阅读说明：本技术 一种硒化锌光学材料的制备方法 (Preparation method of zinc selenide optical material ) 是由 张高峰 张荣实 李特 甘硕文 刘孟寅 李霄鹏 荣景颂 周珺 刘华松 于 2021-10-14 设计创作，主要内容包括：本发明属于光学材料制备技术领域,具体涉及一种硒化锌光学材料的制备方法。首先通过加热使硒化锌(ZnSe)粉体原料使其气化,然后在合适的环境下凝结生长成硒化锌晶坯,再经热等静压处理完善晶格结构,消除内部微观缺陷,提高致密度,制备成可作为光学透镜材料使用的硒化锌光学材料。该方法制备的硒化锌光学材料的品质达到了现有技术制备的硒化锌光学材料品质,能够广泛用于硒化锌光学透镜材料的应用领域,具有制备工艺简单、安全环保、周期短、品质高的特点。(The invention belongs to the technical field of optical material preparation, and particularly relates to a preparation method of a zinc selenide optical material. Firstly, heating to gasify a zinc selenide (ZnSe) powder raw material, then condensing and growing the raw material into a zinc selenide crystal blank in a proper environment, and then completing a lattice structure through hot isostatic pressing treatment to eliminate internal microscopic defects and improve density, thereby preparing the zinc selenide optical material capable of being used as an optical lens material. The quality of the zinc selenide optical material prepared by the method reaches the quality of the zinc selenide optical material prepared by the prior art, can be widely applied to the application field of zinc selenide optical lens materials, and has the characteristics of simple preparation process, safety, environmental protection, short period and high quality.)

1. A preparation method of a zinc selenide optical material is characterized by comprising the following steps:

the method comprises the following steps:

heating and gasifying a zinc selenide powder raw material to obtain zinc selenide gas;

adjusting the temperature to condense the zinc selenide gas to obtain a zinc selenide crystal blank;

and putting the zinc selenide crystal blank into a treatment furnace for lattice treatment to obtain the zinc selenide optical material.

2. The method for preparing a zinc selenide optical material according to claim 1, wherein the method comprises the following steps: heating under vacuum condition to gasify the zinc selenide powder raw material.

3. The method for preparing the zinc selenide optical material according to claim 2, wherein the method comprises the following steps: the grain size of the zinc selenide powder raw material is less than or equal to 20 mu m.

4. The method for preparing the zinc selenide optical material according to claim 3, wherein the method comprises the following steps: the purity of the zinc selenide powder raw material is more than or equal to 99.5 percent.

5. The method for preparing zinc selenide optical material according to claim 2The method is characterized in that: vacuum degree less than or equal to 1 x 10^-3Pa。

6. The method for preparing the zinc selenide optical material according to claim 5, wherein the method comprises the following steps: the heating temperature is 980-1080 ℃, and the heating speed is less than or equal to 3 ℃/min.

7. The method for preparing a zinc selenide optical material according to claim 1, wherein the method comprises the following steps: the condensation temperature of the zinc selenide gas is 950-990 ℃.

8. The method for preparing a zinc selenide optical material according to claim 1, wherein the method comprises the following steps: the condensation speed of the zinc selenide crystal blank is 0.2-0.5 mm/h.

9. The method for preparing a zinc selenide optical material according to claim 8, wherein: and cooling the zinc selenide crystal blank after the condensation is finished, wherein the cooling speed is less than or equal to 100 ℃/h.

10. The method for preparing a zinc selenide optical material according to claim 1, wherein the method comprises the following steps: the treatment furnace is a hot isostatic pressing furnace and mainly comprises the following steps:

heating to 900-950 ℃;

pressurizing to 100-120 MPa.

Technical Field

The invention relates to the technical field of optical material preparation, in particular to a preparation method of a zinc selenide optical material.

Background

Zinc selenide (ZnSe) is an excellent infrared optical material, has the characteristics of wide transmission range (0.5-20 mu m), high transmission ratio (more than 60%), low variation of thermo-optic coefficient with temperature and low absorption coefficient of 10.6 mu m, and is widely used as optical elements such as laser optical windows, optical lenses and the like.

From 70-80 years of the last century, zinc selenide optical materials are mainly prepared by a vacuum hot pressing method and a chemical vapor deposition method. The method for preparing the zinc selenide optical material by adopting the vacuum hot pressing method is simple and has high environmental protection performance, but the obtained optical material has low purity and lower optical performance and is difficult to apply in the high-precision field. The zinc selenide optical material prepared by the chemical vapor deposition method has high optical performance and can be widely applied to various application fields, however, the preparation process needs to use virulent H2Se gas, the post-treatment is needed, the leakage risk exists, serious environmental protection and safety problems exist, the process control difficulty is high, more than two raw materials are needed, the proportion is strictly controlled, the preparation temperature and the pressure are very sensitive, the preparation period is long, and the preparation period is usually about 20 days.

Disclosure of Invention

In view of the above defects or shortcomings in the prior art, the present application aims to provide a method for preparing a zinc selenide optical material, which has a simple preparation process and a short period compared with the prior art, and the material quality reaches the quality of the zinc selenide optical material prepared by the prior art, and can directly replace the zinc selenide optical material prepared by the prior art.

The application provides a preparation method of a zinc selenide optical material, which comprises the following steps:

heating and gasifying a zinc selenide powder raw material to obtain zinc selenide gas;

adjusting the temperature to condense the zinc selenide gas to obtain a zinc selenide crystal blank;

and putting the zinc selenide crystal blank into a treatment furnace for lattice treatment to obtain the zinc selenide optical material.

Preferably, the zinc selenide powder raw material is gasified by heating under vacuum condition.

Preferably, the grain size of the zinc selenide powder raw material is less than or equal to 20 mu m.

Preferably, the purity of the zinc selenide powder raw material is more than or equal to 99.5%.

Preferably, the degree of vacuum is less than or equal to 1X 10^-3Pa。

Preferably, the heating temperature is 980-1080 ℃, and the heating speed is less than or equal to 3 ℃/min.

Preferably, the condensation temperature of the zinc selenide gas is 950-990 ℃.

Preferably, the condensation speed of the zinc selenide crystal blank is 0.2-0.5 mm/h.

Preferably, the temperature of the zinc selenide crystal blank is reduced after the condensation is finished, and the cooling speed is less than or equal to 100 ℃/h.

Preferably, the treatment furnace is a hot isostatic pressing furnace, and mainly comprises the following steps:

heating to 900-950 ℃;

pressurizing to 100-120 MPa.

Unless otherwise specified, any range recited herein includes any value between the endpoints and any sub-range defined by any value between the endpoints or any value between the endpoints.

In conclusion, the application discloses a preparation method of a zinc selenide optical material, and the beneficial effects produced based on the scheme are that a zinc selenide powder raw material is heated under a vacuum condition to be gasified, then zinc selenide gas is condensed into a zinc selenide crystal blank by adjusting the temperature and the heat preservation time, and finally a hot isostatic pressing machine is adopted to perform high-temperature and high-pressure lattice perfection treatment on the zinc selenide crystal blank to obtain the zinc selenide optical material. The method has the advantages of simple process, no toxic gas emission in the preparation process, safety and environmental protection, and the obtained zinc selenide optical material has the quality reaching the preparation level of the prior art, and can be used as a raw material to replace the optical material prepared by the prior art and directly applied to the processing and manufacturing of various optical lens materials.

In addition to the technical problems addressed by the present invention, the technical features constituting the technical solutions, and the advantages brought by the technical features of the technical solutions described above, other technical problems solved by the present invention, other technical features included in the technical solutions, and advantages brought by the technical features will be described in further detail below.

Drawings

Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:

FIG. 1 is a graph showing the transmittance of the zinc selenide optical material prepared in example 1 at a wavelength of 2 to 14 μm.

FIG. 2 is a graph showing the transmittance of the zinc selenide optical material prepared in example 2 at a wavelength of 2 to 14 μm.

Detailed Description

The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention. It should be noted that, for convenience of description, only the portions related to the present invention are shown in the drawings.

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.

Example 1

The embodiment provides a preparation method of a zinc selenide optical material with the diameter of 200mm and the thickness of 20mm, which comprises the following steps:

s1, heating to gasify the zinc selenide powder raw material to obtain zinc selenide gas;

specifically, 5kg of zinc selenide powder raw material is put into a deposition crucible evaporation area, the grain size of the zinc selenide powder raw material is 2-20 mu m, the purity is 99.56%, and then the mixture is vacuumized to 1 multiplied by 10^-3Pa below, and heating at a rate of 3 deg.C/minAnd heating the evaporation zone to 1080 ℃ to gasify the zinc selenide powder raw material to obtain zinc selenide gas.

S2, adjusting the temperature to condense the zinc selenide gas to obtain a zinc selenide crystal blank;

specifically, the temperature of a precipitation zone of a precipitation crucible is adjusted to 980 ℃, heat preservation is carried out for 70 hours, zinc selenide gas is controlled to be condensed into a zinc selenide crystal blank at a speed of about 0.3mm/h, the temperature is reduced to room temperature at a cooling speed of 80 ℃/h after the heat preservation time is finished, and then the zinc selenide crystal blank is taken out.

And S3, carrying out lattice treatment on the zinc selenide crystal blank to obtain the zinc selenide optical material.

Specifically, the zinc selenide crystal blank is placed into a hot isostatic pressing furnace, then is heated to 900 ℃, is pressurized to 100Mpa, is cooled after being kept warm for 5 hours, and is taken out to obtain the zinc selenide optical material. The treatment can eliminate the internal micro-pores of the zinc selenide, reduce the internal defects of the crystal and improve the density, thereby improving the quality of the zinc selenide optical material.

The transmittance of the zinc selenide optical material obtained by the preparation method in the wavelength range of 2-14 μm is shown in fig. 1, the optical transmittance in the medium-long wavelength range of 3-5 μm and the optical transmittance in the 8-10 μm range are not lower than 71%, table 1 shows the refractive index of the zinc selenide optical material prepared in the embodiment 1 in the wavelength range of 2-12 μm, and table 2 shows the temperature coefficient of the zinc selenide optical material prepared in the embodiment 1 in the wavelength range of 3.39 μm. By comparing the performance of the zinc selenide optical material prepared by the chemical vapor deposition method in the table 1, the performance of the zinc selenide optical material prepared by the method is very similar to that of the zinc selenide optical material, and the zinc selenide optical material reaches the level of mutual substitution.

TABLE 1

TABLE 2

Serial number	Temperature/. degree.C	Temperature coefficient of refractive index/. degree.C
			1	39.0	6.36×10-5
2	59.1	6.66×10-5
			3	78.9	6.53×10-5

Example 2

The embodiment provides a preparation method of a zinc selenide optical material with the diameter of 150mm and the thickness of 15mm, which comprises the following steps:

s1, heating to gasify the zinc selenide powder raw material to obtain zinc selenide gas;

specifically, 2kg of zinc selenide powder raw material is put into a deposition crucible evaporation area, the grain size of the zinc selenide powder raw material is 2-20 mu m, the purity is 99.56%, and then the zinc selenide powder raw material is vacuumized to 1 multiplied by 10^-3And (4) heating the evaporation zone to 1050 ℃ at the heating speed of 2.5 ℃/min below Pa to gasify the raw material of the zinc selenide powder to obtain the zinc selenide gas.

S2, adjusting the temperature to condense the zinc selenide gas to obtain a zinc selenide crystal blank;

specifically, the temperature of a precipitation zone of a precipitation crucible is adjusted to 950 ℃, heat preservation is carried out for 75 hours, zinc selenide gas is controlled to be condensed into a zinc selenide crystal blank at a speed of about 0.2mm/h, the temperature is reduced to room temperature at a cooling speed of 80 ℃/h after the heat preservation time is finished, and then the zinc selenide crystal blank is taken out.

And S3, carrying out lattice treatment on the zinc selenide crystal blank to obtain the zinc selenide optical material.

Specifically, the zinc selenide crystal blank is placed into a hot isostatic pressing furnace, then is heated to 900 ℃, is pressurized to 100Mpa, is cooled after being kept warm for 4 hours, and is taken out to obtain the zinc selenide optical material. The treatment can eliminate the internal micro-pores of the zinc selenide, reduce the internal defects of the crystal and improve the density, thereby improving the quality of the zinc selenide optical material.

The thickness of the zinc selenide optical material prepared by the preparation method is 15mm, the transmittance in the wavelength range of 2-14 μm is shown in fig. 1, the optical transmittance in the medium-long wave range of 3-5 μm and the optical transmittance in the wavelength range of 8-10 μm is not lower than 71%, table 3 shows the refractive index of the zinc selenide optical material prepared in the embodiment 2 in the wavelength range of 2-12 μm, and table 4 shows the temperature coefficient of the zinc selenide optical material prepared in the embodiment 2 in the wavelength range of 3.39 μm. By comparing the performance of the optical material prepared by chemical vapor deposition with that of zinc selenide in table 3, it can be seen that the performance of the optical material prepared by the method of the present invention is very similar to that of the optical material, and the optical material reach the level of mutual substitution.

TABLE 3

TABLE 4

Serial number	Temperature/. degree.C	Temperature coefficient of refractive index/. degree.C
			1	39.0	6.36×10-5
2	60.4	6.46×10-5
			3	79.3	6.52×10-5

It can be seen from the above examples that, the invention heats the zinc selenide powder raw material under vacuum condition to gasify the zinc selenide powder, then coagulates the zinc selenide gas into a zinc selenide crystal blank by adjusting the temperature and the heat preservation time, and finally carries out high-temperature and high-pressure lattice perfection treatment on the zinc selenide crystal blank by using a hot isostatic pressing machine to obtain the zinc selenide optical material. The method has the advantages of simple process, no toxic gas emission in the preparation process, safety, environmental protection and short preparation period, the quality of the obtained zinc selenide optical material reaches the preparation level of the prior art usually within about 7 days, and the zinc selenide optical material can be used as a raw material to replace the optical material prepared by the prior art and can be directly applied to the processing and manufacturing of various optical lens materials.

It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be made within the scope of the present invention.

The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.