阅读说明：本技术 一种掺硫硒粒的制备方法 (Preparation method of sulfur-doped selenium particles ) 是由 付勇 王波 陈应红 陈秋旭 叶道明 于 2020-12-30 设计创作，主要内容包括：本发明涉及一种掺硫硒粒的制备方法,其包括如下步骤：S1：熔料：将高纯硒原料分为第一部分和第二部分,第一部分所占的质量分数为60～90%,将第一部分的高纯硒原料投入坩埚内,并将坩埚置于熔料炉中,将坩埚内温度控制在250℃～380℃,直到第一部分的高纯硒原料熔融完全；S2：掺硫：控制高纯硒温度在250～340℃,然后将硫粒和第二部分的高纯硒原料一起加入坩埚内,物料完全熔融后,维持物料温度为250～310℃,然后将物料搅拌适当时间得到掺硫的硒液；S3：制粒干燥：掺硫的硒液经制粒、干燥得到掺硫硒粒。本发明一种掺硫硒粒的制备方法首创性的制备出稳定的硫含量为10～1000ppm的掺硫硒粒,其操作便捷、工艺简单,可以大规模生产,且制备的硒粒氧含量低于5ppm。(The invention relates to a preparation method of sulfur-doped selenium particles, which comprises the following steps: s1: melting: dividing a high-purity selenium raw material into a first part and a second part, wherein the first part accounts for 60-90% by mass, putting the first part of the high-purity selenium raw material into a crucible, placing the crucible into a melting furnace, and controlling the temperature in the crucible to be 250-380 ℃ until the first part of the high-purity selenium raw material is completely melted; s2: blending sulfur: controlling the temperature of the high-purity selenium to be 250-340 ℃, then adding the sulfur particles and a second part of high-purity selenium raw material into a crucible together, maintaining the temperature of the material to be 250-310 ℃ after the material is completely melted, and then stirring the material for a proper time to obtain a sulfur-doped selenium liquid; s3: granulating and drying: and granulating and drying the sulfur-doped selenium liquid to obtain sulfur-doped selenium granules. The preparation method of the sulfur-doped selenium particles initiatively prepares the stable sulfur-doped selenium particles with the sulfur content of 10-1000 ppm, is convenient to operate, simple in process and capable of realizing large-scale production, and the oxygen content of the prepared selenium particles is lower than 5 ppm.)

1. A preparation method of sulfur-doped selenium particles is characterized by comprising the following steps: which comprises the following steps:

s1: melting: dividing a high-purity selenium raw material into a first part and a second part, wherein the first part accounts for 60-90% by mass, putting the first part of the high-purity selenium raw material into a crucible, placing the crucible into a melting furnace, and controlling the temperature in the crucible to be 250-380 ℃ until the first part of the high-purity selenium raw material is completely melted;

s2: blending sulfur: controlling the temperature of the high-purity selenium to be 250-340 ℃, then adding the sulfur particles and a second part of high-purity selenium raw material into a crucible together, maintaining the temperature of the material to be 250-310 ℃ after the material is completely melted, and then stirring the material for a proper time to obtain a sulfur-doped selenium liquid;

s3: granulating and drying: and granulating and drying the sulfur-doped selenium liquid to obtain sulfur-doped selenium granules.

2. The method of claim 1, wherein: the purity of the high-purity selenium raw material is 5N or more.

3. The method of claim 1, wherein: the crucible is a quartz crucible.

4. The method of claim 1, wherein: the sulfur particles have a purity of 5N or more.

5. The method of claim 1, wherein: the particle size of the sulfur particles is 1-6 mm.

6. The method of claim 1, wherein: the appropriate time is 3 to 5 minutes.

7. The method of claim 1, wherein: the stirring is carried out by using a quartz rod or a quartz tube.

8. The method of claim 1, wherein: the granulation refers to pouring the selenium liquid doped with sulfur into a quartz funnel, and cooling the liquid drop-shaped selenium in pure water to obtain selenium granules.

9. The method of claim 8, wherein: during the granulation process, the temperature of pure water is lower than 50 ℃.

10. The method of claim 1, wherein: the drying specifically means drying in an oven at 40-45 ℃.

Technical Field

The invention relates to the field of preparation of thin-film solar raw materials, in particular to a preparation method of sulfur-doped selenium particles.

Background

At present, selenium is widely applied to the industries of electronics, glass, chemical pigments, metallurgy, agriculture, biology, cosmetics, medicine and health care food; in particular to the high-tech field, such as the manufacturing fields of semiconductor devices, photoelectric devices, selenium solar batteries, laser devices, laser and infrared light guide materials, and the like.

The copper indium gallium selenide thin-film solar cell is considered as a new generation solar cell with the most development prospect due to the advantages of high conversion efficiency, good low-light performance, strong radiation resistance, low manufacturing cost and the like. The CIGS absorbing layer is the core part of the CIGS thin-film solar cell and is formed by doping sulfur element and properly regulating and controlling the element proportion_xSe_1-x) The material can adjust the band gap to improve the light absorption efficiency. The forming mode of the copper indium gallium sulfur selenium layer mainly comprises the following steps: the CIGS layer is placed at a high temperature, a precursor containing a sulfur simple substance is introduced, sulfur and the CIGS are subjected to chemical reaction to replace part of selenium elements on the surface of the original CIGS layer, and a CIGS/CIGS double-layer structure is formed, which is generally called a (surface) vulcanization process. And then, continuing to grow an n-type semiconductor layer on the copper indium gallium sulfur selenium layer and performing a back-end process to obtain the complete thin-film solar cell.

In the prior art, the sulfidation process uses primarily H₂S、H₂S/O₂The gaseous precursor is used as the source of the elemental sulfur. However, hydrogen sulfide itself is toxic and needs to be carried out in a highly safe state, which increases the production equipment, detection and monitoring equipment, and maintenance costs, and also has potential safety hazards to workers. In addition, when the gas precursor is used for the process, the time required by the process is long, and the process parameters such as gas concentration, gas flow field distribution and the like need to be additionally tested and controlled, so that the time is consumed, and the requirements of large area, uniform, continuous production, stability and the like required by the industry are not easily met.

Therefore, the demand for products doped with 10-1000 ppm of sulfur in high-purity selenium is met, and the sulfur-doped selenium is used as a raw material for preparing the copper indium gallium selenium. Therefore, how to stably and uniformly dope sulfur into high-purity selenium without introducing other impurities is a technical problem to be solved urgently.

Therefore, it is necessary to design a method for preparing sulfur-doped selenium particles to solve the above technical problems.

Disclosure of Invention

The invention aims to provide a preparation method of sulfur-doped selenium particles, which takes high-purity selenium and sulfur particles as raw materials and prepares the sulfur-doped selenium particles in a crucible.

In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of sulfur-doped selenium particles comprises the following steps:

s1: melting: dividing a high-purity selenium raw material into a first part and a second part, wherein the first part accounts for 60-90% by mass, putting the first part of the high-purity selenium raw material into a crucible, placing the crucible into a melting furnace, and controlling the temperature in the crucible to be 250-380 ℃ until the first part of the high-purity selenium raw material is completely melted;

s2: blending sulfur: controlling the temperature of the high-purity selenium to be 250-340 ℃, then adding the sulfur particles and a second part of high-purity selenium raw material into a crucible together, maintaining the temperature of the material to be 250-310 ℃ after the material is completely melted, and then stirring the material for a proper time to obtain a sulfur-doped selenium liquid;

s3: granulating and drying: and granulating and drying the sulfur-doped selenium liquid to obtain sulfur-doped selenium granules.

The invention has the beneficial effects that: the preparation method of the sulfur-doped selenium particles initiatively prepares the stable sulfur-doped selenium particles with the sulfur content of 10-1000 ppm, is convenient to operate, simple in process and capable of realizing large-scale production, and the oxygen content of the prepared selenium particles is lower than 5 ppm.

Detailed Description

The technical solutions will be described clearly and completely in the following with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a preparation method of sulfur-doped selenium particles, which comprises the following steps.

S1: melting: the method comprises the steps of dividing a high-purity selenium raw material into a first part and a second part, wherein the first part accounts for 60-90% by mass, putting the first part of the high-purity selenium raw material into a crucible, placing the crucible into a melting furnace, and controlling the temperature in the crucible to be 250-380 ℃ until the first part of the high-purity selenium raw material is completely melted.

S2: blending sulfur: controlling the temperature of the high-purity selenium to be 250-340 ℃, then adding the sulfur particles and the second part of high-purity selenium raw material into a crucible together, maintaining the temperature of the materials to be 250-310 ℃ after the materials are completely melted, and then stirring the materials for a proper time to obtain the sulfur-doped selenium liquid.

S3: granulating and drying: and granulating and drying the sulfur-doped selenium liquid to obtain sulfur-doped selenium granules.

The sulfur doping mode of the invention is to melt part of selenium firstly, then add selenium and sulfur particles into a crucible together, bring the sulfur particles into the selenium liquid through selenium, and immediately melt sulfur into the selenium liquid. If the selenium and the sulfur particles are mixed and then added into the crucible for melting, the sulfur is completely volatilized before the selenium material is melted and cannot be mixed into the crucible; if the selenium is completely melted and then doped with sulfur, the sulfur will float on the surface of the selenium liquid due to low sulfur density, and the sulfur will be volatilized quickly due to the melting temperature being higher than 250 ℃, thereby affecting the sulfur doping effect.

As a further improvement of the invention, the purity of the high-purity selenium raw material is 5N or more.

As a further improvement of the invention, the crucible is a quartz crucible.

As a further improvement of the present invention, the purity of the sulfur particles is 5N or more.

As a further improvement of the invention, the particle size of the sulfur particles is 1-6 mm.

As a further improvement of the invention, the appropriate time is 3-5 minutes.

As a further improvement of the invention, the stirring is carried out by using a quartz rod or a quartz tube.

As a further improvement of the invention, the granulation is that the selenium liquid doped with sulfur is poured into a quartz funnel, and the liquid drop-shaped selenium is cooled in pure water to obtain selenium granules. Further, the temperature of pure water during granulation is below 50 ℃.

As a further improvement of the invention, the drying specifically means drying in an oven at 40-45 ℃.

Example 1.

9kg of high-purity selenium raw material is put into a crucible, the crucible is placed in a melting furnace, and the temperature in the crucible is controlled at 250 ℃ until the high-purity selenium raw material is completely melted. Controlling the temperature of the high-purity selenium at 250 ℃, then adding 0.16g of sulfur particles and the rest 1kg of high-purity selenium raw material into a crucible together, maintaining the temperature of the material at 250 ℃ after the material is completely melted, and then stirring the material for 5 minutes to obtain the sulfur-doped selenium liquid. And granulating the sulfur-doped selenium solution, and drying at 40 ℃ to obtain sulfur-doped selenium granules. The sulfur content of the two samples is respectively 10.64ppm and 10.98ppm by sampling detection, and the oxygen content is less than 5 ppm.

Example 2.

7kg of high-purity selenium raw material is put into a crucible, the crucible is placed in a melting furnace, and the temperature in the crucible is controlled at 300 ℃ until the high-purity selenium raw material is completely melted. Controlling the temperature of the high-purity selenium to be 300 ℃, then adding 2.00g of sulfur particles and the rest 3kg of high-purity selenium raw material into a crucible together, maintaining the temperature of the material to be 280 ℃ after the material is completely melted, and then stirring the material for 4 minutes to obtain the sulfur-doped selenium liquid. The sulfur-doped selenium liquid is granulated and dried at 42 ℃ to obtain sulfur-doped selenium granules. The sulfur content of the two samples is 135.74ppm and 136.35ppm by sampling detection, and the oxygen content is less than 5 ppm.

Example 3.

6kg of high-purity selenium raw material is put into a crucible, the crucible is placed in a melting furnace, and the temperature in the crucible is controlled at 380 ℃ until the high-purity selenium raw material is completely melted. Controlling the temperature of the high-purity selenium at 340 ℃, then adding 15.00g of sulfur particles and the rest 4kg of high-purity selenium raw material into a crucible together, maintaining the temperature of the material at 310 ℃ after the material is completely melted, and then stirring the material for 3 minutes to obtain the sulfur-doped selenium liquid. And granulating the sulfur-doped selenium solution, and drying at 45 ℃ to obtain sulfur-doped selenium granules. The sulfur content of the two samples is 997.17ppm and 999.62ppm by sampling detection, and the oxygen content is less than 5 ppm.

The preparation method of the sulfur-doped selenium particles initiatively prepares the stable sulfur-doped selenium particles with the sulfur content of 10-1000 ppm, is convenient to operate, simple in process and capable of realizing large-scale production, and the oxygen content of the prepared selenium particles is lower than 5 ppm.

Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.