CN115418719A - Preparation method of low-oxygen compact ultra-high-purity arsenic rod - Google Patents
Preparation method of low-oxygen compact ultra-high-purity arsenic rod Download PDFInfo
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Abstract
The invention relates to a preparation method of a low-oxygen compact ultra-high-purity arsenic rod, which comprises the following steps: s1, preparing a sublimation pipe and a forming die; s2, carrying out sublimation deoxidation purification treatment on the ultra-pure arsenic block material in a sublimation tube at high temperature in a hydrogen atmosphere; s3, crushing, and then loading into a forming die; deoxidizing in high temperature and vacuum environment; s4, liquefying at high pressure and high temperature in an inert gas atmosphere; s5, directionally solidifying and crystallizing from bottom to top under the high pressure and inert gas atmosphere, cooling to room temperature after complete solidification, relieving pressure, taking out the forming die in the inert gas atmosphere environment, and demoulding to obtain the ultra-pure arsenic rod. The preparation method of the low-oxygen compact ultra-high-purity arsenic rod can effectively reduce the oxygen content of the formed ultra-high-purity arsenic rod; the whole preparation method has the advantages of complete process, simple flow and easy operation, and ensures that the purity of the formed arsenic rod can meet the development requirement of the semiconductor material industry.
Description
Technical Field
The invention relates to the field of arsenic rod forming, in particular to a preparation method of a low-oxygen compact ultra-high-purity arsenic rod.
Background
Ultra-high purity arsenic means the total amount of impurities<1ppm of metallic arsenic, a non-metallic element widely distributed in nature, is gradually oxidized into black on the surface contacting air. The high-purity arsenic can be used for preparing III-V group compound semiconductor materials such As GaAs, inA and the like and monocrystalline dopants of silicon and germanium, and can also be used for preparing As 2 Se 3 (infrared ray transmitting glass, laser printer, etc.), as 2 S 3 (infrared ray transmitting glass) and the like. Its primary function is to synthesize gallium arsenide, and the demand for high purity arsenic is largely determined by the market for gallium arsenide. Gallium arsenide is now widely used in the fabrication of diodes, infrared emitting tubes, lasers, solar cells, etc., and is also playing an increasing role in the advanced technological fields of microelectronics, optoelectronics, military, aerospace, computers, etc.
At present, ultra-high-purity arsenic is mainly used for compound semiconductors, the adopted ultra-high-purity arsenic is in an irregular block shape, other impurities are inevitably introduced or the oxygen content is higher in the processing process, but with the rapid development requirement of the semiconductor material technology, particularly the development of the molecular beam epitaxy technology, the downstream industry has higher requirements on the shape and the oxygen content of the ultra-high-purity arsenic.
The conventional arsenic rod forming method generally adopts a direct casting method or mechanical processing. However, arsenic has special properties, the melting point of which is 814 ℃, but sublimation is started when the arsenic is heated to 615 ℃ to form gaseous arsenic, that is, solid high-purity arsenic is heated and then sublimated to form arsenic vapor at 615 ℃, and the arsenic vapor is liquefied to form high-purity liquid when the arsenic vapor is heated to 814 ℃, and the direct casting method cannot be adopted according to the special properties of arsenic. Meanwhile, high-purity arsenic is brittle and is difficult to machine into a required shape in a machining mode, and the high-purity arsenic is contacted with other metals or substances during machining, so that the high-purity arsenic is easily polluted.
Therefore, the preparation process of the environment-friendly ultra-high-purity arsenic rod needs to be researched to meet the development requirement of the semiconductor material industry. The current available data is not the preparation method of the low-oxygen compact ultra-high-purity arsenic rod.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a low-oxygen compact ultra-high-purity arsenic rod, which can effectively reduce the oxygen content of the formed ultra-high-purity arsenic rod; the whole preparation method has the advantages of complete process, simple flow and easy operation, and ensures that the purity of the formed arsenic rod can meet the development requirement of the semiconductor material industry.
The technical scheme adopted by the invention for solving the technical problem is as follows: a preparation method of a low-oxygen compact ultra-high-purity arsenic rod comprises the following steps:
s1, preparing a sublimation pipe and a forming mold;
s2, weighing an ultra-pure arsenic block material, filling the ultra-pure arsenic block material into a sublimation tube, and sealing the tube opening by using a quartz ground opening; continuously introducing hydrogen to form a hydrogen atmosphere, heating to 600-700 ℃, sublimating arsenic in the hydrogen atmosphere, and carrying out first deoxidation treatment under a high-temperature condition;
s3, after the first deoxidation treatment is finished, taking out the arsenic in the sublimation pipe in an inert gas atmosphere environment, crushing the arsenic, and then filling the crushed arsenic into a forming die; the forming die is arranged in a forming furnace and is vacuumized to 10 DEG -4 Pa below, heating to 530-580 deg.C by heating mechanism, and heating to 10 deg.C -4 Keeping the temperature constant under a vacuum environment below Pa, and performing secondary deoxidation treatment under a high-temperature condition;
s4, after the second deoxidation treatment is finished, continuing heating and raising the temperature, meanwhile, introducing high-pressure inert gas to form an inert gas atmosphere and provide a high-pressure environment, and after the temperature is raised to 815-850 ℃, keeping the temperature and the pressure constant;
and S5, controlling the heating mechanism to move upwards relative to the forming mold, gradually cooling the forming mold from bottom to top, further directionally solidifying and crystallizing the arsenic liquid in the forming mold from bottom to top, cooling to room temperature after complete solidification, relieving pressure, taking out the forming mold in an inert gas atmosphere environment, and demolding to obtain the ultra-pure arsenic rod.
The sublimation pipe and the forming die prepared in the step S1 are sequentially soaked in aqua regia, washed clean by high-purity water and dried.
In the step S2, in the process of temperature rise, gas is discharged and leaching treatment is carried out; in the step S3, when vacuumizing is performed, exhausting the extracted gas and performing leaching treatment; and step S5, carrying out rinsing treatment on the gas discharged by pressure relief.
The leaching treatment adopts 5-10% NaOH aqueous solution.
In the step S2, the hydrogen is high-purity hydrogen, and the purity of the hydrogen at least reaches 99.999 percent; the hydrogen flow is 400-800mL/min.
In step S4, the heating rate is 1 ℃/min; the high pressure environment is 3.8-4.2MPa.
In step S3, the forming furnace and the heating mechanism form a forming device; the forming furnace comprises a furnace body, a furnace chamber is formed in the furnace body, a forming die fixing seat is installed in the furnace chamber, and the forming die is placed in the forming die fixing seat in the furnace chamber of the forming furnace; the outer side of the furnace body is also provided with a gas pipeline assembly which is communicated with the furnace chamber and used for controlling and operating the gas in the furnace chamber; the gas control operation at least comprises vacuum pumping operation, high-pressure inert gas introducing operation and exhaust operation; the heating mechanism comprises a heating part, wherein a heating channel with an upper opening and a lower opening is formed in the heating part; the heating channel is matched with the forming furnace and used for heating the forming furnace.
The gas pipeline assembly comprises a gas pipeline busbar communicated with the furnace chamber; the gas path busbar is connected with a vacuumizing pipeline, an inert gas pressurizing pipeline and a tail gas discharging pipeline; a vacuum control valve is arranged on the vacuumizing pipeline, and a pressurizing control valve is arranged on the inert gas pressurizing pipeline; and the tail gas discharge pipeline is provided with a discharge valve.
The heating mechanism further comprises a temperature sensor arranged on the heating part, and the working end of the temperature sensor is close to the heating channel.
The forming device also comprises a bracket for mounting the forming furnace and the heating mechanism; the bracket is also provided with a lifting mechanism; the heating mechanism is fixed with the lifting moving end of the lifting mechanism; the lifting mechanism is used for driving the heating mechanism to move up and down so as to enable the heating channel to move up and down relative to the forming furnace; the forming die is a quartz tube, the diameter of the forming die is 15-150mm, and the length of the forming die is 30-130mm; in step S5, the speed of the heating mechanism moving upwards relative to the forming die is 10-50mm/h.
The invention has the advantages that: according to the preparation method of the low-oxygen compact ultra-high-purity arsenic rod, the oxygen content of the formed ultra-high-purity arsenic rod can be effectively reduced through sublimation in a hydrogen atmosphere and two-stage deoxidation under a vacuum heating condition; the whole preparation method has the advantages of complete process, simple flow and easy operation, and ensures that the purity of the formed arsenic rod can meet the development requirement of the semiconductor material industry.
Drawings
FIG. 1 is a flow chart of a method for preparing a low-oxygen dense ultra-high-purity arsenic rod according to an embodiment;
FIG. 2 is a schematic view of a forming apparatus in a method for preparing a low-oxygen dense ultra-high-purity arsenic rod according to an embodiment;
FIG. 3 is a schematic view of a forming furnace in a method of manufacturing a low-oxygen dense ultra-high-purity arsenic rod according to an embodiment;
the device comprises a support 1, a heating mechanism 2, a forming furnace 3, a lifting mechanism 4, a heating part 21, a heating channel 22, a temperature sensor 23, a furnace body 31, a furnace chamber 32, a forming mold fixing seat 33, a gas pipeline assembly 34, a gas pipeline bus 341, a vacuum pumping pipeline 342, an inert gas pressurizing pipeline 343, a tail gas exhaust pipeline 344, a safety protection pipeline 345, a vacuum control valve 346, a pressure control valve 347, an exhaust valve 348, a safety valve 349, a lead screw assembly 41, a lifting driving element 42 and a mounting rack 43.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the present invention as illustrated in the accompanying drawings.
As shown in fig. 1 to 3, the present embodiment provides a method for preparing a low-oxygen dense ultra-high-purity arsenic rod, which comprises the following steps:
s1, preparing a sublimation pipe and a forming die;
s2, weighing an ultra-pure arsenic block material, filling the ultra-pure arsenic block material into a sublimation tube, and sealing the tube opening by using a quartz ground opening; continuously introducing hydrogen to form a hydrogen atmosphere, heating to 600-700 ℃, sublimating arsenic in the hydrogen atmosphere, and carrying out first deoxidation treatment under a high-temperature condition;
s3, after the first deoxidation treatment is finished, taking out arsenic in the sublimation pipe in an inert gas atmosphere environment, crushing the arsenic, and then loading the crushed arsenic into a forming mold; the forming die is put into a forming furnace and vacuumized to 10 degrees -4 Pa below, heating to 530-580 deg.C by heating mechanism, and heating to 10 deg.C -4 Keeping the temperature constant under a vacuum environment below Pa, and performing secondary deoxidation treatment under a high-temperature condition;
s4, after the second deoxidation treatment is finished, continuously heating and raising the temperature, simultaneously introducing high-pressure inert gas to form an inert gas atmosphere and provide a high-pressure environment, and after the temperature is raised to 815-850 ℃, keeping the temperature and the pressure constant;
and S5, controlling the heating mechanism to move upwards relative to the forming mold, gradually cooling the forming mold from bottom to top, further directionally solidifying and crystallizing the arsenic liquid in the forming mold from bottom to top, cooling to room temperature after complete solidification, relieving pressure, taking out the forming mold in an inert gas atmosphere environment, and demolding to obtain the ultra-pure arsenic rod.
In the method for preparing a low-oxygen compact ultra-high-purity arsenic rod according to the embodiment, the sublimation tube and the forming mold prepared in the step S1 are sequentially soaked in aqua regia, washed clean with high-purity water, and dried.
In the preparation method of the low-oxygen compact ultra-high-purity arsenic rod of the embodiment, in the step S2, in the process of temperature rise, gas is discharged and leaching treatment is performed; in the step S3, when vacuumizing is performed, exhausting the extracted gas and performing leaching treatment; and step S5, leaching the gas discharged by pressure relief.
In the preparation method of the low-oxygen compact ultra-high-purity arsenic rod, the leaching treatment adopts 5-10% of NaOH aqueous solution by mass concentration; specifically, the gas in the steps S2, S3 and S5 can be discharged after two-stage high-efficiency leaching absorption treatment.
In the preparation method of the low-oxygen compact ultra-high-purity arsenic rod of the embodiment, in the step S2, hydrogen is high-purity hydrogen, and the purity of the hydrogen is at least 99.999%; the hydrogen flow is 400-800mL/min.
In the preparation method of the low-oxygen compact ultra-high-purity arsenic rod of the embodiment, in the step S4, the heating rate is 1 ℃/min; the high pressure environment is 3.8-4.2MPa.
In the method for preparing a low-oxygen compact ultra-high-purity arsenic rod according to the embodiment, in step S3, the forming furnace 3 and the heating mechanism 2 form a forming device; the forming furnace 3 comprises a furnace body 31, a furnace chamber 32 is formed inside the furnace body, a forming mold fixing seat 33 is installed in the furnace chamber 32, and the forming mold is placed on the forming mold fixing seat 33 in the furnace chamber 32 of the forming furnace 3; a gas pipeline assembly 34 is further arranged on the outer side of the furnace body 31, and the gas pipeline assembly 34 is communicated with the furnace chamber 32 and used for controlling and operating gas in the furnace chamber 32; the gas control operation at least comprises vacuum pumping operation, high-pressure inert gas introducing operation and exhaust operation; the heating mechanism 2 comprises a heating part 21, and a heating channel 22 with an upper opening and a lower opening is formed in the heating part 21; the heating channel 22 is matched with the forming furnace 3 and used for heating the forming furnace 3. The heating unit 21 may be a resistance heating furnace.
In the preparation method of the present embodiment, the gas pipe assembly 34 includes a gas pipe bus 341 communicating with the furnace chamber 32; the gas path busbar is connected with a vacuumizing pipeline 342, an inert gas pressurizing pipeline 343 and a tail gas discharging pipeline 344; a vacuum control valve 346 is arranged on the vacuumizing pipeline 342, and a pressure control valve 347 is arranged on the inert gas pressurizing pipeline 343; the exhaust gas discharge pipeline 344 is provided with a discharge valve 348; the gas pipeline assembly 34 further comprises a safety protection pipeline 345, and a safety valve 349 is further arranged on the safety protection pipeline 345; the vacuum control valve 346, the pressurization control valve 347, the discharge valve 348 and the relief valve 349 are valves which can be opened and closed in response to a control command of a control system; the molding apparatus further comprises a control system; the furnace body 31 is also provided with a pressure sensor for monitoring the pressure of the furnace chamber; the control system is configured to: in response to the evacuation command, the vacuum control valve 346 is controlled to open; responding to a horizontal rotation instruction, and controlling a horizontal rotation mechanism to start; in response to the pressurization command, controlling the vacuum control valve 346 to close and controlling the pressurization control valve 347 to open, receiving furnace chamber pressure data monitored by the pressure sensor, and controlling the pressurization control valve 347 to close when the pressure value reaches a first set value; in response to the tapping command, the discharge valve 348 is controlled to open. In this embodiment, the vacuum pumping pipeline 342 is used for connecting a vacuum pumping system (vacuum pump), the inert gas pressurizing pipeline 343 is used for connecting a high-pressure high-purity inert gas source, and the tail gas discharging pipeline 344 is used for connecting a tail gas leaching system; under control of the control system: the vacuum control valve 346 is opened when vacuuming and closed when pressurizing; the pressurizing control valve 347 is opened when pressurizing, high-purity inert gas is filled into the furnace chamber, the pressurizing control valve 347 and the pressure sensor form interlocking control, and the pressure of the gas filled into the furnace chamber is regulated until the required pressure (a first set value) is reached; the exhaust valve 348 remains closed during the forming process and is opened only when it is ready to be discharged, the chamber is depressurized, and the exhaust gas is treated by the off-gas leaching system. The control system is further configured to: and receiving the furnace chamber pressure data monitored by the pressure sensor, and controlling the safety valve 349 to open when the pressure value reaches a second set value.
In the preparation method of the low-oxygen compact ultra-high-purity arsenic rod according to the embodiment, the vacuumizing pipeline 342 is used for connecting a vacuumizing system (vacuum pump), the inert gas pressurizing pipeline 343 is used for connecting a high-pressure high-purity inert gas source, and the tail gas discharging pipeline 344 is used for connecting a tail gas leaching system; under control of the control system: the vacuum control valve 346 is opened when vacuuming and closed when pressurizing; the pressurizing control valve 347 is opened when pressurizing, high-purity inert gas is filled into the furnace chamber, the pressurizing control valve 347 and the pressure sensor form interlocking control, and the pressure of the gas filled into the furnace chamber is regulated until the required pressure (a first set value) is reached; the exhaust valve 348 remains closed during the forming process and is opened only when it is ready to be discharged, the chamber is depressurized, and the exhaust gas is treated by the off-gas leaching system.
In the method for preparing the low-oxygen compact ultra-high-purity arsenic rod according to the embodiment, the outlet end of the safety protection pipeline 345 may be connected to the outlet end of the tail gas discharge pipeline 344; under the control of the control system, the safety valve 349 forms an interlocking control with the pressure sensor; when the pressure in the furnace chamber is too high (the second set value), the safety valve 349 is opened to release the pressure in the furnace chamber, and the discharged gas is treated by the tail gas leaching system.
In the preparation method of the low-oxygen dense ultra-high-purity arsenic rod of the present embodiment, the heating mechanism 2 further includes a temperature sensor 23 installed on the heating portion 21, and a working end of the temperature sensor 23 is close to the heating channel 22; wherein, temperature sensor can adopt accuse temperature thermocouple, and through the real-time feedback of accuse temperature thermocouple, heating mechanism carries out accurate accuse temperature.
In the preparation method of the low-oxygen compact ultra-high-purity arsenic rod of the embodiment, the forming device further comprises a bracket 1 for mounting the forming furnace 3 and the heating mechanism 2; the bracket 1 is also provided with a lifting mechanism 4; the heating mechanism 2 is fixed with the lifting moving end of the lifting mechanism 4; the lifting mechanism 4 is used for driving the heating mechanism 2 to move up and down, so that the heating channel 22 moves up and down relative to the forming furnace; the forming die is a quartz tube, the diameter of the forming die is 15-150mm, and the length of the forming die is 30-130mm; in step S5, the speed of the heating mechanism moving upwards relative to the forming die is 10-50mm/h. In addition, the lifting mechanism 4 may include a screw assembly 41 mounted to the bracket 1, a lifting driving element 42 (servo motor) for driving the screw, and a mounting bracket 43 fixed to the screw nut, wherein the mounting bracket 43 is fixed to the heating mechanism 2 as a lifting moving end of the lifting mechanism 4. The drive of elevating system 4 makes heating mechanism 2 can reciprocate, the design of upper and lower open-ended heating channel in the heating mechanism 2, make heating mechanism when the solidification shaping of arsenic stick, can adopt the mode of rebound, make forming die can follow supreme cooling down gradually down, such cooling shaping mode, can make the arsenic material cool off earlier from the bottom and solidify, the top surface solidifies at last, directional solidification shaping can guarantee the compactness of shaping arsenic stick, and in this embodiment, through the mode of heating channel for forming die rebound, still can guarantee the arsenic stick and solidify the back, the top is level and smooth, no shrinkage cavity.
In the preparation method of the low-oxygen compact ultra-high-purity arsenic rod of the embodiment, the control system adopts DCS centralized remote control, and the method comprises the steps of setting a temperature-rising program, adjusting gas pressure, setting and adjusting pressure in a cavity, and controlling speed and temperature during directional solidification and crystallization.
In the preparation method of the low-oxygen compact ultra-high-purity arsenic rod according to the embodiment, the crushing, charging, demolding and other operations performed in the steps S2, S3, S4 and S5 are performed in a glove box into which high-purity inert gas is introduced, and are performed under an environment in which the inert gas is high-purity argon (the purity is not less than 99.999%).
In the preparation method of the low-oxygen compact ultra-high-purity arsenic rod in the embodiment, in the step S2 and the step S3, a process combining sublimation deoxidation and high-temperature deoxidation in vacuum needs to be adopted for two-stage deoxidation treatment, meanwhile, a certain purification and impurity removal effect can be achieved by controlling the hydrogen flow and sublimation temperature in the sublimation process, and if only the single sublimation deoxidation or high-temperature deoxidation process in vacuum is adopted, the purity and oxygen content of the high-purity arsenic rod can be influenced.
The effects of the present invention will be demonstrated by combining examples and comparative examples, and the related examples are only for explaining the present invention and do not limit the scope of the present invention.
The following examples and comparative examples each used ultra-high purity arsenic having a purity of 99.999992%.
Example one
A. Soaking auxiliary parts such as a sublimation pipe and five flat-bottom high-purity quartz forming dies with the diameter of 35 mm and the diameter of 300mm in aqua regia for 24 hours, washing the auxiliary parts with high-purity water, and drying the auxiliary parts for later use;
B. firstly, charging the weighed ultra-pure arsenic block material, then loading the material into a sublimation tube, and sealing the tube opening by using a quartz grinding opening; opening a hydrogen valve, adjusting the hydrogen flow, continuously introducing hydrogen for 4-6h, starting a heating device, carrying out sublimation operation according to a set temperature-raising program, controlling the temperature during sublimation to be 600-700 ℃, and enabling tail gas generated in the process to enter a tail gas leaching system;
C. after the sublimation is finished, atDischarging and crushing the materials in the glove operating box under the protection of inert gas, weighing 445g of high-purity arsenic 5 parts, and respectively and correspondingly filling the weighed materials into 5 high-purity quartz forming molds; finally, the forming die is simultaneously placed in a forming die fixing seat and is fixed in a furnace chamber of a forming furnace, a furnace cover is covered, fastening and sealing are carried out, a vacuum system is started for vacuumizing, and the requirement of vacuum degree is better than 10 -4 Pa, starting a heating program after the vacuum is achieved, heating to 530-580 ℃, keeping the temperature for 1h, and carrying out deoxidation treatment again at high temperature;
D. after the deoxidation process is finished, continuing to heat according to a set heating program, filling high-purity argon into a furnace chamber of a forming furnace in the heating process, keeping the temperature for a period of time after the temperature is raised to 815-850 ℃, and keeping the pressure constant at the constant temperature; after the constant temperature is finished, starting a directional solidification program, and moving the heating mechanism from bottom to top at a certain speed until the heating mechanism moves to the position above the region corresponding to the forming mold in the furnace cavity.
E. After the temperature is reduced to the room temperature, the pressure in the cavity is released, and the quartz tube mold is taken out for demolding treatment; thus completing the preparation of the low-oxygen compact ultra-pure arsenic rod.
The arsenic rods molded in the examples were tested:
1. the weight of each of 5 arsenic rods is respectively weighed, the weight of each arsenic rod is 435-442g, and the surface of each ultra-high purity arsenic rod is smooth and compact and has no air holes.
2. Randomly selecting a high-purity arsenic rod, and carrying out sample detection, wherein the purity of the arsenic rod reaches 99.999995%, and the oxygen content in the arsenic rod is less than 1PPm.
Example two
The present embodiment is different from the first embodiment in that: in the step A, a flat-bottom high-purity quartz forming die with the diameter of 115 mm multiplied by 300mm is selected; in step C, 7072g of high-purity arsenic was weighed and placed in the molding die prepared in step S1. The rest is the same as the first embodiment.
The arsenic rods molded in the examples were tested:
1. weighing 7064g of arsenic rod, wherein the surface of the high-purity arsenic rod is smooth, compact and pore-free.
2. And (5) carrying out sample sending detection on the arsenic rod, wherein the purity reaches 99.999995%, and the oxygen content in the arsenic rod is less than 1PPm.
Comparative example 1
In the process of the first embodiment, the sublimation deoxidation purification process in the hydrogen atmosphere in the step B is omitted, and the rest processes are not changed. In the step B, after the raw materials are weighed and loaded, the die is directly placed into a forming device.
Comparative example a shaped arsenic bar was tested:
1. respectively weighing 5 arsenic rods, wherein the weight of each arsenic rod is in the range of 432-443g, and the surface of each high-purity arsenic rod is smooth, compact and free of air holes.
2. Randomly selecting a high-purity arsenic rod, and carrying out sample detection, wherein the purity of the arsenic rod is 99.999992%, and the oxygen content in the arsenic rod is less than 10PPm.
Comparative example No. two
In the process of the first embodiment, the high-temperature deoxidation process under high vacuum in the step C is omitted, and the rest processes are not changed. And C, starting a molding temperature-rising program to heat and pressurize to prepare the arsenic rod only after the air in the cavity is replaced by low vacuum in the step C.
The comparative example two shaped arsenic rods were tested:
1. the weight of each of 5 arsenic rods is measured, the weight of each arsenic rod is within the range of 432-442g, and the surface of the high-purity arsenic rod is smooth, compact and free of air holes.
2. Randomly selecting a high-purity arsenic rod, and carrying out sample detection, wherein the purity of the arsenic rod is 99.999995%, and the oxygen content in the arsenic rod is less than 10PPm.
Comparative example No. three
In the process of the first embodiment, the directional solidification process with constant temperature in the step D is omitted, and the rest of the process is unchanged. And D, after the arsenic rod is prepared by heating and pressurizing according to the forming temperature-rising program, closing a heating power supply, and naturally cooling.
1. The weight of each of 5 arsenic rods is measured, the weight of each arsenic rod is within the range of 436-443g, the surface of the high-purity arsenic rod is provided with a groove, and the top surface of the arsenic rod is provided with a small amount of shrinkage holes.
2. Randomly selecting a high-purity arsenic rod, and carrying out sample detection, wherein the purity of the arsenic rod is 99.999995%, and the oxygen content in the arsenic rod is less than 1PPm.
In the above embodiment, by combining the chemical and physical characteristics of arsenic, sublimation for oxygen removal of high-purity arsenic, crushing in a low-oxygen environment, vacuum high-temperature oxygen removal, pressurization and liquefaction of inert gas, directional solidification, and tail gas treatment in the process, the forming devices (heating mechanism, forming mold, forming furnace, lifting mechanism, tail gas leaching system, and control system) supporting corresponding operations form a set of complete preparation process; the preparation process has the advantages of simple flow, easy operation, high automation control degree, strong preparation operability and capability of preparing ultra-pure arsenic rods with different sizes.
The comparison between the above embodiment and the comparative example shows that the sublimation in the hydrogen atmosphere and the stepwise two-stage deoxidation process carried out at high temperature and high vacuum have a certain effect on the impurity removal of high-purity arsenic, and the oxygen content in the ultra-high-purity arsenic rod can be effectively reduced, so that the oxygen content is lower than 1PPm.
The comparison between the above examples and comparative examples shows that the molding die in the furnace cavity is slowly directionally solidified by adopting a directional solidification mode under high pressure, and the prepared ultra-pure arsenic rod is compact, smooth and bright in surface and has no pores.
In the above embodiment, sublimation of high-purity arsenic is performed in a hydrogen atmosphere, which can achieve two effects: not only can reduce the oxygen content, but also can purify the raw material high-purity arsenic again.
In the above embodiment, no chemical reagent is added in the whole molding process of the ultra-high purity arsenic rod, the inert gas used can be high-purity argon, and the whole process is carried out in a closed environment (glove box), so that the purity of the prepared arsenic rod can further reach 99.999995%.
In the embodiment, the whole preparation process of the ultra-high-purity arsenic rod adopts automatic control, and the forming device adopts safety protection facilities (a safety valve and a pressure sensor are cooperated), so that the remote control and monitoring of an operator are realized, and the safety is guaranteed.
The above embodiments should not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent transformations fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a low-oxygen compact ultra-pure arsenic rod is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, preparing a sublimation pipe and a forming mold;
s2, weighing an ultra-pure arsenic block material, filling the ultra-pure arsenic block material into a sublimation tube, and sealing the tube opening by using a quartz ground opening; continuously introducing hydrogen to form a hydrogen atmosphere, then heating to 600-700 ℃, sublimating arsenic in the hydrogen atmosphere, and carrying out first deoxidation treatment under a high-temperature condition;
s3, after the first deoxidation treatment is finished, taking out arsenic in the sublimation pipe in an inert gas atmosphere environment, crushing the arsenic, and then loading the crushed arsenic into a forming mold; the forming die is arranged in a forming furnace and is vacuumized to 10 DEG -4 Pa below, heating to 530-580 deg.C by heating mechanism, and heating at 10 deg.C -4 Keeping the temperature constant under a vacuum environment below Pa, and performing secondary deoxidation treatment under a high-temperature condition;
s4, after the second deoxidation treatment is finished, continuing heating and raising the temperature, meanwhile, introducing high-pressure inert gas to form an inert gas atmosphere and provide a high-pressure environment, and after the temperature is raised to 815-850 ℃, keeping the temperature and the pressure constant;
and S5, controlling the heating mechanism to move upwards relative to the forming mold, gradually cooling the forming mold from bottom to top, further directionally solidifying and crystallizing the arsenic liquid in the forming mold from bottom to top, cooling to room temperature after complete solidification, relieving pressure, taking out the forming mold in an inert gas atmosphere environment, and demolding to obtain the ultra-pure arsenic rod.
2. The method for preparing the low-oxygen dense ultra-high-purity arsenic rod as claimed in claim 1, wherein: the sublimation pipe and the forming die prepared in the step S1 are sequentially soaked in aqua regia, washed clean by high-purity water and dried.
3. The method for preparing the low-oxygen dense ultra-high-purity arsenic rod as claimed in claim 1, wherein: in the step S2, in the process of temperature rise, gas is discharged and leaching treatment is carried out; in the step S3, when vacuumizing is performed, exhausting the extracted gas and performing leaching treatment; and step S5, carrying out rinsing treatment on the gas discharged by pressure relief.
4. The method for preparing the low-oxygen dense ultra-high-purity arsenic rod as claimed in claim 1, wherein: the leaching treatment adopts 5-10% NaOH aqueous solution.
5. The method for preparing a low-oxygen dense ultra-high-purity arsenic rod as claimed in any one of claims 1 to 4, wherein: in the step S2, the hydrogen is high-purity hydrogen, and the purity of the hydrogen at least reaches 99.999 percent; the hydrogen flow is 400-800mL/min.
6. The method for preparing the low-oxygen dense ultra-high-purity arsenic rod as claimed in claim 5, wherein: in the step S4, the heating rate is 1 ℃/min; the high pressure environment is 3.8-4.2MPa.
7. The method for preparing the low-oxygen dense ultra-high-purity arsenic rod as claimed in claim 6, wherein the method comprises the following steps: in step S3, the forming furnace and the heating mechanism form a forming device; the forming furnace comprises a furnace body, a furnace cavity is formed inside the furnace body, a forming die fixing seat is installed in the furnace cavity, and the forming die is placed on the forming die fixing seat in the furnace cavity of the forming furnace; the outer side of the furnace body is also provided with a gas pipeline assembly which is communicated with the furnace chamber and used for controlling and operating the gas in the furnace chamber; the gas control operation at least comprises vacuum pumping operation, high-pressure inert gas introducing operation and exhaust operation; the heating mechanism comprises a heating part, and a heating channel with an upper opening and a lower opening is formed in the heating part; the heating channel is matched with the forming furnace and used for heating the forming furnace.
8. The method for preparing the low-oxygen dense ultra-high-purity arsenic rod as claimed in claim 7, wherein: the gas pipeline assembly comprises a gas pipeline busbar communicated with the furnace chamber; the gas path busbar is connected with a vacuumizing pipeline, an inert gas pressurizing pipeline and a tail gas discharging pipeline; a vacuum control valve is arranged on the vacuumizing pipeline, and a pressurizing control valve is arranged on the inert gas pressurizing pipeline; and the tail gas discharge pipeline is provided with a discharge valve.
9. The method for preparing the low-oxygen dense ultra-high-purity arsenic rod as claimed in claim 8, wherein: the heating mechanism further comprises a temperature sensor arranged on the heating part, and the working end of the temperature sensor is close to the heating channel.
10. The method for preparing a low-oxygen dense ultra-high-purity arsenic rod as claimed in any one of claims 7 to 9, wherein: the forming device also comprises a bracket for mounting the forming furnace and the heating mechanism; the bracket is also provided with a lifting mechanism; the heating mechanism is fixed with the lifting moving end of the lifting mechanism; the lifting mechanism is used for driving the heating mechanism to move up and down so as to enable the heating channel to move up and down relative to the forming furnace; the forming die is a quartz tube, the diameter of the forming die is 15-150mm, and the length of the forming die is 30-130mm; in step S5, the speed of the heating mechanism moving upwards relative to the forming die is 10-50mm/h.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899712A (en) * | 2012-08-30 | 2013-01-30 | 东方电气集团峨嵋半导体材料有限公司 | Preparation method of ultra-high-purity arsenic monocrystal pieces |
| JP2015189996A (en) * | 2014-03-27 | 2015-11-02 | Jx日鉱日石金属株式会社 | High-purity strontium and production method thereof |
| CN107881351A (en) * | 2017-11-30 | 2018-04-06 | 广东先导先进材料股份有限公司 | The device for deoxidizing and method of high purity arsenic |
| CN110923457A (en) * | 2019-12-27 | 2020-03-27 | 中国科学院电工研究所 | Preparation method of high-purity arsenic crystal |
| CN211497744U (en) * | 2019-12-27 | 2020-09-15 | 中国科学院电工研究所 | Preparation device of high-purity arsenic crystal |
| CN112011827A (en) * | 2019-05-31 | 2020-12-01 | 东泰高科装备科技有限公司 | Device and method for manufacturing high-purity arsenic rod |
| CN112030224A (en) * | 2020-09-03 | 2020-12-04 | 武汉拓材科技有限公司 | Method for manufacturing arsenic rod for molecular beam epitaxy |
| CN215246044U (en) * | 2021-06-11 | 2021-12-21 | 山东恒邦冶炼股份有限公司 | Vertical high-purity arsenic sublimation purification equipment for packing |
-
2022
- 2022-08-22 CN CN202211007240.5A patent/CN115418719B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899712A (en) * | 2012-08-30 | 2013-01-30 | 东方电气集团峨嵋半导体材料有限公司 | Preparation method of ultra-high-purity arsenic monocrystal pieces |
| JP2015189996A (en) * | 2014-03-27 | 2015-11-02 | Jx日鉱日石金属株式会社 | High-purity strontium and production method thereof |
| CN107881351A (en) * | 2017-11-30 | 2018-04-06 | 广东先导先进材料股份有限公司 | The device for deoxidizing and method of high purity arsenic |
| CN112011827A (en) * | 2019-05-31 | 2020-12-01 | 东泰高科装备科技有限公司 | Device and method for manufacturing high-purity arsenic rod |
| CN110923457A (en) * | 2019-12-27 | 2020-03-27 | 中国科学院电工研究所 | Preparation method of high-purity arsenic crystal |
| CN211497744U (en) * | 2019-12-27 | 2020-09-15 | 中国科学院电工研究所 | Preparation device of high-purity arsenic crystal |
| CN112030224A (en) * | 2020-09-03 | 2020-12-04 | 武汉拓材科技有限公司 | Method for manufacturing arsenic rod for molecular beam epitaxy |
| CN215246044U (en) * | 2021-06-11 | 2021-12-21 | 山东恒邦冶炼股份有限公司 | Vertical high-purity arsenic sublimation purification equipment for packing |
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