CN111392699B - Preparation method of cadmium selenide - Google Patents
Preparation method of cadmium selenide Download PDFInfo
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- CN111392699B CN111392699B CN202010227264.6A CN202010227264A CN111392699B CN 111392699 B CN111392699 B CN 111392699B CN 202010227264 A CN202010227264 A CN 202010227264A CN 111392699 B CN111392699 B CN 111392699B
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- C01B19/00—Selenium; Tellurium; Compounds thereof
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Abstract
The invention discloses a preparation method of cadmium selenide, which comprises the steps of fully mixing cadmium powder and selenium powder according to a certain proportion; putting the mixture into a carbon-coated quartz tube, vacuumizing, introducing inert gas into the tube, and sealing the quartz tube; preheating the bottom of the quartz tube, and then heating and reacting in a moving heating mode; cooling to obtain the cadmium selenide product. The method solves the technical problems of environmental pollution risk, complex equipment, uncontrolled reaction process, low utilization rate of reaction raw materials, high preparation cost and the like in the high temperature and high pressure in the conventional cadmium selenide synthesis process.
Description
Technical Field
The invention belongs to the field of semiconductor materials, and particularly relates to a preparation method of cadmium selenide.
Background
Cadmium selenide (CdSe) is a compound N-type semiconductor material, has an energy gap value of about 1.74eV, is in an ideal energy gap range of a solar cell, and has good photoelectric conversion efficiency. With the rapid development of the thin film industry, thin film science and technology and thin film materials have become hot spots of research in the field of materials science. Cadmium selenide is used as an N-type thin-film solar material and can be combined with cadmium telluride to form a P-N junction to replace the conventional cadmium sulfide layer, so that the efficiency of a cadmium telluride solar cell can be improved, and the research on the synthesis method is favorable for the development of the thin-film solar material. Meanwhile, the cadmium selenide compound can also be used for manufacturing infrared modulators, infrared detection and the like.
The conventional preparation method of cadmium selenide is to prepare cadmium selenide by co-heating metal cadmium and hydrogen selenide, and can also prepare cadmium selenide by directly combining metal cadmium and selenium at high temperature. However, the prior art mainly has the following defects: 1. the high temperature and high pressure in the preparation process can cause the generation of pollution sources; 2. the reaction vessel in the preparation process is disposable, so that the preparation cost is increased; 3. the reaction is violent and uncontrolled; 4. the gas-phase reaction preparation method has higher requirements on equipment; 5. when the reaction vessel is a quartz tube, cadmium can be adhered to the reaction vessel at high temperature, so that waste of reaction raw materials and difficulty in taking materials are caused.
Patent document CN108083239A discloses a method for synthesizing high-purity cadmium selenide, which specifically comprises the steps of uniformly mixing selenium particles and cadmium particles according to a certain proportion, then loading into a graphite cylinder, then loading into a quartz tube, vacuumizing and sealing the tube, placing into a rocking furnace, heating to 800-. The method has high reaction temperature, violent reaction in a reaction tube, difficult control, and the phenomenon of coating elemental selenium or cadmium under the violent reaction condition, reduces the reaction efficiency, and has to adopt the operation of hydrogenation impurity removal in the follow-up process. In addition, the quartz tube is not used for one time, and waste is large.
Patent document CN108017042A discloses a preparation method of high-purity cadmium selenide, which specifically comprises the steps of uniformly mixing selenium particles and cadmium particles according to a certain proportion, placing the mixture in a high-temperature and high-pressure furnace, heating to 800-. The method is carried out at high temperature and high pressure, the risk of cadmium source leakage is easy to occur in the synthesis process or during material taking, the high-temperature and high-pressure reaction conditions are harsh, the preparation cost is high, and the energy consumption is serious.
Patent document CN107675251A discloses a method for preparing cadmium selenide, which uses a low-temperature gas phase synthesis method to prepare a cadmium selenide material, and the prepared product is cadmium selenide powder with small yield.
Patent document CN106477536A discloses a method for preparing ultra-pure cadmium selenide, in which raw materials are filled into a quartz ampoule, a tube is sealed by vacuumizing, liquid phase synthesis is performed at high temperature, the yield is small, and the quartz ampoule can be used only once, and the cost is high.
In order to overcome the defects of the prior art, the invention provides the preparation method of the cadmium selenide, the reaction temperature is mild, the reaction efficiency is higher while the energy is saved, and the cadmium selenide with higher purity can be obtained without subsequent hydrogenation and impurity removal. In addition, the quartz tube in the preparation method provided by the invention is not used for one time, so that the resource waste is avoided, and the production cost is saved.
Disclosure of Invention
The invention aims to provide a preparation method of cadmium selenide, which mainly solves the technical problems of environmental pollution risk, complex equipment, uncontrolled reaction process, low utilization rate of reaction raw materials and the like in the high-temperature and high-pressure synthesis process of the existing cadmium selenide, and the problem of high preparation cost caused by the fact that a reaction container cannot be reused.
The purpose of the invention is realized by the following technical scheme.
In a first aspect, the present invention provides a method for preparing cadmium selenide, comprising the following steps:
(1) weighing cadmium powder and selenium powder according to the molar ratio of 1 (1.05-1.08), and fully mixing the cadmium powder and the selenium powder;
(2) placing the mixture of cadmium powder and selenium powder into a carbon-coated quartz tube, vacuumizing the quartz tube, introducing inert gas into the tube, and sealing the quartz tube;
(3) starting a heating device, preheating the bottom of the quartz tube at the temperature of 250-;
(4) and (4) cooling, taking down the quartz tube, picking off the quartz tube sealing plug, and inverting the quartz tube to take out the cadmium selenide block.
Preferably, in the step (1), the cadmium powder and the selenium powder are put into a homogenizing device and homogenized for 1-2 h.
Preferably, the quartz tube is sealed in the step (2) by selecting a sealing plug matched with the tube mouth of the quartz tube for sealing.
After the quartz tube is sealed in the step (2), the cadmium powder and the selenium powder are deposited at the bottom of the quartz tube, the upper part of the quartz tube is filled with inert gas, and the volume of the inert gas in the quartz tube accounts for 80-85% of the space of the quartz tube.
The inert gas in the step (2) includes but is not limited to one or a combination of two or more of nitrogen, helium and argon.
In the most preferred embodiment of the present invention, the inert gas is nitrogen.
The carbon-coated quartz tube used in the step (2) can be replaced by a quartz tube loaded with a graphite reaction boat.
The moving heating in the step (3) means that when the heating device is heated to 580-650 ℃, the quartz tube is moved so that the bottom of the quartz tube slowly passes through the heating zone, and the heating device can also be moved slowly so that the heating device slowly passes through the bottom of the quartz tube. Compared with a fixed heating mode, the moving heating mode can reduce the intensity of reaction in the quartz tube, so that heat passes through reaction raw materials in a layer-by-layer scanning mode, and the reaction efficiency is higher.
The moving heating has the advantages that only the cadmium powder and the selenium powder at the bottom are heated in the reaction process, the inert gas area at the upper part is not heated, the reaction is not violent at a mild reaction temperature, the unreacted cadmium, the selenium simple substance and the oxide thereof gradually rise along with the reaction and meet nitrogen, a simple substance film layer is formed on the upper pipe wall of the quartz pipe, and finally the prepared cadmium selenide has less impurities and high purity.
In a preferred embodiment of the invention, an inventor specially customizes a vertical moving heating furnace to realize moving heating, the vertical moving heating furnace comprises a heating furnace and a heating furnace lifting device, a quartz tube is arranged on the vertical moving heating furnace, a heating program is started, the temperature is increased to 300 ℃ at the temperature increasing rate of 5 ℃/min, and the bottom of the quartz tube is subjected to heat preservation for 30 min; then the temperature is raised to the reaction temperature of 580-650 ℃ at the temperature raising rate of 20 ℃/min, a heating furnace moving device is started, the heating furnace is made to move slowly, the moving speed is 10-12mm/h, the heating furnace is made to pass through a reaction raw material zone at the bottom of the quartz tube in a reciprocating manner, the heating reaction is carried out for 4-5h, and the reciprocating frequency of the heating furnace is more than or equal to 1.
Preferably, the cadmium selenide block obtained in the step (4) is crushed by a crusher, the crushed cadmium selenide can be placed in a ball milling tank for ball milling, and products with different particle sizes can be obtained by screening after ball milling. The ball milling mode and the type of the ball milling tank are not particularly limited and can be selected according to actual requirements, and the applicable ball milling tank can be selected from a polyurethane ball milling tank or a zirconia ball milling tank.
In the preferred embodiment of the invention, the cadmium powder and the selenium powder which are used as reaction raw materials have the purity of 99.999 percent and the particle size of 0.2-0.6 mm. The homogenizing device used by the invention is an HJ series horizontal homogenizing device, the diameter of the quartz tube is 70-90mm, the length is 800-900mm, the wall thickness is 2-3mm, the carbon-coated quartz tube can avoid the contact of cadmium powder and the quartz tube, the adhesion problem of cadmium and the quartz tube at high temperature is avoided, the discharging is easier, and the coated quartz tube can be repeatedly used.
The carbon-coated quartz tube used in the present invention may be a quartz tube having a carbon film coated on the surface thereof prepared in any manner, and is preferably a carbon-coated quartz tube treated by the coating method disclosed in the present patent publication No. CN 108996916A.
The vertical moving heating furnace used in the embodiment of the invention is a self-made heating furnace, is similar to zone melting equipment, and only moves the heating furnace longitudinally. The quartz tube is arranged on the vertical moving heating furnace, and the verticality deviation of the quartz tube and the verticality deviation of the heating furnace are not more than 1%.
The invention has the following beneficial effects: 1. the reaction process is a low-pressure closed process, so that the risk of environmental pollution is avoided; 2. the reaction temperature is lower, and the electric energy consumption is less; 3. the reaction speed is mild, and the utilization rate of raw materials is high; 4. the carbon film-plated quartz tube of the reaction vessel can avoid the contact of cadmium powder and the quartz tube, avoid the adhesion problem of cadmium and the quartz tube, and the carbon film-plated quartz tube can be used repeatedly; 5. the reaction is complete, the product purity is high, and the purity of the synthesized cadmium selenide product is 99.999 percent; 6. the yield is high, and 1.5-2kg of cadmium selenide products can be synthesized by each quartz tube at one time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some 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.
Preparation of cadmium selenide
Example 1
S1: 1034.33g of cadmium powder and 765.67g of selenium powder are weighed, and the cadmium powder and the selenium powder are put into HJ series horizontal homogenization equipment to be homogenized for 1 hour;
s2: putting the homogenized mixture of the cadmium powder and the selenium powder into a graphite reaction boat, then putting the graphite reaction boat into a quartz tube, vacuumizing the quartz tube, introducing nitrogen into the tube, and sealing the quartz tube, wherein the volume of the nitrogen is 80% of that of the quartz tube;
s3: installing a quartz tube on a vertical movable heating furnace, starting a heating program to preheat the bottom of the quartz tube, wherein the preheating temperature is 250 ℃, the preheating time is 0.5h, continuing to heat to 580 ℃, starting a moving device of the heating furnace to enable the heating furnace to slowly pass through a reaction raw material area at the bottom of the quartz tube in a reciprocating manner, heating the raw material at the bottom of the quartz tube in a movable heating manner, and carrying out heating reaction for 5 h;
s4: and (3) after the furnace body is cooled, taking down the quartz tube, removing a little powder on the wall of the quartz tube, picking off the sealing plug of the quartz tube, and inverting the quartz tube to take out the cadmium selenide block.
Example 2
S1: 1078.69g of cadmium powder and 821.31g of selenium powder are weighed, and the cadmium powder and the selenium powder are put into HJ series horizontal homogenization equipment to be homogenized for 1 hour;
s2: the homogenized mixture of cadmium powder and selenium powder is filled into a carbon-coated quartz tube, the quartz tube is vacuumized, nitrogen is introduced into the tube, and the quartz tube is sealed, wherein the volume of the nitrogen is 85 percent of that of the quartz tube;
s3: installing a quartz tube on a vertical movable heating furnace, starting a heating program to preheat the bottom of the quartz tube, wherein the preheating temperature is 300 ℃, the preheating time is 0.5h, continuing to heat to 650 ℃, starting a moving device of the heating furnace to enable the heating furnace to slowly pass through a reaction raw material area at the bottom of the quartz tube in a reciprocating manner, heating the raw material at the bottom of the quartz tube in a movable heating manner, and carrying out heating reaction for 4 h;
s4: and (3) after the furnace body is cooled, taking down the quartz tube, removing a little powder on the wall of the quartz tube, picking off the sealing plug of the quartz tube, and inverting the quartz tube to take out the cadmium selenide block.
Comparative example 1
The amount of the reaction raw materials is the same as that in example 2 (1078.69 g of cadmium powder and 821.31g of selenium powder), and the preparation method is the same as that in example 2, except that no preheating step is performed in step S3, the heating furnace is directly heated to 650 ℃, and the heating furnace moving device is started to move and heat the bottom of the quartz tube for 4 hours.
Comparative example 2
The reaction materials were used in the same amount as in example 2 (1078.69 g cadmium powder, 821.31g selenium powder) and the preparation method was the same as in example 2 except that no moving heating was used in step S3, and the bottom of the quartz tube was preheated to 650 ℃ as in example 2, and then the bottom of the quartz tube was subjected to a fixed heating reaction for 4 hours.
Comparative example 3
The reaction raw material consumption is the same as that of example 2 (1078.69 g of cadmium powder and 821.31g of selenium powder), and the preparation method is the same as that of example 2, except that in step S2, the mixture of cadmium powder and selenium powder is filled into a carbon-film-plated quartz tube, then vacuum pumping and sealing are carried out, nitrogen is not introduced into the tube, the reaction temperature disclosed in patent CN108083239A is referred, the heating furnace is directly heated to 1000 ℃, and a heating furnace moving device is started to move and heat the bottom of the quartz tube for 4 hours.
Effects of the embodiment
After the heating reaction of the cadmium selenide prepared in examples 1 to 2 and comparative examples 1 to 3 is finished, the cadmium selenide is obtained by cooling and discharging, samples are respectively taken, and purity analysis is performed by inductively coupled plasma mass spectrometry (ICP-MS), and specific results are shown in tables 1 and 2.
TABLE 1 product yield and purity results for cadmium selenide preparation
TABLE 2 impurity content of cadmium selenide product
According to the results in table 1, the cadmium selenide product prepared by the preparation method provided by the invention has high purity which reaches 99.999%, and the utilization rate of raw materials is more than 99%. The preparation method described in comparative example 1, which was not preheated before the heating reaction, had product purity and raw material utilization of only 99.9% and 85.12%. The preparation method described in comparative example 2 does not adopt a moving heating mode in the heating process, so that the product purity is only 99%, and the raw material utilization rate is as low as 79.82%. The preparation method described in comparative example 3 refers to the method disclosed in patent CN108083239A for preparing cadmium selenide, the reaction conditions are severe, preheating and moving heating operations are not performed, the heating furnace is directly heated to 1000 ℃ for reaction, the purity of the finally prepared product is 99.9%, and the utilization rate of raw materials is 95.23%. According to the result analysis, the method provided by the application has mild reaction conditions, and the product purity and the raw material utilization rate are effectively improved through the reaction modes of preheating and moving heating.
As can be seen from the data results in Table 2, the cadmium selenide prepared by the method disclosed by the application has lower impurity content, which is mainly reflected in the content of five elements of Ca, Cr, Fe, Na and Sn. Especially Fe, the content of Fe in the cadmium selenide prepared by the method described in the present application is 0.2ppm, while the content of Fe in the cadmium selenide prepared by the method disclosed in patent document CN108083239A is 0.62ppm, which is 3 times as high as that of the present application, which indicates that the impurity content of the product prepared by the direct high temperature violent reaction method described in comparative example 3 is high. The content of Ca element in the cadmium selenide prepared in the comparative example 1 and the comparative example 2 is 4-5 times higher than that in the example 1 and the example 2, and the impurity content in the product can be effectively reduced in the preheating link and the moving heating link in the preparation method disclosed by the application.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. A method for preparing cadmium selenide, comprising the steps of:
(1) weighing cadmium powder and selenium powder according to a molar ratio of 1 (1.05-1.08), wherein the purity of the cadmium powder and the selenium powder is 99.999%, and the particle size of the cadmium powder and the selenium powder is 0.2-0.6mm, and putting the cadmium powder and the selenium powder into a homogenizing device for homogenizing for 1-2 hours;
(2) placing the mixture of cadmium powder and selenium powder into a carbon-coated quartz tube, vacuumizing the quartz tube, introducing inert atmosphere into the tube, and sealing the quartz tube;
(3) starting a heating device, preheating the bottom of the quartz tube at the temperature of 250-; heating to the reaction temperature of 580-650 ℃ at the heating rate of 20 ℃/min, starting a heating furnace moving device to enable the heating furnace to move slowly at the moving speed of 10-12mm/h, enabling the heating furnace to pass through a reaction raw material zone at the bottom of the quartz tube in a reciprocating manner, and carrying out heating reaction for 4-5h, wherein the reciprocating frequency of the heating furnace is more than or equal to 1;
(4) and (4) cooling, taking down the quartz tube, picking off the quartz tube sealing plug, and inverting the quartz tube to take out the cadmium selenide block.
2. The preparation method according to claim 1, wherein in the step (2), the quartz tube is sealed by selecting a sealing plug matched with the tube opening of the quartz tube.
3. The preparation method as claimed in claim 1, wherein the quartz tube in step (2) has a tube diameter of 70-90mm, a length of 800-900mm and a wall thickness of 2-3 mm.
4. The method as set forth in claim 1, wherein after the quartz tube is sealed in the step (2), the cadmium powder and the selenium powder are deposited on the bottom of the quartz tube, and the upper portion of the quartz tube is filled with an inert gas, wherein the volume of the inert gas in the quartz tube is 80-85% of the space of the quartz tube.
5. The method according to claim 1, wherein the inert atmosphere in step (2) includes but is not limited to one or a combination of two or more of nitrogen, helium and argon.
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