CN113999981A - Impurity removal method for high-purity metal through vacuum sublimation - Google Patents

Impurity removal method for high-purity metal through vacuum sublimation Download PDF

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Publication number
CN113999981A
CN113999981A CN202111288177.2A CN202111288177A CN113999981A CN 113999981 A CN113999981 A CN 113999981A CN 202111288177 A CN202111288177 A CN 202111288177A CN 113999981 A CN113999981 A CN 113999981A
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quartz boat
sublimation
carbon
quartz
vacuum
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黄杰杰
何志达
李清宇
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Guangdong Vital Micro Electronics Technology Co Ltd
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Guangdong Vital Micro Electronics Technology Co Ltd
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Priority to CN202111288177.2A priority Critical patent/CN113999981A/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/04—Refining by applying a vacuum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/02—Elemental selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B17/00—Obtaining cadmium
    • C22B17/02—Obtaining cadmium by dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B17/00—Obtaining cadmium
    • C22B17/06—Refining
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/32—Refining zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/02—Obtaining antimony
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention provides an impurity removing method for vacuum sublimation of high-purity metal, which comprises the following steps: carrying out carbon plating treatment on the quartz boat to obtain a carbon-plated quartz boat; putting the material to be purified into a carbon-plated quartz boat for sublimation treatment. The invention provides a method for removing impurities on the surface of a product, which is characterized in that the impurities on the surface of the product are condensed to a condensation crucible along with antimony vapor by setting reasonable vacuum degree, heating temperature and constant temperature time and a sublimation mode; the method provided by the invention can remove impurities such as carbon, oxygen, silicon, calcium and the like on the surface of antimony, and the produced product has a bright surface, is free of oxides and is tellurium metal. The high-purity antimony vacuum sublimation method provided by the invention has the advantages of simple process, low cost, high efficiency and good purification effect.

Description

Impurity removal method for high-purity metal through vacuum sublimation
Technical Field
The invention belongs to the technical field of high-purity metal materials, and particularly relates to an impurity removal method for vacuum sublimation of high-purity metal.
Background
The purity of high-purity antimony reaches 99.9999% (6N and above), and the 6N antimony is mainly used for doping elements of semiconductor silicon and germanium and preparing semiconductors such as indium antimonide, gallium antimonide and the like. The single crystal film material prepared by MBE molecular beam epitaxy needs to use 7N high-purity tellurium, and the process has extremely high requirement on the content of high-purity antimony impurities. The preparation method of the 7N high-purity antimony mainly adopts a vacuum distillation method and a zone melting method, and the material of the vessel for containing materials in the production process is generally a graphite boat or a quartz boat. During the production process, the graphite boat is easy to decarbonize and enter the product and gather on the surface of the product. Meanwhile, the graphite boat is easy to absorb water vapor in the air, and part of tellurium can be oxidized and float on the surface of a product in the production process; the use of the quartz boat can lead the contact surface of the product and the quartz boat to have higher content of Si, Ca and other impurities; the current method for treating impurities on the surface of materials is mainly to corrode the surface by nitric acid, and the method has the risk of introducing other impurities. Meanwhile, steps of washing, drying and the like are needed after acid washing, so that the workload, the safety risk and the risk of introducing impurities are increased; the high-purity antimony of 7N grade has high requirements on field environment and personnel operation, and the surface of a product is easily polluted. The detection of a part of manufacturers for producing high-purity antimony on products is carried out by detecting the interior of the products, and the products are detected by an instrument after being subjected to surface pickling before detection, so that the detected result cannot completely represent the impurity content of the products; the use of high purity antimony, 7N, at the detector level poses a significant risk and it is therefore necessary to develop a method for treating surface impurities without melting the material.
Disclosure of Invention
In view of the above, the present invention provides a method for removing impurities by vacuum sublimation of high-purity metals, and the method provided by the present invention has a good impurity removal effect.
The invention provides an impurity removing method for vacuum sublimation of high-purity metal, which comprises the following steps:
carrying out carbon plating treatment on the quartz boat to obtain a carbon-plated quartz boat;
putting the material to be purified into a carbon-plated quartz boat for sublimation treatment.
Preferably, the carbon plating treatment further comprises:
and (4) carrying out acid soaking on the quartz boat and then cleaning.
Preferably, the acid is hydrofluoric acid.
Preferably, the method of carbon plating treatment comprises:
methane cracking process or ethanol cracking process.
Preferably, the material to be purified is one or more selected from antimony, zinc, cadmium and tellurium.
Preferably, the amount of the material to be subjected to impurity removal is 8-10 kg.
Preferably, the vacuum degree in the sublimation treatment process is 0.1-1 Pa.
Preferably, the temperature of the sublimation treatment is 580-600 ℃.
Preferably, the time of the sublimation treatment is 2 to 3 hours.
Preferably, the mass of the material subjected to sublimation treatment is 80-90% of the mass of the material to be subjected to impurity removal.
The invention provides a method for removing impurities on the surface of high-purity antimony by using a vacuum sublimation mode, and the method can be used for removing impurities on the surfaces of products such as high-purity zinc, cadmium, tellurium (6N or more) and the like. The invention provides a method for removing impurities on the surface of a product, which is characterized in that the impurities on the surface of the product are condensed to a condensation crucible along with antimony vapor by setting reasonable vacuum degree, heating temperature and constant temperature time and a sublimation mode; the method provided by the invention can remove impurities such as carbon, oxygen, silicon, calcium and the like on the surface of antimony, and the produced product has a bright surface, is free of oxides and is in a metal natural color. The high-purity antimony vacuum sublimation method provided by the invention has the advantages of simple process, low cost, high efficiency and good purification effect.
Detailed Description
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 an impurity removing method for vacuum sublimation of high-purity metal, which comprises the following steps:
carrying out carbon plating treatment on the quartz boat to obtain a carbon-plated quartz boat;
and putting the material to be purified into a carbon-plated quartz boat for sublimation treatment.
In the invention, the inner bottom surface of the quartz boat is preferably provided with a supporting point, so that each surface of the material to be purified can be uniformly sublimated.
In the present invention, it is preferable that the carbon plating treatment further comprises:
and (4) carrying out acid soaking on the quartz boat and then cleaning.
In the present invention, the acid is preferably hydrofluoric acid, more preferably a hydrofluoric acid solution, most preferably an aqueous hydrofluoric acid solution; the mass concentration of the hydrofluoric acid solution is preferably 2-5%, more preferably 3-4%, and most preferably 3.5%; the soaking time is preferably 8 hours or more, more preferably 8 to 12 hours, more preferably 9 to 11 hours, and most preferably 10 hours. In the invention, the acid soaking can remove impurities on the surface of the quartz boat.
In the present invention, the cleaning is preferably water cleaning, more preferably pure water cleaning.
In the present invention, the carbon plating treatment is preferably performed in a carbon plating furnace.
In the present invention, the method of carbon plating treatment preferably includes:
methane cracking process or ethanol cracking process.
In the present invention, the method of carbon plating treatment more preferably includes:
introducing methane into the carbon-plated furnace under the high-vacuum and high-temperature environment, so that the methane is cracked and a carbon film is deposited on the surface of the quartz boat; the quartz boat is placed in a carbon-plated furnace.
In the present invention, the high vacuum environment is preferably 10-1～10-3Pa, more preferably 10-2Pa; the high temperature is preferably 950-1100 ℃, more preferably 1000-1050 ℃, and most preferably 1020-1030 ℃; the introduction speed of methane is preferably 10-15 ml-min, more preferably 11-14 ml/min, and most preferably 12-13 ml/min; the introduction amount of the methane is preferably 300-400 ml, more preferably 330-370 ml, and most preferably 350 ml.
In the invention, the thickness of the carbon film is preferably 300-400 nm, more preferably 330-370 nm, and most preferably 350 nm; the thickness of the carbon film can be adjusted by adjusting the introduction amount of methane.
In the present invention, the carbon plating treatment preferably further comprises:
and wiping the carbon-plated quartz boat clean by using dust-free cloth and ethanol for later use.
In the present invention, the ethanol is preferably anhydrous ethanol, and more preferably UP grade anhydrous ethanol.
In the invention, the amount of the material to be purified is preferably 8-10 kg, more preferably 8.5-9.5 kg, and most preferably 9 kg.
In the present invention, the sublimation treatment is preferably performed in a heating furnace; the sublimation treatment preferably further comprises:
and wiping the quartz tube of the heating furnace by using dust-free cloth and ethanol for later use.
In the present invention, the ethanol is preferably anhydrous ethanol, and more preferably UP grade anhydrous ethanol.
In the invention, in the sublimation treatment process, the quartz boat is preferably placed in the quartz tube, the quartz boat is positioned at the center of the heating furnace, the condensation crucible is preferably placed outside the heating zone of the heating furnace, and the quartz cap is covered.
In the present invention, it is preferable that the sublimation treatment further includes:
and wiping the condensation crucible clean by using dust-free cloth and ethanol for later use.
In the present invention, the condensation crucible is preferably a condensation quartz crucible; the ethanol is preferably absolute ethanol, and more preferably UP grade absolute ethanol.
In the invention, the vacuum degree of the sublimation treatment is preferably 0.1-1 Pa, more preferably 0.3-0.8 Pa, more preferably 0.4-0.6 Pa, and most preferably 0.5 Pa; the temperature of the sublimation treatment is preferably 580-600 ℃, more preferably 585-595 ℃, and most preferably 590 ℃; the time for the sublimation treatment is preferably 2 to 3 hours, more preferably 2.3 to 2.7 hours, and most preferably 2.5 hours.
In the invention, a dust filter is preferably added in front of a vacuum system of the sublimation equipment in the sublimation treatment process, so that dust is prevented from entering the vacuum pump and influencing the service life of the vacuum pump.
In the invention, the melting point of antimony at the vacuum degree of 0.1-1 Pa is about 650 ℃, and the constant temperature (sublimation treatment temperature) is ensured to be below 650 ℃ so as to avoid melting materials.
In the invention, in the constant temperature process (sublimation treatment process), the surface of the material is gradually sublimated into steam, and impurities are condensed into the condensation crucible along with the steam.
In the present invention, it is preferable that the sublimation treatment further comprises:
cooling to room temperature after sublimation treatment, taking out the materials in the quartz boat, weighing and packaging.
In the invention, the room temperature is preferably 20-30 ℃, more preferably 23-27 ℃, and most preferably 25 ℃.
In the present invention, the cooling process is preferably performed under vacuum conditions; the degree of vacuum is preferably 0.1 to 1Pa, more preferably 0.3 to 0.8Pa, more preferably 0.4 to 0.6Pa, and most preferably 0.5 Pa.
In the present invention, after the temperature is decreased to room temperature, the method preferably further comprises:
and closing the vacuum pump, opening the inflation valve, and inflating inert gas to restore the quartz tube to normal pressure.
In the present invention, the inert gas is preferably nitrogen and/or argon; the nitrogen is preferably high-purity nitrogen; the argon is preferably high purity argon.
In the invention, the material after sublimation treatment is preferably 80-90% of the material to be purified, more preferably 83-87%, and most preferably 85%; the invention preferably adjusts the amount of the residual material by controlling the time of the sublimation treatment, if the amount of the residual material is lower than 80%, the time of the sublimation treatment is reduced, and if the amount of the residual material is higher than 90%, the time of the sublimation treatment is increased.
In the present invention, the method for removing impurities by vacuum sublimation of high purity metal preferably comprises:
soaking the quartz boat for more than 8 hours by using a hydrofluoric acid solution with the mass concentration of 2-5%, removing impurities on the surface of the quartz boat, cleaning the quartz boat by using pure water after soaking is finished, and finally performing film coating operation on the surface of the quartz boat by using a carbon coating furnace according to a carbon coating process;
wiping clean a condensation quartz crucible, a quartz boat and a quartz tube of a heating furnace by using dust-free cloth and UP-grade absolute ethyl alcohol for later use;
putting 8-10 kg of material to be sublimated into a carbon-plated quartz boat, putting the quartz boat into a quartz tube, keeping the quartz boat at the central position of a heating furnace, putting the quartz boat into a condensation crucible (arranged outside a heating area), and covering a quartz cap;
starting a vacuum pump to vacuumize to 0.1-1 Pa, starting heating, keeping the temperature at 580-600 ℃ for 2-3 hours, gradually sublimating the surface of the material into steam in the constant temperature process, and condensing impurities into a condensation crucible along with the steam;
and after the constant temperature is finished, closing the heating, cooling to room temperature, taking out the materials in the quartz boat, weighing, and carrying out vacuum packaging, wherein the residual weight of the materials in the quartz boat is preferably 80-90% of the input amount, and the materials can be adjusted by the constant temperature time.
The invention removes the impurities on the surface of the material by using a vacuum sublimation mode; a dust filter is added in front of the vacuum system to prevent dust from entering the vacuum pump and affecting the service life of the vacuum pump; avoiding impurity to get into the material through coating carbon to the quartz boat, the bottom surface design strong point in the quartz boat can ensure that every face of material all evenly sublimates. The method provided by the invention can effectively remove carbon powder and oxides in the zone-melting antimony and impurities such as silicon, calcium and the like brought by auxiliary materials, and through GDMS detection, C, O content in the processed (impurity-removed) material is less than 100ppb, and Si and Ca are less than 10 ppb; the method provided by the invention is simple to operate and high in yield, and the size and the process parameters of the quartz boat can be designed according to requirements.
Example 1
Soaking the required quartz boat for more than 8 hours by using 2-5% hydrofluoric acid solution, removing impurities on the surface of the quartz boat, cleaning the quartz boat by using pure water after soaking, and placing the quartz boat in a carbon plating furnaceMedium vacuum degree of 10-1pa, at 1050 ℃, introducing methane at a speed of 10ml/min, and performing film coating operation on the quartz boat under the condition that the total amount of methane is 300ml, wherein the thickness of the obtained carbon film is 334 nm;
wiping clean the required auxiliary materials (quartz boat, quartz condensation crucible, etc.), the quartz tube of the heating furnace by using dust-free cloth and UP-grade absolute ethyl alcohol for later use;
weighing 9kg of antimony product, placing the antimony product in a quartz boat, placing the quartz boat in a quartz tube, placing the quartz boat in the center of a heating body, placing the quartz boat in a quartz condensation crucible, and covering a tube cap;
opening a vacuum pump, opening a furnace body for heating when the vacuum degree is pumped to 0.1-1 Pa, setting the constant temperature at 600 ℃ for 2h, and waiting for the material sublimation to finish;
after the constant temperature is finished, starting to cool, continuously vacuumizing in the cooling process until the temperature is reduced to room temperature, closing the vacuum pump, opening the inflation valve, and inflating high-purity nitrogen; and after the pressure in the quartz tube is recovered to the normal pressure, taking out the materials in the quartz boat, weighing and carrying out vacuum packaging to obtain 7.95kg of the product, wherein the yield is 88.3%.
Example 2
Soaking the required quartz boat for more than 8 hours by using 2-5% hydrofluoric acid solution, removing impurities on the surface of the quartz boat, cleaning the quartz boat by using pure water after soaking, and placing the quartz boat in a carbon plating furnace with the vacuum degree of 10-2pa, at the temperature of 1000 ℃, at the methane introducing speed of 10ml/min and at the total methane amount of 350ml, performing film coating operation on the quartz boat to obtain a carbon film with the thickness of 354 nm;
wiping clean the required auxiliary materials (quartz boat, quartz condensation crucible, etc.), the quartz tube of the heating furnace by using dust-free cloth and UP-grade absolute ethyl alcohol for later use;
weighing 10kg of antimony product, placing the antimony product in a quartz boat, placing the quartz boat in a quartz tube, placing the quartz boat in the center of a heating body, placing the quartz boat in a quartz condensation crucible, and covering a tube cap;
opening a vacuum pump, opening a furnace body for heating when the vacuum degree is pumped to 0.1-1 Pa, setting the constant temperature at 580 ℃ for 3 hours, and waiting for the material sublimation to finish;
after the constant temperature is finished, starting to cool, continuously vacuumizing in the cooling process until the temperature is reduced to room temperature, closing the vacuum pump, opening the inflation valve, and inflating high-purity nitrogen; and after the pressure in the quartz tube is restored to the normal pressure, taking out the materials in the quartz boat, weighing and carrying out vacuum packaging to obtain 8.55kg of the product, wherein the yield is 85.5%.
Example 3
Soaking the required quartz boat for more than 8 hours by using 2-5% hydrofluoric acid solution, removing impurities on the surface of the quartz boat, cleaning the quartz boat by using pure water after soaking, and placing the quartz boat in a carbon plating furnace with the vacuum degree of 10-1pa, at the temperature of 1000 ℃, at the methane introducing speed of 13ml/min and under the condition of the total methane amount of 360ml, performing film coating operation on the quartz boat to obtain a carbon film with the thickness of 365 nm;
wiping clean the required auxiliary materials (quartz boat, quartz condensation crucible, etc.), the quartz tube of the heating furnace by using dust-free cloth and UP-grade absolute ethyl alcohol for later use;
weighing 8.5kg of antimony product, placing the antimony product in a quartz boat, placing the quartz boat in a quartz tube, placing the quartz boat in the center of a heating body, placing the quartz boat in a quartz condensation crucible, and covering a tube cap;
opening a vacuum pump, opening a furnace body for heating when the vacuum degree is pumped to 0.1-1 Pa, setting the constant temperature at 590 ℃, keeping the constant temperature for 2.5 hours, and waiting for the material sublimation to finish;
after the constant temperature is finished, starting to cool, continuously vacuumizing in the cooling process until the temperature is reduced to room temperature, closing the vacuum pump, opening the inflation valve, and inflating high-purity nitrogen; and after the pressure in the quartz tube is recovered to the normal pressure, taking out the materials in the quartz boat, weighing and carrying out vacuum packaging to obtain 7.05kg of the product, wherein the yield is 82.9%.
Example 4
Soaking the required quartz boat for more than 8 hours by using 2-5% hydrofluoric acid solution, removing impurities on the surface of the quartz boat, cleaning the quartz boat by using pure water after soaking, and placing the quartz boat in a carbon plating furnace with the vacuum degree of 10-3pa, at 1050 ℃, performing film coating operation on the quartz boat under the conditions that the methane introducing speed is 10ml/min and the total methane amount is 320ml, wherein the thickness of the obtained carbon film is 344 nm;
wiping clean the required auxiliary materials (quartz boat, quartz condensation crucible, etc.), the quartz tube of the heating furnace by using dust-free cloth and UP-grade absolute ethyl alcohol for later use;
weighing 9kg of antimony product, placing the antimony product in a quartz boat, placing the quartz boat in a quartz tube, placing the quartz boat in the center of a heating body, placing the quartz boat in a quartz condensation crucible, and covering a tube cap;
opening a vacuum pump, opening a furnace body for heating when the vacuum degree is pumped to 0.1-1 Pa, setting the constant temperature at 600 ℃ for 3h, and waiting for the material sublimation to finish;
after the constant temperature is finished, starting to cool, continuously vacuumizing in the cooling process until the temperature is reduced to room temperature, closing the vacuum pump, opening the inflation valve, and inflating high-purity nitrogen; and after the pressure in the quartz tube is recovered to the normal pressure, taking out the materials in the quartz boat, weighing and carrying out vacuum packaging to obtain 7.26kg of the product, wherein the yield is 80.7%.
Example 5
Soaking the required quartz boat for more than 8 hours by using 2-5% hydrofluoric acid solution, removing impurities on the surface of the quartz boat, cleaning the quartz boat by using pure water after soaking, and placing the quartz boat in a carbon plating furnace with the vacuum degree of 10-2pa, at the temperature of 1000 ℃, at the methane introducing speed of 10ml/min and at the total methane amount of 300ml, performing film coating operation on the quartz boat to obtain a carbon film with the thickness of 338 nm;
wiping clean the required auxiliary materials (quartz boat, quartz condensation crucible, etc.), the quartz tube of the heating furnace by using dust-free cloth and UP-grade absolute ethyl alcohol for later use;
weighing 10kg of antimony product, placing the antimony product in a quartz boat, placing the quartz boat in a quartz tube, placing the quartz boat in the center of a heating body, placing the quartz boat in a quartz condensation crucible, and covering a tube cap;
opening a vacuum pump, opening a furnace body for heating when the vacuum degree is pumped to 0.1-1 Pa, setting the constant temperature at 600 ℃ for 3h, and waiting for the material sublimation to finish;
after the constant temperature is finished, starting to cool, continuously vacuumizing in the cooling process until the temperature is reduced to room temperature, closing the vacuum pump, opening the inflation valve, and inflating high-purity nitrogen; and after the pressure in the quartz tube is recovered to the normal pressure, taking out the materials in the quartz boat, weighing and carrying out vacuum packaging to obtain 8.65kg of the product, wherein the yield is 86.5%.
Performance detection
Detecting the contents of carbon, oxygen, silicon and calcium on the surface of the product subjected to sublimation treatment in the detection embodiment of GDMS equipment, and observing the surface condition; the results are shown in Table 1.
TABLE 1 product performance test results after treatment in the examples of the present invention
Comparative example (untreated) Example 1 Example 2 Example 3 Example 4 Example 5
Carbon content (ppb) 1260 <100 <100 <100 <100 <100
Oxygen content (ppb) 2304 <50 85 77 64 56
Silicon content (ppb) 126 <10 <10 <10 <10 <10
Calcium content (ppb) 43 <10 <10 <10 <10 <10
Surface condition of the surface Blackening hair Light brightness Light brightness Light brightness Light brightness Light brightness
As can be seen from Table 1, after the treatment by the method provided by the embodiment of the invention, the contents of carbon and oxygen in the material are both less than 100ppb, and the contents of silicon and calcium are less than 10ppb, so that the method meets the use requirements of customers. After testing and setting corresponding process parameters, the method and the equipment provided by the invention can also be used for removing surface impurities of high-purity cadmium, tellurium and zinc products.
The invention removes the impurities on the surface of the material by using a vacuum sublimation mode; a dust filter is added in front of the vacuum system to prevent dust from entering the vacuum pump and affecting the service life of the vacuum pump; avoiding impurity to get into the material through coating carbon to the quartz boat, the bottom surface design strong point in the quartz boat can ensure that every face of material all evenly sublimates. The method provided by the invention can effectively remove carbon powder and oxide in zone-melting tellurium and impurities such as silicon, calcium and the like brought by auxiliary materials, and through GDMS detection, C, O content in the processed (after impurity removal) material is less than 100ppb, and Si and Ca are less than 10 ppb; the method provided by the invention is simple to operate and high in yield, and the size and the process parameters of the quartz boat can be designed according to requirements.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.

Claims (10)

1. An impurity removing method for high-purity metal vacuum sublimation comprises the following steps:
carrying out carbon plating treatment on the quartz boat to obtain a carbon-plated quartz boat;
putting the material to be purified into a carbon-plated quartz boat for sublimation treatment.
2. The method of claim 1, wherein the carbon plating process further comprises, prior to:
and (4) carrying out acid soaking on the quartz boat and then cleaning.
3. The method of claim 2, wherein the acid is hydrofluoric acid.
4. The method of claim 1, wherein the method of carbon plating comprises: methane cracking process or ethanol cracking process.
5. The method according to claim 1, wherein the material to be decontaminated is selected from one or more of antimony, zinc, cadmium and tellurium.
6. The method according to claim 1, wherein the amount of the material to be decontaminated is 8-10 kg.
7. The method according to claim 1, wherein the degree of vacuum during the sublimation treatment is 0.1 to 1 Pa.
8. The method according to claim 1, wherein the temperature of the sublimation treatment is 580 to 600 ℃.
9. The method according to claim 1, wherein the time for the sublimation treatment is 2 to 3 hours.
10. The method according to claim 1, wherein the mass of the material after sublimation is 80-90% of the mass of the material to be purified.
CN202111288177.2A 2021-11-02 2021-11-02 Impurity removal method for high-purity metal through vacuum sublimation Pending CN113999981A (en)

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