and pressure.
In practical application, the heating and boosting process during the hot isostatic pressing sintering is to raise the temperature of the hot isostatic pressing sintering to the target temperature, then boost the pressure of the hot isostatic pressing cavity, and raise the pressure of the hot isostatic pressing cavity to the target pressure. In addition, the temperature and pressure reduction process during the hot isostatic pressing sintering is to reduce the temperature of the hot isostatic pressing sintering to below 1000 ℃ and then to decompress the hot isostatic pressing cavity, so that the pressure of the hot isostatic pressing cavity is reduced to normal atmospheric pressure.
The Ho ion doped sesquioxide transparent ceramic and the preparation method thereof can be obtained, and refer to fig. 2. The Ho ion doped sesquioxide transparent ceramic is applied to a solid laser gain medium of a laser. Wherein a fixed laser gain medium is used for a 2.1 μm laser.
Example 1
Selecting commercial high purity Y 2 O 3 And Ho 2 O 3 The powder is used as raw material and is expressed by the chemical formula (Ho 0.005 Y 0.995 ) 2 O 3 The raw materials were weighed, with yttria being 100 g. Adding 120 mL absolute ethyl alcohol and 700 g zirconia grinding balls, and then performing 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 oven at 70deg.C for about 36 h, grinding and sieving, and calcining in muffle furnace at 600deg.C for 5 h to obtain Ho:Y 2 O 3 And (3) powder.
Ho: 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 200 MPa to obtain Ho: Y 2 O 3 Ceramic greenware.
Sintering the biscuit at 1550 deg.c under high vacuum for 5 hr with vacuum degree less than 5 x 10 -3 Pa。
Then, the sintered product was sintered by hot isostatic pressing under an argon atmosphere of 180 MPa. The technological parameters of the hot isostatic pressing sintering are as follows: the furnace chamber vacuum degree for hot isostatic pressing sintering is firstly pumped to 1 multiplied by 10 -2 Under Pa, the temperature of the hearth is then increased to 1500 ℃ at a heating rate of 10 ℃/min and the heat preservation is started. After 1 minute of heat preservation, pumping argon into the hearth to pressurize the hearth. And after the pressure of the hearth is increased to 180 MPa, keeping the temperature and the pressure for 2 hours. After the heat preservation and pressure maintaining are finished, the temperature of the hearth is reduced to 1000 ℃ at the speed of 4 ℃/min, and the pressure of the hearth is enabled by intermittent pressure supplementing means during the periodMaintaining the pressure between 150 and 180 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 and no pressure compensation is performed. 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 ceramics.
Example 2 of the embodiment
Selecting commercial high purity Y 2 O 3 And Ho 2 O 3 The powder is used as raw material and is expressed by the chemical formula (Ho 0.04 Y 0.96 ) 2 O 3 The raw materials were weighed, with yttria being 100 g. Adding 120 mL absolute ethyl alcohol and 700 g zirconia grinding balls, and then performing 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, drying in oven at 70deg.C for about 36 h, grinding and sieving, and calcining in muffle furnace at 600deg.C for 5 h to obtain Ho:Y 2 O 3 And (3) powder.
Ho: 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 200 MPa to obtain Ho: Y 2 O 3 Ceramic greenware.
Sintering the biscuit at 1450 deg.c under high vacuum for 5 hr with vacuum degree less than 5 x 10 -3 Pa. Then, the sintered product was sintered by hot isostatic pressing under an argon atmosphere of 196 MPa. The technological parameters of the hot isostatic pressing sintering are as follows: the furnace chamber vacuum degree for hot isostatic pressing sintering is firstly pumped to 1 multiplied by 10 -2 Under Pa, then the temperature of the hearth is increased to 1450 ℃ at a heating rate of 10 ℃/min, and heat preservation is started. After 1 minute of heat preservation, pumping argon into the hearth to pressurize the hearth. And after the pressure of the hearth is increased to 196MPa, keeping the temperature and the pressure for 2 hours. After the heat preservation and pressure maintaining 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 MPa and 180 MPa by an intermittent pressure supplementing means. 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 and no pressure compensation is performed. 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 ceramics.
Example 3
Selecting commercial high purity Y 2 O 3 And Ho 2 O 3 The powder is used as a raw material. According to the chemical formula (Ho 0.02 Y 0.98 ) 2 O 3 The raw materials were weighed, with yttria being 100 g. Adding 120 mL absolute ethyl alcohol and 700 g zirconia grinding balls, and then performing 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 oven at 70deg.C for about 36 h, grinding and sieving, and calcining in muffle furnace at 600deg.C for 5 h to obtain Ho:Y 2 O 3 And (3) powder.
Ho: 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 200 MPa to obtain Ho: Y 2 O 3 Ceramic greenware.
Sintering the biscuit at 1700 deg.c in high vacuum for 1 hr with vacuum degree less than 5 x 10 -3 Pa. Then, the sintered product was sintered by hot isostatic pressing under an argon atmosphere of 196 MPa. The technological parameters of the hot isostatic pressing sintering are as follows: the furnace chamber vacuum degree for hot isostatic pressing sintering is firstly pumped to 1 multiplied by 10 -2 Under Pa, the temperature of the hearth is then raised to 1650 ℃ at a heating rate of 10 ℃/min and the heat preservation is started. After 1 minute of heat preservation, pumping argon into the hearth to pressurize the hearth. And after the pressure of the hearth is increased to 196MPa, keeping the temperature and the pressure for 2 hours. After the heat preservation and pressure maintaining 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 MPa and 170 MPa by an intermittent pressure supplementing means. 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 and no pressure compensation is performed. 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 ceramics.
Example 4
Selecting commercial high purity Y 2 O 3 And Ho 2 O 3 The powder is used as a raw material. According to the chemical formula (Ho 0.0008 Y 0.9992 ) 2 O 3 The raw materials were weighed, with yttria being 100 g. Adding 120 mL absolute ethyl alcohol and 700 g zirconia grinding balls, and then performing 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 oven at 70deg.C for about 36 h, grinding and sieving, and calcining in muffle furnace at 600deg.C for 5 h to obtain Ho:Y 2 O 3 And (3) powder.
Ho: 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 200 MPa to obtain Ho: Y 2 O 3 Ceramic greenware.
Sintering the biscuit at 1530 deg.C under high vacuum for 5 hr, the vacuum degree is less than 5×10 -3 Pa. Then, the sintered product was sintered by hot isostatic pressing under an argon atmosphere of 160 MPa. The technological parameters of the hot isostatic pressing sintering are as follows: the furnace chamber vacuum degree for hot isostatic pressing sintering is firstly pumped to 1 multiplied by 10 -2 Under Pa, then the temperature of the hearth is increased to 1520 ℃ at a heating rate of 10 ℃/min, and heat preservation is started. After 1 minute of heat preservation, pumping argon into the hearth to pressurize the hearth. And after the pressure of the hearth is increased to 160 MPa, keeping the temperature and the pressure for 2 hours. After the heat preservation and pressure maintaining 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 140 MPa and 160 MPa by an intermittent pressure supplementing means. 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 and no pressure compensation is performed. 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 ceramics.
Comparative example 1
Comparative example 1 differs from example 1 in the temperature and pressure increasing process of the hot isostatic pressing sintering.
The hot isostatic pressing sintering of this comparative example had the following temperature and pressure rise processes:
argon is pumped into the hearth, so that the pressure of the hearth is increased to 30 MPa. Then the temperature of the hearth is increased to 1500 ℃ at the heating rate of 10 ℃/min, heat preservation is started, meanwhile, the pressure in the hearth is increased to 180 MPa, and heat preservation and pressure maintaining are continued for 2 hours.
Comparative example 2
Comparative example 1 differs from example 1 in the cooling and depressurization process of the hot isostatic pressing sintering.
The cooling and depressurization process of the hot isostatic pressing sintering of the comparative example is as follows:
after the heat preservation and pressure maintaining are finished, the temperature of the hearth is reduced to the room temperature at the speed of 10 ℃/min, the pressure is reduced along with the reduction of the temperature, and the pressure is not supplemented in the process of temperature reduction and pressure reduction. After sintering, the ceramic is subjected to air annealing in a muffle furnace at 1000 ℃ for 30 h to obtain Ho: Y 2 O 3 And (3) ceramics.
As can be seen from Table 1, ho: Y obtained in examples 1 to 4 2 O 3 The ceramics each have a porosity of less than 0.0004% and a visible light linear transmittance of more than 80%, see fig. 3. Comparative example 1 and comparative example 2 Ho: Y 2 O 3 The ceramic also achieved transparency, but compared with examples 1-4, the Ho: Y obtained in comparative example 1 and comparative example 2 2 O 3 The residual porosity of the ceramic is larger. Too many residual pores affect the visible light in-line transmittance, and thus Ho: Y obtained in comparative example 1 and comparative example 2 2 O 3 The visible light linear transmittance of the ceramic is lower than 80 percent.
TABLE 1 Properties of Ho ion doped sesquioxide transparent ceramics
Straight line transmittance (600 nm straight line light) 2.1 Oblique efficiency of μm laser output 2.1 μm 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 experiments, ho: Y 2 O 3 The residual air holes of the ceramic scatter laser, so that scattering loss is increased, and a thermal effect is prominent, and laser output power and laser output oblique efficiency are difficult to further improve.
Example 4 the absorption of pump light by the material was insufficient due to too low a concentration of Ho ion doping, failing to obtain a high power light extraction of 2.1 μm. However, the high optical quality Ho:Y prepared in examples 1-3 2 O 3 Transparent ceramics, which can utilize Ho under excitation of a suitable pump source 3+ The energy level of the ion is transited, and the high-power 2.1 mu m laser output is realized.
Referring to FIG. 4, there is obtained 0.5. 0.5 at.% Ho:Y from example 1 2 O 3 The laser output power of the ceramics at 2117 and nm wavelength changes along with the absorption power, and when the ceramic is applied, the pumping source is a thulium fiber laser with the wavelength of 1931 nm, namely, under the excitation of the pumping source of the thulium fiber, the pump source of example 1 obtains 0.5 at percent Ho: Y 2 O 3 Ceramic utilization Ho 3+ Ion excited state [ ] 5 I 7 ) To the ground state% 5 I 8 ) Can realize high-efficiency 2.1 mu m laser output.
In conclusion, the Ho ion doped sesquioxide transparent ceramic prepared by the application can be used as an ideal laser gain medium in the fields of laser radar, laser ranging, atmosphere detection and the like.
The foregoing is merely a preferred embodiment of the present application, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present application, and such modifications and variations should also be regarded as being within the scope of the application.

Claims (8)

  1. The preparation method of the Ho ion doped sesquioxide transparent ceramic is characterized by comprising the following steps of:
    y is set to 2 O 3 And Ho ion-containingThe dopants are all of 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 Powder, wherein x is more than or equal to 0.001 and less than or equal to 0.05;
    ho: Y 2 O 3 Shaping the powder to obtain a blank;
    sequentially performing vacuum sintering, hot isostatic pressing sintering, annealing and polishing treatment on the green body to obtain Ho:Y 2 O 3 A transparent ceramic;
    the hot isostatic pressing sintering comprises a heating and boosting process and a cooling and depressurization process;
    the heating and boosting process is to firstly raise the sintering temperature of the hot isostatic pressing to the target temperature, keep the temperature for 1 minute, then boost the pressure of the hot isostatic pressing cavity, raise the pressure of the hot isostatic pressing cavity to the target pressure, and keep the temperature and the pressure for 2 hours;
    the cooling and depressurization process is to reduce the sintering temperature of the hot isostatic pressing to below 1000 ℃ and then to depressurize the hot isostatic pressing cavity, so that the pressure of the hot isostatic pressing cavity is reduced to normal atmospheric pressure.
  2. 2. The method for preparing the Ho ion doped sesquioxide transparent ceramic according to claim 1, wherein during the hot isostatic pressing sintering treatment:
    the target temperature for hot isostatic pressing sintering is: 1400-1700 ℃;
    the hot isostatic pressing sintering time is as follows: 0.5-6 h;
    the inert gas for hot isostatic pressing sintering comprises argon or nitrogen;
    the gas pressure of the inert gas is as follows: 196MPa;
    the target pressure for the 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 treatment:
    the vacuum degree of the vacuum environment is less than or equal toAt 10 -3 Pa；
    The vacuum sintering temperature is 1400-1700 ℃;
    the duration of vacuum sintering 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 for preparing a Ho ion doped sesquioxide transparent ceramic according to claim 1, wherein Y is selected from the group consisting of 2 O 3 And a Ho ion-containing dopant are both of the formula (Ho x Y 1-x ) 2 O 3 Weighing, mixing, ball milling, drying, grinding, sieving and calcining in sequence, wherein the method comprises the following steps:
    absolute ethyl alcohol is added into the mixed powder to obtain slurry with the powder content of 10-30 Vol percent, and ball milling treatment is carried out 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 duration of the ball milling treatment is 3-48 h;
    and/or the mass ratio of the grinding balls subjected to ball milling to the mixed powder is 3:1-8:1;
    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.
  7. A Ho ion doped sesquioxide transparent ceramic, characterized in that it is 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 application of the Ho ion doped sesquioxide transparent ceramic as claimed in claim 7, wherein 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.
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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
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
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
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