CN114622272B - Impurity removal method for single crystal germanium waste with impurity contained in slag - Google Patents
Impurity removal method for single crystal germanium waste with impurity contained in slag Download PDFInfo
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- CN114622272B CN114622272B CN202210196199.4A CN202210196199A CN114622272B CN 114622272 B CN114622272 B CN 114622272B CN 202210196199 A CN202210196199 A CN 202210196199A CN 114622272 B CN114622272 B CN 114622272B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/08—Germanium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the technical field of germanium single crystal growth, and particularly discloses a method for removing impurities from slag inclusion and impurity-containing germanium waste, which comprises the following steps: melting single crystal germanium growth waste; cooling and recrystallizing waste slag inclusion: after the germanium waste is completely melted into a molten state, adjusting heating power to reduce the temperature by 15-50 ℃ so as to recrystallize the melt; and (3) cavity flow field control: the germanium melt after recrystallization treatment is controlled to be pressure and crucible rotation speed, and the opening of a butterfly valve of a vacuum pump is kept to be 60% -80%; moving oxide dross on the surface of the germanium melt to the center of the melt; and (3) floating slag lifting and dipping: the rotating speed of the seed rod is controlled, the seed rod moves downwards to contact with the scum, the seed rod is pulled, when the crystal grows to 80-100 mm in diameter, the crystal is rapidly cooled, impurities are removed, the impurities are removed from the slag-inclusion impurity-containing germanium waste generated in the single crystal germanium growth process, the purity of the impurity-removed germanium waste reaches more than 6N, and the raw material completely accords with the raw materials required by the P-type and N-type single crystal germanium Czochralski method growth.
Description
Technical Field
The invention belongs to the technical field of germanium single crystal growth, and particularly relates to a method for removing impurities from slag-included impurity-contained germanium waste materials, which is used for preparing raw materials for growing infrared germanium single crystals and solar laminated compound battery germanium single crystal substrates.
Background
With the development of infrared optical technology, the requirements on the performance indexes of optical transmittance of an infrared optical germanium lens and a germanium window are higher and higher, and a germanium raw material with higher purity is required to be manufactured into an infrared light transmission material with better quality. Similarly, part of metal germanium is also used in the aspect of manufacturing space solar cell substrates, and in order to enable the photoelectric conversion efficiency of the satellite solar germanium substrate laminated compound cell to meet the use requirement, the requirement on the purity of germanium raw materials is higher.
Along with the repeated use of the metal germanium raw material for the growth of the single crystal germanium, part of the metal germanium is oxidized by oxygen in the air and reacts with moisture to generate oxide, and the generated oxide can form scum to float on the surface of a germanium melt in the process of melting materials in a crystal growth furnace, and the part of scum can cause serious degradation of the product quality for the growth of the single crystal of the germanium by a Czochralski method. For the raw materials with more impurities in the part of slag inclusion, the traditional treatment method is to directly send smelting reduction and zone melting purification treatment, and the raw materials which are in line with the growth of the monocrystalline germanium can be better obtained. However, this conventional treatment method increases the amount of waste treatment and the treatment process is long, resulting in high production costs.
Disclosure of Invention
The main purpose of the invention is to provide a method for removing impurities from slag-included and impurity-contained germanium waste, which is used for removing impurities from slag-included and impurity-contained germanium waste generated in the growth process of monocrystalline germanium, and the purity of the impurity-removed germanium waste reaches more than 6N, so that the impurity-contained and impurity-contained germanium waste completely meets the raw materials required by the growth of P-type and N-type monocrystalline germanium Czochralski method. More importantly, compared with the traditional treatment means, the method can reduce the waste treatment amount, shorten the treatment flow, reduce the production cost and create good economic benefits for enterprises.
A method for removing impurities from single crystal germanium scraps containing impurities in slag comprises the following steps:
(1) Melting single crystal germanium growth waste;
(2) Cooling and recrystallizing waste slag inclusion: after the germanium waste is completely melted into a molten state, adjusting heating power to reduce the temperature by 15-50 ℃, cooling the melt, and recrystallizing partial oxide with germanium metal in the cooled melt; lowering the seed rod towards the melt direction and welding the seed rod with the recrystallized substance for a period of time; pulling up the seed rod, pulling up the recrystallized material together with the germanium melt, pulling up the recrystallized material to the secondary chamber of the crystal growth furnace, and cutting off the recrystallized material in the secondary chamber; filling nitrogen into the secondary chamber for growing crystal until the pressure in the secondary chamber is equal to the atmospheric pressure, cooling the recrystallized substance for a period of time, taking out, and delivering to a zone melting purification process;
(3) And (3) cavity flow field control: the pressure in the chamber is controlled to be 10-15 torr, and the rotating speed of the graphite crucible is set to be 8-10 rad/min; after the pressure in the furnace is stable, keeping the pressure in the furnace for 25-35 min, closing a valve for air intake and vacuum pumping, stopping the rotation of the crucible, filling protective gas into the cavity in 3-5 min, enabling the gas to flow to the liquid level of the melt through reflection of the guide cylinder until the pressure in the cavity is stable at 200-350 torr, and meanwhile keeping the opening of a butterfly valve of the vacuum pump at 60-80%; moving oxide dross on the surface of the germanium melt to the center of the melt; the method comprises the steps of carrying out a first treatment on the surface of the
(4) And (3) floating slag lifting and dipping: the pressure in the chamber is adjusted to 15-50 torr by implementing the flow field control treatment of the chamber for multiple times; controlling the rotating speed of a seed rod to be 1-6 rad/min by using seed crystals with a <111> crystal orientation, downwards moving the seed rod to be in contact with scum transferred to the center of a melt, upwards pulling the seed rod, and when the grown crystal is hexagonal and grows to 80-100 mm in diagonal length, enabling the seed rod to be upwards to a position 200-300 mm away from the melt, so that the crystal is rapidly cooled; then controlling the seed rod to downwards move the cooled crystals so that the crystals just sink into the melt, keeping the crystals to sink into the melt for 5-10 seconds, and then upwards moving the crystals again, and cooling the crystals to a position 200-300 mm away from the melt for 5-10 minutes; this step is repeated a number of times to remove the dross from the surface of the melt.
Further, in the step (1), the method for melting the single crystal germanium growth waste material comprises the following steps: placing germanium waste into a high-purity graphite crucible of a crystal growth furnace, closing a furnace cover of the crystal growth furnace to form a closed cavity, vacuumizing the cavity, continuously starting a vacuum pump to keep the vacuum degree constant, heating the high-purity graphite crucible, heating to 937.4-1200 ℃, and keeping the temperature constant for a period of time to melt the germanium waste.
Further, in the step (1), the chamber is vacuumized until the vacuum degree is 5-100 torr.
Further, in the step (2), the time for the seed rod to be fused with the recrystallized substance is 3-5 min.
Further, the germanium waste comprises pot bottom materials, partial crystal bar broken ends and tails or partial numerical control milling machine nesting remainder which are used repeatedly for single crystal germanium growth.
Further, the protective gas in the step (3) is argon or nitrogen.
Drawings
FIG. 1 is a flow chart of a process for removing impurities from slag-included impurity-containing monocrystalline germanium scraps;
FIG. 2 is a schematic diagram of a flip chip shoulder;
FIG. 3 is a schematic diagram of a slag extraction and impurity removal thermal field;
Detailed Description
In order to enable the technical scheme of the invention to be better understood by those skilled in the art, the method for removing impurities from slag-included impurity-contained monocrystalline germanium waste provided by the invention is described in detail below with reference to the accompanying drawings.
Referring to fig. 1, the method for removing impurities from single crystal germanium scraps with impurities in slag comprises the following steps:
(1) Melting single crystal germanium growth waste: the single crystal germanium grows and repeatedly uses pot bottom materials, partial crystal bar broken ends and tails, partial numerical control milling machine nesting remainder and the like, the waste materials are placed in a high-purity graphite crucible, and a furnace cover of a crystal growth furnace is closed to form a closed cavity; vacuumizing the cavity to a certain vacuum degree by using a mechanical vacuum pump, wherein the vacuum degree is 5-100 torr, and continuously starting the vacuum pump to keep the vacuum degree constant; the high purity graphite crucible is slowly heated to slowly raise the temperature in the chamber, gradually melt the waste material, raise the temperature of the waste material to 937.4 ℃ higher than that required by melting germanium metal, optionally raise the temperature to 937.4 ℃ to 1200 ℃, and maintain the constant temperature for a period of time.
(2) Cooling and recrystallizing waste slag inclusion: after the scrap melts and is held at a constant temperature for a period of time, the germanium metal is completely melted to a molten state, and a part of the non-melted oxide is wrapped in the molten state germanium metal, and a majority of the oxide floats on the surface of the germanium melt. At the moment, the temperature of the melt is required to be reduced, the heating power is adjusted to reduce the temperature by 15-50 ℃, and part of oxide in the cooled melt is recrystallized together with germanium metal; lowering the seed rod towards the melt direction to contact with the recrystallized substance for a period of time, welding for 3-5 min, exchanging heat at the contact part, and transferring the crystallization latent heat of the molten germanium on the surface of the hotter recrystallized substance through the seed rod to firmly adhere to the seed rod; pulling up the seed rod, pulling up the recrystallized material together with the germanium melt, pulling up the recrystallized material to the secondary chamber of the crystal growth furnace, and cutting off the recrystallized material in the secondary chamber; filling nitrogen into the secondary chamber for growing crystal until the pressure in the secondary chamber is equal to the atmospheric pressure, cooling the recrystallized substance for a period of time, and taking out; the recrystallized material slag is taken out to contain more impurities and is sent to a zone melting and purifying process.
(3) And (3) cavity flow field control: the waste material after cooling and recrystallization treatment floats a part of oxide slag blocks with smaller caking size on the upper part of the germanium melt, the part of slag blocks can not be removed well in the recrystallization working procedure section, and the germanium melt flow field in the cavity needs to be controlled, so that the part of finely crushed slag blocks are concentrated towards the center of the melt, and the adsorption and the extraction are convenient. Controlling the pressure in the chamber to be 10-15 torr by controlling the flow of the protective gas entering the crystal growth chamber and the opening of a vacuum pump suction butterfly valve, and setting the rotating speed of the graphite crucible to be 8-10 rad/min; after the pressure in the furnace is stable, the furnace is kept for about 30min, the valves for air intake and vacuum pumping are closed, the crucible is stopped rotating, protective gas argon or nitrogen is filled into the cavity within 3 min-5 min, the gas flows to the melt liquid level through reflection of the guide cylinder until the pressure in the cavity is stable at 200-350 torr, and meanwhile, the opening of a butterfly valve of the vacuum pump is kept at 60% -80%; at this time, because of the drastic changes of the pressure and the air flow in the chamber and the abrupt stop of the rotation of the crucible, the germanium melt continues to rotate in the crucible according to inertia to cause friction between the melt and the crucible, the melt can present a slight boiling phenomenon, and the generated force pushes the surface oxide dross to move towards the center of the melt.
(4) And (3) floating slag lifting and dipping: through carrying out the cavity flow field control treatment for multiple times, the floating slag is better concentrated in the center of the surface of the melt, and then the pressure in the cavity is adjusted to 15-50 torr; controlling the rotating speed of a seed rod to be 1-6 rad/min by using seed crystals with a <111> crystal orientation, and downwards moving to contact with the scum transferred to the center of the melt; slowly pulling up the seed rod in the presence of supercooling degree, and crystallizing and growing the molten germanium at the seed crystal, wherein most of oxide scum is wrapped in the crystal in the process; when the crystallization length is 80-100 mm, the seed rod is pulled up to 200-300 mm away from the melt, the temperature is lower at 500-700 ℃, and the crystallization can be cooled rapidly; at the moment, a small amount of oxide scum is also required to be adhered on the surface of the melt by using the cooled crystal again, namely, a seed rod with the rotating speed of 1-6 rad/min is downwards moved to contact with the scum, the contact is that the crystal just submerges into the melt, the crystal is kept to be upwards moved again after being submerged into the melt for 5-10 s, and the crystal is moved to a position 200-300 mm away from the melt for cooling for 5-10 min; and repeating the steps for a plurality of times, so that oxide scum on the surface of the melt is attached to crystals as much as possible, and finally, the scum on the surface of the melt is removed completely and is in a uniform and transparent form.
Example 1
The impurity removing method for the single crystal germanium waste material with impurity contained in the slag comprises the following steps:
step 101, material melting: namely, heating the crystal growth graphite crucible to melt the waste material of the single crystal germanium growth.
Step 1011: the pot bottom material, part of crystal bar broken ends and tails, part of numerical control milling machine nesting remainder and the like which are repeatedly used for single crystal germanium growth inevitably generate some waste materials in the processes of crystal growth and material forming processing, the waste materials are placed in a high-purity graphite crucible, and the furnace cover of a crystal growth furnace is closed to form a closed cavity;
step 1012: preferably, a mechanical vacuum pump is used for vacuumizing the cavity to the vacuum degree of 15torr, and the vacuum pump is continuously started to keep the vacuum degree constant;
step 1013: preferably, the high purity graphite crucible is slowly heated to slowly raise the temperature in the chamber, the waste gradually melts, and the waste temperature is maintained at a constant temperature for 5 hours at 980 ℃.
Step 102, cooling and recrystallizing: the temperature of molten slag inclusion waste in the graphite crucible is reduced, the melting point of large-particle slag is higher than that of germanium metal, and recrystallization can occur along with the reduction of the temperature. After the scrap melts and is held at a constant temperature for a period of time, the germanium metal is completely melted to a molten state, and a part of the non-melted oxide is wrapped in the molten state germanium metal, and a majority of the oxide floats on the surface of the germanium melt.
Step 1021: preferably, the temperature of the melt is reduced by 25 ℃, and part of oxide in the melt after the temperature reduction is reduced is recrystallized together with germanium metal;
step 1022: lowering the seed rod towards the melt direction to contact with the recrystallized substance for 3-5 min, wherein heat exchange exists at the contact part, and the molten germanium on the surface of the hotter recrystallized substance transfers the latent heat of crystallization through the seed rod and is firmly adhered to the seed rod;
step 1023: pulling up the seed rod, pulling up the recrystallized material together with the germanium melt, pulling up the recrystallized material to the secondary chamber of the crystal growth furnace, and cutting off the recrystallized material in the secondary chamber;
step 1024: filling nitrogen into the secondary chamber for growing crystal until the pressure in the secondary chamber is equal to the atmospheric pressure, cooling the recrystallized substance for a period of time, and taking out;
step 1025: the recrystallized material slag is taken out to contain more impurities and is sent to the processes of reduction and zone-melting purification. And after multiple zone melting, selecting an intermediate section with proper length as a qualified zone-melted germanium ingot.
Step 103, controlling a scum flow field: namely, the molten state flow field in the crystal growth chamber is controlled.
Step 1031: preferably, the pressure in the chamber is controlled to be 15torr, and the graphite crucible rotation speed is set to be 8 rad/min;
step 1032: preferably, after the pressure in the furnace is stable, the furnace is kept for about 30 minutes, and valves for air intake and vacuum pumping are closed to stop the rotation of the crucible;
step 1033: preferably, as shown in fig. 3, a chamber formed by a high-purity graphite crucible 303 is filled with protective gas 301 argon or nitrogen, the protective gas 301 flows onto a guide cylinder 302 at a certain angle, then flows to a waste melt liquid level 305 in a reflection way for 3-5 min to enable the pressure in the chamber to be stabilized at 250torr, then the opening of a butterfly valve of a vacuum pump is kept at 60% -80%, and the gas in the furnace is quickly replaced to enable the temperature and the gas flow in the furnace to be changed drastically;
step 1034: the force generated by the drastic change pushes the surface oxide dross toward the center of the melt.
Step 104, extracting slag and removing slag: i.e., by moving the seed crystal to pull the attached dross, a crystalline slag head, i.e., slag inclusion crystalline 304 as shown in fig. 3 is formed.
Step 1041: through carrying out the cavity flow field control treatment for a plurality of times, the scum is better concentrated in the center of the surface of the melt, and then, the pressure in the cavity is preferably adjusted to be 15torr;
step 1042: preferably, as shown in FIG. 2, seeding shoulder 202 is performed using a seed crystal 201 with a crystal orientation <111>, the seed rod speed is controlled to be 2 rad/min, and the seed rod is moved downwards to contact with the dross transferred to the center of the melt;
step 1043: slowly pulling up the seed rod in the presence of supercooling degree, and crystallizing and growing the molten germanium at the seed crystal, wherein most of oxide scum is wrapped in the crystal in the process;
step 1044: preferably, the shape of the grown crystal is hexagonal, as shown by the seeding shoulder 202 in FIG. 2, when the crystal grows to 80mm in diagonal length, the seed rod is pulled upwards to a position 200mm away from the melt, the temperature of the position is lower than 500-700 ℃, and the crystal can be rapidly cooled;
step 1045: at the moment, a small amount of oxide scum is also required to be adhered on the surface of the melt by using the cooled crystal again, namely, a seed rod with the rotating speed of 1 rad/min is downwards moved to contact with the scum, the contact is that the crystal just submerges into the melt, the crystal is kept to be upwards moved again after being submerged into the melt for 5-10 s, and the crystal is moved to a position 200-300 mm away from the melt for cooling for 5-10 min;
step 1046: step 1045 is repeated as many times as possible to adhere oxide dross on the surface of the melt to the crystals.
Finally, oxide dross is fully adhered to crystals to form slag heads, a seed rod is pulled upwards to cut off the slag heads and taken out, and the impurity removal of the single crystal germanium waste materials with impurities in the slag is completed. Specifically, the method is used for treating the slag inclusion and impurity germanium-containing waste, so that oxide scum of large particles and small particles can be removed to a large extent, and the influence of crystal form check on crystal growth is reduced. When the crystallization nucleation is reduced, the edge of the grown single crystal is not easy to crystallize along with the increase of the radial size of the grown single crystal, namely, the grown single crystal is not easy to crystallize, and the grown large-diameter germanium single crystal with the diameter of phi 450mm or more is more easy to succeed.
Comparative example 1
Other steps are the same as in example 1 except for step 1021;
the temperature of the melt is lower than 15 ℃, the recrystallized amount of the melt oxide after the temperature is reduced is less, the melt oxide needs to be dipped and pulled for many times, and more scum appears in the subsequent cavity flow field control and scum pulling dipping stage, so that the operation of the step is more difficult.
Comparative example 2
Other steps are the same as in example 1 except for step 1033;
the opening of a butterfly valve of the vacuum pump is kept 10% -30%, the gas replacement in the cavity is slow, the temperature reduction range caused by the gas replacement is small, the force generated by the change of the gas flow is small, the quantity of recrystallized substances is reduced, slag concentrated to the center of the crucible is also small, and the slag extraction efficiency is correspondingly reduced.
Comparative example 3
The guide cylinder is not used, or the flow direction of protective gas is not reflected by the guide cylinder, the protective gas directly flows to the liquid level of the melt, crystallization generated on the surface of the melt does not start from the middle of the liquid level, scum is not well concentrated in the middle, and the slag lifting operation is difficult or the efficiency is not high.
Comparative example 4
Other steps are the same as in example 1 except for step 1042;
the crystal external shape of the seeding shoulder growth is difficult to realize in a hexagonal shape without using the seed crystal with the crystal orientation of <111>, using the seed crystal with other crystal orientations, and is easy to change into a circular shape along with the progress of the seeding shoulder, so that the adhesion is difficult to realize during the operation of adhering and extracting slag, and the adhesion efficiency is low.
The rotating speed of the seed rod is regulated to be more than 6rad/min, and when the seeding is shouldered, the crystal is turned into a circle too early, so that scum is not easy to adhere.
Comparative example 5
Other steps are the same as in example 1 except for step 1045;
the rotation speed of the seed rod is regulated to 3 rad/min, and no obvious change exists.
Comparative example 6
Other steps are the same as in example 1 except for step 1045;
the rotating speed of the seed rod is regulated to be more than 6rad/min, the fine broken scum is not easy to adhere, and the impurity removal efficiency is reduced.
Claims (6)
1. The impurity removal method for the single crystal germanium waste material with impurities in the slag is characterized by comprising the following steps:
(1) Melting single crystal germanium growth waste;
(2) Cooling and recrystallizing waste slag inclusion: after the germanium waste is completely melted into a molten state, adjusting heating power to reduce the temperature by 15-50 ℃, cooling the melt, and recrystallizing partial oxide with germanium metal in the cooled melt; lowering the seed rod in the direction of the melt and welding the seed rod with the recrystallized material for a period of time; pulling up the seed rod, pulling up the recrystallized material together with the germanium melt, pulling up the recrystallized material to the secondary chamber of the crystal growth furnace, and cutting off the recrystallized material in the secondary chamber; filling nitrogen into the secondary chamber for growing crystal until the pressure in the secondary chamber is equal to the atmospheric pressure, cooling the recrystallized substance for a period of time, taking out, and delivering to a zone melting purification process;
(3) And (3) cavity flow field control: the pressure in the chamber is controlled to be 10-15 torr, and the rotating speed of the graphite crucible is set to be 8-10 rad/min; after the pressure in the furnace is stable, keeping the pressure in the furnace for 25-35 min, closing a valve for air intake and vacuum pumping, stopping the rotation of the crucible, filling protective gas into the cavity in 3-5 min, enabling the gas to flow to the liquid surface of the melt through reflection of the guide cylinder until the pressure in the cavity is stable at 200-350 torr, and meanwhile keeping the opening of a butterfly valve of the vacuum pump to be 60-80%; moving oxide dross on the surface of the germanium melt to the center of the melt;
(4) And (3) floating slag lifting and dipping: the pressure in the chamber is adjusted to 15-50 torr by implementing the flow field control treatment of the chamber for multiple times; controlling the rotating speed of a seed rod to be 1-6 rad/min by using seed crystals with a <111> crystal orientation, downwards moving the seed rod to be in contact with scum transferred to the center of a melt, upwards lifting the seed rod, and when the grown crystal is hexagonal and grows to 80-100 mm in diagonal length, enabling the seed rod to be upwards to be 200-300 mm away from the melt, so that the crystal is rapidly cooled; then controlling the seed rod to downwards move the cooled crystals, so that the crystals just sink into the melt, keeping the crystals to sink into the melt for 5-10 seconds, then upwards moving the crystals again, and cooling the crystals for 5-10 minutes at a position 200-300 mm away from the melt; this step is repeated a number of times to remove the dross from the surface of the melt.
2. The method for removing impurities from single crystal germanium waste with impurities contained in slag according to claim 1, wherein in the step (1), the method for melting the single crystal germanium growth waste is as follows: placing germanium waste into a high-purity graphite crucible of a crystal growth furnace, closing a furnace cover of the crystal growth furnace to form a closed cavity, vacuumizing the cavity, continuously starting a vacuum pump to keep the vacuum degree constant, heating the high-purity graphite crucible, heating to 937.4-1200 ℃, and keeping the temperature constant for a period of time to melt the germanium waste.
3. The method for removing impurities from single crystal germanium waste with slag and impurities according to claim 2, wherein in the step (1), the chamber is vacuumized to a vacuum degree of 5-100 torr.
4. The method for removing impurities from single crystal germanium scraps containing impurities by slag inclusion according to claim 1, wherein in the step (2), the time for welding seed rods and recrystallized substances is 3 min-5 min.
5. The method for removing impurities from single crystal germanium waste containing impurities from slag according to claim 1, wherein the germanium waste comprises a pot bottom material, a part of crystal rod broken end tail material or a part of numerical control milling machine set material residue which is repeatedly used for single crystal germanium growth.
6. The method for removing impurities from single crystal germanium waste with slag and impurities according to claim 1, wherein the protective gas in the step (3) is argon or nitrogen.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3573108A (en) * | 1968-10-30 | 1971-03-30 | Gen Electric | Purification of germanium |
| CN101748483A (en) * | 2008-11-28 | 2010-06-23 | 北京有色金属研究总院 | Germanium melt dross removing device and method |
| CN105401214A (en) * | 2015-11-25 | 2016-03-16 | 昆明云锗高新技术有限公司 | Germanium melt scum removal method |
| CN113337738A (en) * | 2021-06-04 | 2021-09-03 | 安徽光智科技有限公司 | Method for recovering germanium waste |
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- 2022-03-01 CN CN202210196199.4A patent/CN114622272B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3573108A (en) * | 1968-10-30 | 1971-03-30 | Gen Electric | Purification of germanium |
| CN101748483A (en) * | 2008-11-28 | 2010-06-23 | 北京有色金属研究总院 | Germanium melt dross removing device and method |
| CN105401214A (en) * | 2015-11-25 | 2016-03-16 | 昆明云锗高新技术有限公司 | Germanium melt scum removal method |
| CN113337738A (en) * | 2021-06-04 | 2021-09-03 | 安徽光智科技有限公司 | Method for recovering germanium waste |
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