CN114622272A - Impurity removing method for slag-inclusion impurity-containing monocrystalline germanium waste - Google Patents
Impurity removing method for slag-inclusion impurity-containing monocrystalline germanium waste Download PDFInfo
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- CN114622272A CN114622272A CN202210196199.4A CN202210196199A CN114622272A CN 114622272 A CN114622272 A CN 114622272A CN 202210196199 A CN202210196199 A CN 202210196199A CN 114622272 A CN114622272 A CN 114622272A
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- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
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- 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
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Abstract
The invention belongs to the technical field of germanium single crystal growth, and particularly discloses a slag inclusion impurity-containing germanium waste impurity removal method, which comprises the following steps: melting the growth waste of the single crystal germanium; cooling and recrystallizing the waste slag inclusion: after the germanium waste is completely melted into a molten state, adjusting the heating power to reduce the temperature by 15-50 ℃ so as to recrystallize the melt; controlling a flow field of the cavity: controlling the pressure intensity and the crucible rotation speed of the germanium melt subjected to recrystallization treatment, and keeping the opening of a butterfly valve of a vacuum pump to be 60-80%; oxide scum on the surface of the germanium melt is moved to the center of the melt; lifting and adhering scum: the seed rod is pulled up by controlling the rotating speed of the seed rod, the seed rod moves downwards to contact with scum, crystals are rapidly cooled and impurities are removed when crystals grow to be 80-100 mm in diameter, impurities in the impurity-containing germanium-contained slag generated in the growth process of the single crystal germanium are removed through the scheme of the invention, and the purity of the impurity-removed germanium waste reaches more than 6N, so that the raw material is required by growth of P-type and N-type single crystal germanium by a Czochralski method.
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-containing impurity-containing germanium waste, which is used for preparing a raw material for growing infrared germanium single crystals and germanium single crystal substrates of solar laminated compound batteries.
Background
With the development of infrared optical technology, the requirements on the light transmittance performance indexes of infrared optical germanium lenses and germanium windows are higher and higher, and a germanium raw material with higher purity is needed to manufacture an infrared light transmission material with better quality. Similarly, part of metal germanium is also used in the manufacturing aspect of the space solar cell substrate, so that the photoelectric conversion efficiency of the satellite solar germanium substrate laminated compound cell meets the use requirement, and the requirement on the purity of the germanium raw material is higher.
With the repeated use of the metal germanium raw material for growing the single crystal germanium, part of the metal germanium is oxidized by oxygen in the air and reacts with moisture to generate oxide, the generated oxide can form scum on the surface of a germanium melt in the material melting process in a crystal growing furnace, and the scum can cause serious reduction on the product quality of the growth of the single crystal of the direct-pulling germanium. For the raw materials with a part of slag inclusion containing more impurities, the traditional treatment method is to directly send the raw materials to smelting reduction and zone melting purification treatment, and the raw materials meeting the growth requirement of the single crystal germanium can be well obtained. However, this conventional treatment method increases the amount of waste material to be treated and requires a long treatment process, resulting in high production costs.
Disclosure of Invention
The invention mainly aims to provide a method for removing impurities from slag-inclusion impurity-containing germanium waste, which is used for removing impurities from slag-inclusion impurity-containing germanium waste generated in the growth process of single crystal germanium, wherein the purity of the impurity-removed germanium waste reaches more than 6N, and the impurity-removed germanium waste becomes a raw material completely meeting the growth requirements of a P-type and N-type single crystal germanium Czochralski method. More importantly, compared with the traditional treatment means, the method can reduce the waste treatment capacity, shorten the treatment process, reduce the production cost and create good economic benefits for enterprises.
The impurity removing method of the slag-inclusion impurity-containing monocrystalline germanium waste material comprises the following steps:
(1) melting the growth waste of the single crystal germanium;
(2) cooling and recrystallizing the waste slag inclusion: after the germanium waste is completely melted into a molten state, adjusting the heating power to reduce the temperature by 15-50 ℃, cooling the melt, and recrystallizing partial oxide together with germanium metal in the cooled melt; lowering the seed rod towards the melt direction to be connected and welded with the recrystallized material for a period of time; pulling the seed rod upwards, pulling the recrystallized substances out of the germanium melt, pulling the recrystallized substances into an auxiliary chamber of the crystal growing furnace, and cutting off the recrystallized substances in the auxiliary chamber; filling nitrogen into the crystal growth auxiliary chamber until the air pressure in the auxiliary chamber is equal to the atmospheric pressure, cooling the recrystallized substance for a period of time, taking out, and sending to a zone melting purification process;
(3) controlling a flow field of the cavity: controlling the pressure in the chamber to be 10-15 torr and setting the rotation speed of the graphite crucible to be 8-10 rad/min for the germanium melt subjected to recrystallization treatment; keeping the pressure in the furnace for 25-35 min after the pressure in the furnace is stable, closing a gas inlet and vacuumizing valve, stopping the rotation of the crucible, filling protective gas into the cavity within 3-5 min, and reflecting the gas to the liquid level of the melt through a guide cylinder until the pressure in the cavity is stable at 200-350 torr, and meanwhile, keeping the opening of a butterfly valve of a vacuum pump at 60-80%; oxide scum on the surface of the germanium melt is moved to the center of the melt; (ii) a
(4) Lifting and adhering scum: adjusting the pressure in the chamber to be 15-50 torr by carrying out chamber flow field control processing for multiple times; controlling the rotation speed of a seed rod to be 1-6 rad/min by using a seed crystal with a <111> crystal orientation, moving downwards to contact with scum transferred to the center of a melt, pulling the seed rod upwards, wherein the grown crystal is hexagonal, and when a crystal grows to a diagonal length of 80-100 mm, the seed rod upwards reaches a position 200-300 mm away from the melt to rapidly cool the crystal; then controlling the seed rod to move the cooled crystal downwards to enable the crystal to just sink into the melt, keeping the crystal sink 5-10 s later, moving the crystal upwards again, and moving the crystal to a position 200-300 mm away from the melt to cool for 5-10 min; the step is repeated for a plurality of times to remove the scum on the surface of the melt.
Further, in the step (1), the method for melting the monocrystalline germanium growth waste material comprises the following steps: placing the 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 to 937.4-1200 ℃, keeping the temperature constant for a period of time, and melting 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 melting the seed rod and the recrystallized material is 3-5 min.
Further, the germanium waste material comprises pot bottom materials, partial crystal bar broken end tailing materials or partial numerical control milling machine nesting excess materials which are repeatedly used in the growth of the single crystal germanium.
Further, the protective gas in the step (3) is argon or nitrogen.
Drawings
FIG. 1 is a flow chart of impurity removal process of slag inclusion impurity-containing monocrystalline germanium waste;
FIG. 2 is a schematic view of a seeding shouldering;
FIG. 3 is a schematic diagram of a thermal field for extracting and removing slag;
Detailed Description
In order to make the technical scheme of the invention better understood by those skilled in the art, the method for removing impurities from slag inclusion impurity-containing 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 slag-inclusion impurity-containing monocrystalline germanium waste provided by the invention comprises the following steps:
(1) melting the growth waste of the single crystal germanium: repeatedly using pot bottom materials, partial crystal bar broken end tailings, partial numerical control milling machine nesting excess materials and the like for growing the single crystal germanium, placing waste materials into a high-purity graphite crucible, closing a furnace cover of a crystal growing furnace, and forming a closed chamber; 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; and slowly heating the high-purity graphite crucible to slowly raise the temperature in the chamber, gradually melting the waste material, and optionally raising the temperature of the waste material to 937.4 ℃ higher than that required by melting germanium metal, and keeping the temperature constant for a period of time at 937.4-1200 ℃.
(2) Cooling and recrystallizing the waste slag inclusion: after the scrap is melted and held at a constant temperature for a period of time, the germanium metal is completely melted into a molten state, the molten germanium metal wraps a part of oxides which are not melted, and most of the oxides float on the surface of the germanium melt. At the moment, the melt is required to be cooled, the heating power is adjusted to reduce the temperature by 15-50 ℃, and partial oxide and germanium metal are recrystallized in the melt after the temperature is reduced; lowering the seed crystal rod to the melt direction to contact with the recrystallized substance for a period of time, carrying out contact welding for 3-5 min, wherein heat exchange exists at the contact part, and the hot molten germanium on the surface of the recrystallized substance is firmly attached to the seed crystal rod by transferring latent heat of crystallization through the seed crystal rod; pulling the seed rod upwards, pulling the recrystallized substances out of the germanium melt, pulling the recrystallized substances into an auxiliary chamber of the crystal growing furnace, and cutting off the recrystallized substances in the auxiliary chamber; filling nitrogen into the crystal growth auxiliary chamber until the air pressure in the auxiliary chamber is equal to the atmospheric pressure, cooling the recrystallized substance for a period of time, and taking out; the taken-out recrystallized substances contain more slag inclusions and are sent to a zone melting purification process.
(3) Controlling a flow field of the cavity: the waste material after temperature reduction and recrystallization treatment floats a part of oxide slag blocks with smaller agglomeration size on the upper part of the germanium melt, the part of slag blocks can not be well removed in the recrystallization process section, and the flow field of the germanium melt 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 are convenient to absorb and take out. Controlling the pressure in the chamber to be 10-15 torr by controlling the flow of protective gas entering the crystal growth chamber and the opening of a vacuum pump exhaust butterfly valve, and setting the rotation speed of the graphite crucible to be 8-10 rad/min; after the pressure in the furnace is stable, keeping the pressure for about 30min, closing a gas inlet and vacuumizing valve, stopping the rotation of the crucible, filling protective gas argon or nitrogen into the cavity within 3-5 min, and reflecting the gas to the liquid level of the melt through a guide cylinder until the pressure in the cavity is stable at 200-350 torr, and meanwhile, keeping the opening of a butterfly valve of a vacuum pump at 60-80%; at this time, because of the drastic changes of pressure and air flow in the chamber and the sudden stop of the rotation of the crucible, the germanium melt continuously rotates in the crucible according to inertia to cause the friction between the melt and the crucible, the melt can present a slight boiling phenomenon, and the generated force pushes the oxide scum on the surface to move towards the center of the melt.
(4) Lifting and adhering scum: through multiple times of implementation of chamber flow field control treatment, scum is better concentrated at the center of the surface of the melt, and then the pressure in the chamber is adjusted to be 15-50 torr; using seed crystals with the <111> crystal orientation, controlling the rotating speed of a seed crystal rod to be 1-6 rad/min, and moving downwards to contact with scum transferred to the center of the melt; in the presence of supercooling degree, slowly pulling the seed rod upwards, crystallizing and growing the molten germanium at the seed crystal, and wrapping most of oxide scum into the crystals in the process; when the crystal grows to be 80-100 mm in diameter, the seed crystal rod is lifted upwards to a position 200-300 mm away from the melt, the temperature at the position is lower than 500-700 ℃, and the crystal body can be rapidly cooled; at the moment, a small amount of oxide scum is on the surface of the melt, and cooled crystals are required to be adhered again, namely, a seed rod moving downwards at the rotating speed of 1-6 rad/min is in contact with the scum, the seed rod is preferably in contact with the scum, the crystals just sink into the melt, the crystals are kept sinking into the melt for 5-10 s and then move upwards again, and the crystals move to a position 200-300 mm away from the melt and are cooled for 5-10 min; the step is repeated for many times, 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 and presents a uniform and transparent form.
Example 1
The impurity removing method of the slag-inclusion impurity-containing monocrystalline germanium waste specifically comprises the following steps:
Step 1011: the method comprises the following steps of repeatedly using pot bottom materials, partial crystal bar broken end tailings, partial numerical control milling machine nesting excess materials and the like for growing the single crystal germanium for many times, inevitably generating some waste materials in the processes of crystal growth and material forming, placing the waste materials into a high-purity graphite crucible, closing a furnace cover of a crystal growing furnace, and forming a closed chamber;
step 1012: preferably, a mechanical vacuum pump is used for vacuumizing the chamber 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, so that the temperature in the chamber is slowly increased, the waste materials are gradually melted, and the temperature of the waste materials is kept constant for 5 hours when the temperature of the waste materials is 980 ℃.
Step 1021: preferably, the temperature of the melt is reduced by 25 ℃, and partial oxide and germanium metal in the melt after temperature reduction are recrystallized;
step 1022: descending the seed crystal rod to 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 is used for transmitting crystallization latent heat through the seed crystal rod and firmly attached to the seed crystal rod;
step 1023: pulling the seed rod upwards, pulling the recrystallized substances out of the germanium melt, pulling the recrystallized substances into an auxiliary chamber of the crystal growing furnace, and cutting off the recrystallized substances in the auxiliary chamber;
step 1024: filling nitrogen into the crystal growth auxiliary chamber until the air pressure in the auxiliary chamber is equal to the atmospheric pressure, cooling the recrystallized substance for a period of time, and taking out;
step 1025: the taken-out recrystallized substances contain more impurities in slag and are sent to the working procedures of reduction and zone melting purification. And after multiple zone melting, selecting a middle section with a proper length as a qualified zone-melting germanium ingot.
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 rotation speed of the graphite crucible is set to be 8 rad/min;
step 1032: preferably, after the pressure in the furnace is stable, the pressure is kept for about 30min, the valves for air inlet and vacuum pumping are closed, and the crucible rotation is stopped;
step 1033: preferably, as shown in fig. 3, a protective gas 301, such as argon or nitrogen, is filled into a chamber formed by a high-purity graphite crucible 303, the protective gas 301 flows onto a guide cylinder 302 at a certain angle, and then flows onto a waste melt liquid level 305 in a reflection manner, the pressure in the chamber is stabilized at 250torr within 3min to 5min, then, the opening of a butterfly valve of a vacuum pump is maintained at 60% to 80%, the gas in the furnace is rapidly replaced, and the temperature and the gas flow in the furnace are changed violently;
step 1034: the force generated by the drastic changes pushes the surface oxide dross towards the center of the melt.
Step 1041: through carrying out the flow field control treatment of the chamber for multiple times, scum is well concentrated on the center of the surface of the melt, and then, preferably, the pressure in the chamber is adjusted to 15 torr;
step 1042: preferably, as shown in FIG. 2, a seed crystal 201 with a crystal orientation of <111> is used for seeding and shouldering 202, the rotating speed of a seed crystal rod is controlled to be 2 rad/min, and the seed crystal rod moves downwards to be in contact with scum transferred to the center of a melt;
step 1043: slowly pulling up the seed rod in the presence of supercooling degree, crystallizing and growing the germanium in a molten state at the seed crystal, and wrapping most of oxide scum into crystals in the process;
step 1044: preferably, the shape of the growing crystal is hexagonal, such as the crystal shape formed by the seeding shouldering 202 in fig. 2, when the crystal grows to 80mm of the diagonal length, the seed crystal rod is pulled upwards to a position 200mm away from the melt, the temperature at 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 on the surface of the melt, and cooled crystals are needed to be adhered again, namely, a seed rod moving downwards at the rotating speed of 1 rad/min is in contact with the scum, the crystals are preferably just immersed into the melt, the crystals are kept immersed into the melt for 5 s-10 s and then move upwards again, and the crystals move to a position 200 mm-300 mm away from the melt and are cooled for 5 min-10 min;
step 1046: step 1045 is repeated several times to make the oxide scum on the surface of the melt adhere to the crystals as much as possible.
Finally, oxide scum is completely attached to crystals to form slag heads, the seed crystal rods are lifted upwards to cut off the slag heads and taken out, impurity removal of the impurity-contained monocrystalline germanium waste material with slag is completed, the purity of the impurity-removed germanium reaches more than 6N by the method of the embodiment, and the melt can be continuously used for growing single crystals, particularly for growing infrared large-diameter germanium single crystals with the diameter of more than phi 450 mm. Specifically, the method is used for treating the impurity-containing germanium-contained slag, so that large-particle and small-particle oxide scum can be removed to a large extent, and the influence of crystal nucleus on crystal growth can be reduced. When the reduction of crystallization nucleation approaches zero, the edge of the growing single crystal is not easy to crystallize at the position close to the crucible along with the increase of the radial size of the growing single crystal, namely, the growing single crystal is not easy to change crystal, and the growing of the infrared large-diameter germanium single crystal with the diameter of more than phi 450mm is easier to succeed.
Comparative example 1
The other steps are the same as those in embodiment 1, except for step 1021;
the temperature of the melt is reduced to be lower than 15 ℃, the recrystallization amount of the melt oxide after temperature reduction is less, multiple times of adhering and lifting are needed, more scum appears in the subsequent flow field control and scum lifting and adhering stages of the chamber, and the operation of the step is difficult.
Comparative example 2
The other steps are identical to those of example 1, except for step 1033;
the opening of a butterfly valve of the vacuum pump is kept at 10% -30%, gas in the cavity is replaced slowly, the temperature reduction amplitude caused by the gas replacement is small, the force generated by the change of the gas flow is small, the amount of recrystallized substances is reduced, less slag is concentrated in the center of the crucible, and the corresponding slag extraction efficiency is reduced.
Comparative example 3
The guide cylinder is not used, or the flow direction of the protective gas is not reflected by the guide cylinder, the protective gas directly flows to the liquid level of the melt, the crystallization generated on the surface of the melt does not start from the middle of the liquid level, the scum is not well concentrated in the middle, the slag extraction operation is difficult, or the efficiency is not high.
Comparative example 4
The other steps are the same as those in example 1 except for the step 1042;
the crystal with the <111> crystal orientation is not used, the crystal with other crystal orientations is used, the external shape of the crystal grown by crystal seeding shouldering is difficult to realize hexagon, the external shape of the crystal is easy to change into round along with the crystal seeding shouldering, the attachment is difficult to realize during the operation of attaching and slag extracting, and the attachment efficiency is not high.
The rotating speed of the seed crystal rod is adjusted to be more than 6rad/min, crystal rounding occurs too early when the seed crystal is placed on the shoulder, and floating slag is not attached favorably.
Comparative example 5
The other steps are identical to example 1, except for step 1045;
the rotating speed of the seed crystal rod is adjusted to be 3 rad/min without obvious change.
Comparative example 6
The other steps are identical to example 1, except for step 1045;
the rotating speed of the seed crystal rod is adjusted to be more than 6rad/min, so that fine and broken scum is not easy to adhere, and the impurity removal efficiency is reduced.
Claims (6)
1. The impurity removing method of the slag-inclusion impurity-containing monocrystalline germanium waste material is characterized by comprising the following steps of:
(1) melting the growth waste of the single crystal germanium;
(2) cooling and recrystallizing the waste slag inclusion: after the germanium waste is completely melted into a molten state, adjusting the heating power to reduce the temperature by 15-50 ℃, cooling the melt, and recrystallizing partial oxide together with germanium metal in the cooled melt; lowering the seed rod towards the melt direction to be connected and welded with the recrystallized material for a period of time; pulling the seed rod upwards, pulling the recrystallized substances out of the germanium melt, pulling the recrystallized substances into an auxiliary chamber of the crystal growing furnace, and cutting off the recrystallized substances in the auxiliary chamber; filling nitrogen into the crystal growth auxiliary chamber until the air pressure in the auxiliary chamber is equal to the atmospheric pressure, cooling the recrystallized substance for a period of time, taking out, and sending to a zone melting purification process;
(3) controlling a flow field of the cavity: controlling the pressure in the chamber to be 10-15 torr and setting the rotation speed of the graphite crucible to be 8-10 rad/min for the germanium melt after recrystallization treatment; keeping the pressure in the furnace for 25-35 min after the pressure in the furnace is stable, closing a gas inlet and vacuumizing valve, stopping the rotation of the crucible, filling protective gas into the cavity within 3-5 min, and reflecting the gas to the liquid level of the melt through a guide cylinder until the pressure in the cavity is stable at 200-350 torr, and meanwhile, keeping the opening of a butterfly valve of a vacuum pump at 60-80%; oxide scum on the surface of the germanium melt is moved to the center of the melt;
(4) lifting and adhering scum: adjusting the pressure in the chamber to be 15-50 torr by carrying out chamber flow field control processing for multiple times; controlling the rotation speed of a seed rod to be 1-6 rad/min by using a seed crystal with a <111> crystal orientation, moving downwards to contact with scum transferred to the center of a melt, pulling the seed rod upwards, wherein the grown crystal is hexagonal, and when a crystal grows to a diagonal length of 80-100 mm, the seed rod upwards reaches a position 200-300 mm away from the melt to rapidly cool the crystal; then controlling the seed crystal rod to move the cooled crystal downwards to enable the crystal to just sink into the melt, keeping the crystal to sink into the melt for 5 s-10 s, then moving upwards again, and moving the crystal to a position 200 mm-300 mm away from the melt to cool for 5 min-10 min; the step is repeated for a plurality of times to remove the scum on the surface of the melt.
2. The impurity removing method for the inclusion impurity-containing monocrystalline germanium waste material according to claim 1, wherein in the step (1), the method for melting the monocrystalline germanium growth waste material comprises the following steps: placing the 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 to 937.4-1200 ℃, keeping the temperature constant for a period of time, and melting the germanium waste.
3. The impurity removing method for the inclusion impurity-containing monocrystalline germanium waste according to claim 2, wherein in the step (1), the chamber is vacuumized to a vacuum degree of 5 torr-100 torr.
4. The impurity removing method for the inclusion impurity-containing monocrystalline germanium waste material according to claim 1, wherein in the step (2), the time for melting the seed rod and the recrystallized material is 3-5 min.
5. The impurity removing method for the inclusion slag impurity-containing monocrystalline germanium waste material according to claim 1, wherein the germanium waste material comprises pot bottom materials, partial crystal bar broken end materials or partial numerical control milling machine nesting residues which are repeatedly used in the growth of monocrystalline germanium.
6. The impurity removing method for the inclusion impurity-containing monocrystalline germanium waste material 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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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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