CN114574949B - Method for protecting quartz crucible in germanium single crystal pulling process - Google Patents

Method for protecting quartz crucible in germanium single crystal pulling process Download PDF

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CN114574949B
CN114574949B CN202210262673.9A CN202210262673A CN114574949B CN 114574949 B CN114574949 B CN 114574949B CN 202210262673 A CN202210262673 A CN 202210262673A CN 114574949 B CN114574949 B CN 114574949B
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crystal
crucible
ending
cooling
pulling
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CN114574949A (en
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牛晓东
赵青松
狄聚青
顾小英
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Anhui Guangzhi Technology Co Ltd
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Anhui Guangzhi Technology Co Ltd
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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
    • C30B15/20—Controlling or regulating
    • 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
    • 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
    • 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
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Abstract

The invention discloses a method for protecting a quartz crucible in the process of pulling germanium single crystals, which comprises the following steps: melting materials, seeding, shouldering, isodiametric setting, shouldering, ending one, ending two and cooling; wherein, put shoulder two: controlling the uniform cooling and keeping for a certain period of time to enable the crystal to grow gradually; ending one: regulating the crucible temperature, and controlling the uniform cooling according to the low cooling frequency to gradually shrink the crystal; ending two: and (5) regulating the crucible temperature and the crucible rotation, and controlling the uniform cooling according to the high cooling frequency until the melt is lifted. On one hand, the shoulder-putting stage is additionally arranged after the constant diameter stage so as to shorten the crystal pulling period and provide a stable thermal field environment for the ending stage; on the other hand, the ending stage is divided into two stages, so that the ending stage is in a stable and easily-controlled thermal field environment by gradually increasing the cooling frequency, reducing the crucible lifting speed, reducing the crucible rotating speed and other external factors, and the quartz crucible is protected from being burst in the germanium single crystal pulling process.

Description

Method for protecting quartz crucible in germanium single crystal pulling process
Technical Field
The invention relates to the technical field of crystal pulling, in particular to a method for protecting a quartz crucible in the process of germanium single crystal pulling.
Background
The basic principle of the Czochralski method (hereinafter referred to as cz method) is that a raw material for crystal growth is melted by heating in a crucible, and a certain supercooling degree is generated in the melt to generate nucleation driving force. And immersing seed crystals fixed at the lower ends of the seed rods from the upper surface of the melt, and after partial melting of one end of the seed crystals immersed in the melt, lifting the seed rods upwards at a certain speed, wherein heat generated at solid-liquid interfaces in the crystallization process is transmitted through the seed rods. The melt in contact with the seed crystal first acquires a certain supercooling degree and starts the crystallization process. With the slow lifting of the seed rod, continuous crystal growth can be realized by controlling factors such as temperature, pulling speed and the like. The crystal growth dynamics can be observed at any time by the CZ method single crystal pulling, the growth condition of the crystal can be conveniently mastered, and the growth condition is easy to control. In addition, in the crystal growth process, the crystal is not contacted with the crucible wall, and parasitic nucleation generated by the crystal and the crucible wall can be obviously reduced. In addition, the crystal grown by the Czochralski method has high integrity, high growth rate and large crystal size, and can grow crystals with specific crystal orientation according to the crystal orientation of the seed crystal, so that the crystal growth method is widely applied to the field of single crystal growth.
In the single crystal pulling process of high purity germanium, hydrogen is generally used as a shielding gas, a quartz crucible is used for containing germanium materials, the graphite crucible is positioned outside the quartz crucible to absorb radio frequency waves so as to generate heat for heating to melt the germanium materials, and a crucible rod is positioned right below the graphite crucible to control the movement of the crucible. Since the quartz crucible is in direct contact with germanium materials, the requirement is extremely high, and a synthetic quartz crucible with low impurities and low hydroxyl groups is required to be used, and the crucible is extremely expensive, so that the quartz crucible is preferably reused for a plurality of times.
In addition, the single crystal pulling process of the high-purity germanium comprises a material melting stage, a seeding stage, a shouldering stage, an isodiametric stage, a ending stage and the like. In the ending stage of single crystal pulling, less and less molten germanium materials are required, the heat preservation capacity of the crucible bottom, the liquid level descending speed and the crystal crystallization latent heat are obviously different from those in the isodiametric stage, the thermal field condition is complex at the moment, and a plurality of factors such as temperature, pulling speed, crucible lifting, crucible rotation and the like need to be reasonably controlled, so that the last germanium material drop is ensured to be completely pulled; however, due to the difference in thermal expansion coefficients of the quartz and the germanium material, if a residual drop of germanium material is adhered to the inner wall of the quartz crucible to solidify, the quartz crucible is burst. Therefore, protecting the quartz crucible from being broken during the germanium single crystal pulling process is an important technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a method for protecting a quartz crucible in the process of pulling germanium single crystals, on the one hand, on the basis of not affecting the properties of crystal purity, dislocation and the like, a shoulder-release stage is additionally arranged after a constant diameter stage so as to shorten the crystal pulling period, avoid low-temperature protective gas from directly flowing into the bottom of the crucible and reduce the heat loss of the bottom of the crucible, thereby providing a stable thermal field environment for a tail-end stage; on the other hand, the ending stage is split into two stages, so that external factors such as gradually increasing the cooling frequency, reducing the crucible lifting speed and reducing the crucible rotating speed are conveniently used, the ending stage is in a stable and easily-controlled thermal field environment, crystal ending is controlled, germanium material is guaranteed to be completely pulled, and the quartz crucible is protected from being broken in the germanium single crystal pulling process.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for protecting a quartz crucible in the process of pulling a germanium single crystal comprises the following steps: melting, seeding, shouldering, isodiametric ending and cooling, wherein the steps between the isodiametric ending and the ending are as follows:
shoulder placing II: controlling the uniform cooling and keeping for a certain period of time, so that the crystal diameter gradually grows to be larger than the required size;
the ending comprises the following steps:
ending one: regulating the crucible lifting speed, and controlling uniform cooling according to the low cooling frequency to gradually reduce the crystal diameter to a certain crystal size;
ending two: and (3) regulating down the crucible lifting speed and the crucible rotating speed, and controlling the uniform cooling according to the high cooling frequency to ensure that the crystal is continuously ended until the melt is lifted.
Preferably, the shoulder rest two comprises:
and uniformly cooling according to the cooling frequency of 80-100w/h, and keeping for a certain period of time, so that the crystal diameter gradually grows to be larger than the required size, and stopping cooling.
Preferably, the ending first includes:
the crucible raising speed is reduced to 0.3-0.5mm/h, and the uniform cooling is controlled according to the cooling frequency of 80-100w/h and kept for a certain period of time, so that the crystal diameter is gradually reduced to a certain crystal size.
Preferably, the second ending part includes:
and (3) reducing the crucible lifting speed to 0.1-0.3mm/h, reducing the crucible rotating speed to 2-5r/min, controlling uniform cooling according to the cooling frequency of 100-200w/h and keeping for a certain period of time, and continuously ending the crystal until the melt is pulled.
Preferably, the chemical comprises:
etching and cleaning the high-purity germanium raw material, and drying by adopting nitrogen;
placing the high-purity germanium raw material and the high-purity seed crystal into a pulling furnace, sealing the pulling furnace, and introducing hydrogen for purging;
heating power is controlled and the temperature is raised to 1000 ℃, so that the high-purity germanium raw material is completely melted into a melt, the temperature is reduced to 940-970 ℃, the crystal rotation speed is opened by 5-10r/min, the crucible rotation speed is opened by 5-10r/min, and the constant temperature is kept for 30-60min.
Preferably, the seeding includes:
slowly inserting the high-purity seed crystal into the melt, adjusting heating power according to the melt interface, waiting for 10-20min to start seeding after a certain width aperture appears, gradually increasing the pulling speed to 20-30mm/h, and simultaneously maintaining the pulling speed for seeding for 20-40min.
Preferably, the shoulder rest includes:
the crucible lifting speed is controlled to be 0.5-1mm/h, the uniform cooling is controlled and kept for a certain period of time, so that the crystal diameter is gradually increased to the required crystal size, and the cooling is stopped.
Preferably, the controlling the uniform cooling and maintaining for a certain period of time includes:
and uniformly cooling according to the cooling frequency of 100-200w/h and keeping for a certain period of time.
Preferably, the constant diameter includes:
the temperature is controlled according to the crystal diameter, so that the crystal diameter is kept unchanged for a certain period of time.
According to the technical scheme, in the method for protecting the quartz crucible in the germanium single crystal pulling process, on one hand, on the basis of not affecting the properties of crystal purity, dislocation and the like, the shoulder-release stage is additionally arranged after the constant diameter stage so as to shorten the crystal pulling period, prevent low-temperature protective gas from directly flowing into the bottom of the crucible and reduce the heat loss of the bottom of the crucible, and therefore, a stable thermal field environment can be provided for the ending stage; on the other hand, the ending stage is split into two stages, so that external factors such as gradually increasing the cooling frequency, reducing the crucible lifting speed and reducing the crucible rotating speed are conveniently used, the ending stage is in a stable and easily-controlled thermal field environment, crystal ending is controlled, germanium material is guaranteed to be completely pulled, and the quartz crucible is protected from being broken in the germanium single crystal pulling process.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flowchart of a method for protecting a quartz crucible in a germanium single crystal pulling process according to an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The method for protecting the quartz crucible in the germanium single crystal pulling process provided by the embodiment of the invention, as shown in fig. 1, comprises the following steps: melting, seeding, shouldering, isodiametric ending and cooling; the method further comprises the following steps between the constant diameter and the ending:
shoulder placing II: controlling the uniform cooling and keeping for a certain period of time, so that the crystal diameter gradually grows to be larger than the required size;
the ending comprises the following steps:
ending one: regulating the crucible lifting speed, and controlling uniform cooling according to the low cooling frequency to gradually reduce the crystal diameter to a certain crystal size;
ending two: and (3) regulating down the crucible lifting speed and the crucible rotating speed, and controlling the uniform cooling according to the high cooling frequency to ensure that the crystal is continuously ended until the melt is lifted.
According to the technical scheme, in the method for protecting the quartz crucible in the germanium single crystal pulling process, on one hand, on the basis of not affecting various performances such as crystal purity and dislocation, the shoulder-release stage is additionally arranged after the constant diameter stage so as to shorten the crystal pulling period, avoid low-temperature protective gas from directly flowing into the bottom of the crucible and reduce heat loss of the bottom of the crucible, and therefore a stable thermal field environment can be provided for the ending stage; on the other hand, the ending stage is split into two stages, so that external factors such as gradually increasing the cooling frequency, reducing the crucible lifting speed and reducing the crucible rotating speed are conveniently used, the ending stage is in a stable and easily-controlled thermal field environment, crystal ending is controlled, germanium material is guaranteed to be completely pulled, and the quartz crucible is protected from being broken in the germanium single crystal pulling process.
More specifically, the shouldering two parts comprise:
and uniformly cooling according to the cooling frequency of 80-100w/h and keeping for a certain period of time so as to keep the crystal for a certain period of time in the second shouldering, further gradually growing the crystal diameter to a crystal size larger than the required size, and stopping cooling. That is, the shoulder stage is additionally arranged after the constant diameter stage, so that crystals with larger crystal sizes can be pulled out conveniently, and the crystal pulling period can be shortened effectively and conveniently.
In this solution, the ending one includes:
the crucible raising speed is reduced to 0.3-0.5mm/h, and the uniform cooling is controlled according to the cooling frequency of 80-100w/h and kept for a certain period of time, so that the crystal is kept for a certain period of time in the first ending, and the diameter of the crystal is gradually reduced to a certain crystal size. Most preferably, the present stage is such that the crystal diameter is gradually reduced to half the crystal diameter of the previous stage.
Specifically, the second ending part comprises:
and (3) reducing the crucible lifting speed to 0.1-0.3mm/h, reducing the crucible rotating speed to 2-5r/min, and controlling the uniform cooling according to the cooling frequency of 100-200w/h and keeping for a certain period of time so as to keep the crystal for a certain period of time in the second ending, and further keeping the crystal ending until the melt is pulled. Wherein, in order to better make the melt be pulled up, this requires two stages of equal time periods for the first and second ending; accordingly, the duration of the ending one is the same as the duration of the ending two.
In this scheme, the chemical material includes:
(1) Etching and cleaning the high-purity germanium raw material, and drying by adopting nitrogen;
(2) Placing the high-purity germanium raw material and the high-purity seed crystal into a pulling furnace, sealing the pulling furnace, and introducing hydrogen for purging; firstly, placing a quartz crucible with a semicircular bottom in a graphite crucible, then knocking a high-purity germanium raw material into small blocks, placing the small blocks into the quartz crucible, and then fixing a high-purity seed crystal on a seed crystal clamp at the lowest part of a seed crystal rod;
(3) Heating power is controlled and the temperature is raised to 1000 ℃, so that the high-purity germanium raw material is completely melted into a melt, the temperature is reduced to 940-970 ℃, the crystal rotation speed is opened by 5-10r/min, the crucible rotation speed is opened by 5-10r/min, and the constant temperature is kept for 30-60min.
Specifically, the seeding includes:
slowly inserting the high-purity seed crystal into the melt, adjusting heating power according to the melt interface, waiting for 10-20min to start seeding after a certain width aperture appears, gradually increasing the pulling speed to 20-30mm/h, and simultaneously maintaining the pulling speed for seeding for 20-40min.
Further, the shouldering includes:
keeping the pulling speed unchanged, starting the crucible lifting speed to be 0.5-1mm/h, controlling the uniform cooling and keeping for a certain period of time so as to keep the crystal for a certain period of time in the first shouldering, further enabling the diameter of the crystal to gradually grow to the required crystal size, and stopping cooling. Wherein the cooling frequency of the stage is 100-200w/h, namely the uniform cooling is controlled according to the cooling frequency of 100-200w/h and the cooling is kept for a certain period of time. Of course, when germanium single crystals with different diameters are pulled, relevant parameters of the material melting, crystal guiding, shoulder placing and other stages can be correspondingly adjusted.
Still further, the constant diameter includes:
the temperature is controlled according to the crystal diameter, so that the crystal diameter is kept unchanged for a certain period of time. More specifically, the crystal diameter is observed, and the heating power is manually controlled so that the crystal diameter remains unchanged and the constant diameter is maintained for a certain period of time.
The present solution is further described below in connection with specific embodiments:
the method for protecting the quartz crucible in the process of pulling the germanium single crystal provided by the embodiment of the invention is now described by taking a three-inch germanium single crystal with a pulling diameter as an example, and comprises the following steps:
a. preparation (i.e. the above-mentioned material melting step, the following is the same)
(1) Preparing 6-8kg of high-purity germanium raw material, placing into HNO 3 : hf= (2-3): 1, after the surface of the steel is corroded in the corrosive liquid until the surface is bright, taking out, flushing the steel for more than 20 minutes by pure water, and drying the steel by nitrogen for later use;
(2) Preparing a quartz crucible with the diameter of 150mm and the bottom of a semicircle, placing the quartz crucible into a graphite crucible, and knocking high-purity germanium raw materials into small blocks and loading the small blocks into the quartz crucible;
(3) Preparing high-purity seed crystals, and fixing the high-purity seed crystals on a seed crystal clamp at the lowest part of a seed crystal rod;
(4) Sealing the lifting furnace, and blowing high-purity hydrogen for 2-3h;
(5) Heating power is controlled, heating to 1000 ℃ within 4-5h, melting high-purity germanium raw material, cooling to 940-970 ℃ after melting is completed, simultaneously starting crystal rotation for 5-10r/min, starting crucible rotation for 5-10r/min, and keeping constant temperature for 30-60min;
b. seeding
Slowly inserting high-purity seed crystal into the melt, adjusting power according to the melt interface, waiting for 10-20min after a certain width aperture appears, starting seeding, gradually increasing the pulling speed to 20-30mm/h, and maintaining the pulling speed for seeding for 20-40min;
c. shoulder rest I (i.e. shoulder rest step described above, the same applies hereinafter)
Keeping the pulling speed at 20-30mm/h, and opening the crucible to raise: 0.5-1mm/h;
controlling the power to be uniformly cooled, wherein the cooling frequency is 100-200w/h, the shoulder is placed for 2-3h, the crystal diameter is gradually increased to 70-80mm, and cooling is stopped;
d. constant diameter
Observing the crystal diameter, and manually controlling the power to ensure that the crystal diameter is kept to be 70-80mm, and the constant diameter process is carried out for 4-6 hours;
e. shoulder rest two
Controlling the power to be uniformly cooled, wherein the cooling frequency is 80-100w/h, shouldering for 40-60min, gradually growing the crystal diameter to 80-90mm, and stopping cooling;
f. ending one
Lowering the crucible to 0.3-0.5mm/h, controlling the power to be uniformly cooled, controlling the cooling frequency to be 80-100w/h, ending for 60-80min, and gradually reducing the crystal diameter to 35-45mm;
g. ending two
Lowering the crucible to 0.1-0.3mm/h, turning the crucible to 2-5r/min, controlling the power to be uniformly cooled, controlling the cooling frequency to be 100-200w/h, ending for 60-80min, and completely pulling the molten material in the quartz crucible;
h. cooling down
And closing the crystal lifting and the crucible lifting, controlling the power to be uniformly cooled to the room temperature, and then closing the crystal turning and the crucible turning to finish crystal lifting.
Examples:
pulling a three inch diameter germanium single crystal:
a. preparation of
(1) Preparing 7kg of high-purity germanium raw material, placing into HNO 3 : hf=2.5: 1, after the surface of the steel is corroded in the corrosive liquid until the surface is bright, taking out, flushing the steel for 30min by pure water, and drying the steel by nitrogen for later use;
(2) Preparing a quartz crucible with the diameter of 150mm and the bottom of a semicircle, placing the quartz crucible into a graphite crucible, and knocking high-purity germanium raw materials into small blocks and loading the small blocks into the quartz crucible;
(3) Preparing high-purity seed crystals, and fixing the high-purity seed crystals on a seed crystal clamp at the lowest part of a seed crystal rod;
(4) Sealing the lifting furnace, and blowing high-purity hydrogen for 2.5 hours;
(5) Heating power is controlled, heating to 1000 ℃ within 4.5h, melting high-purity germanium raw material, cooling to 950 ℃ after melting is completed, starting crystal rotation for 6r/min, starting crucible rotation for 6r/min, and keeping constant temperature for 45min;
b. seeding
Slowly inserting high-purity seed crystal into the melt, adjusting power according to the melt interface, waiting for 15min after a certain width aperture appears, starting seeding, gradually increasing the pulling speed to 24mm/h, and maintaining the pulling speed for seeding for 30min;
c. shoulder rest
Keeping the pulling speed at 24mm/h, and opening the crucible to raise: 0.8mm/h;
controlling the power to be uniformly cooled, wherein the cooling frequency is 140w/h, the shoulder is placed for 2.5h, the crystal diameter is gradually increased to 78mm, and the cooling is stopped;
d. constant diameter
Observing the crystal diameter, and manually controlling the power to ensure that the crystal diameter is kept to be 78mm, and the constant diameter process is 4.5 hours;
e. shoulder rest two
Controlling the power to be uniformly cooled, wherein the cooling frequency is 95w/h, the shoulder is placed for 45min, the crystal diameter is gradually increased to 83mm, and the cooling is stopped;
f. ending one
Lowering the crucible to 0.4mm/h, controlling the power to be uniformly cooled, wherein the cooling frequency is 95w/h, ending for 70min, and gradually reducing the crystal diameter to 40mm;
g. ending two
Lowering the crucible to 0.25mm/h, turning the crucible to 3r/min, controlling the power to be uniformly cooled, controlling the cooling frequency to 140w/h, ending for 70min, and completely pulling the molten material in the quartz crucible;
h. cooling down
And closing the crystal lifting and the crucible lifting, controlling the power to be uniformly cooled to the room temperature, and then closing the crystal turning and the crucible turning to finish crystal lifting.
Comparative example one:
three-inch germanium single crystals are pulled according to the embodiment, but a shoulder placing procedure is not arranged after the diameter is equal;
comparative example two:
pulling up the three-inch germanium single crystal according to the embodiment, but ending the whole process according to the first ending procedure, and canceling the second ending procedure;
sampling the high-purity germanium single crystal obtained in the example and the two comparative examples at equal diameter and 5cm down at equal diameter, slicing, and detecting the two samples respectivelyPoint purity (i.e. sample carrier concentration in 1/cm 3 ) And dislocation, and counting the pulling period and crucible conditions, respectively, with the results shown in the following table:
Figure BDA0003551169360000091
therefore, the technical scheme is adopted to carry out the pulling of the high-purity germanium single crystal, on the one hand, on the basis of not affecting the properties of crystal purity, dislocation and the like, the shoulder-placing stage is additionally arranged after the constant diameter stage, so that the crystal pulling period is shortened, the direct flow of low-temperature protective gas into the bottom of the crucible is avoided, the heat loss of the bottom of the crucible is reduced, and a stable thermal field environment is provided for the ending stage; on the other hand, the ending stage is split into two stages, so that external factors such as gradually increasing the cooling frequency, reducing the crucible lifting speed and reducing the crucible rotating speed are conveniently used, the ending stage is in a stable and easily-controlled thermal field environment, crystal ending is controlled, germanium material is guaranteed to be completely pulled, and the quartz crucible is protected from being broken in the germanium single crystal pulling process.
The invention has the beneficial effects that:
1. adding a shouldering process II after the constant diameter: on the basis of not affecting the properties of crystal purity, dislocation and the like, the secondary shouldering shortens the crystal pulling period, avoids low-temperature protective gas from directly flowing into the bottom of the crucible, reduces the heat loss of the bottom of the crucible, and provides a stable thermal field environment for the ending stage;
2. the ending is performed in two stages: along with the ending, the quantity of the molten germanium material in the crucible is reduced, and at the moment, external factors such as gradually increasing the cooling frequency, reducing the crucible lifting speed, reducing the crucible rotating speed and the like are adopted, so that the ending stage is in a stable and easily-controlled thermal field environment, the crystal ending is controlled, the germanium material is ensured to be completely pulled, and the quartz crucible is protected from being burst.
Key points and protection points of the invention:
1. adding a shouldering process II after the diameter is equal;
2. the ending is performed in two stages.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (6)

1. A method for protecting a quartz crucible in the process of pulling a germanium single crystal comprises the following steps: the method is characterized by further comprising the following steps of material melting, seeding, shouldering, isodiametric ending and cooling:
shoulder placing II: controlling the uniform cooling according to the cooling frequency of 80-100w/h and keeping for a certain period of time, so that the crystal diameter gradually grows to be larger than the required size, and stopping cooling; wherein the certain time period is 40-60min;
the ending comprises the following steps:
ending one: reducing the crucible raising speed to 0.3-0.5mm/h, and controlling the uniform cooling according to the cooling frequency of 80-100w/h and keeping for a certain period of time so that the crystal diameter is gradually reduced to a certain crystal size; wherein the certain time period is 60-80min;
ending two: reducing the crucible lifting speed to 0.1-0.3mm/h, reducing the crucible rotating speed to 2-5r/min, controlling uniform cooling according to the cooling frequency of 100-200w/h and keeping for a certain period of time, and continuously ending the crystal until the melt is pulled; wherein the certain time period is 60-80min.
2. The method of protecting a quartz crucible during the pulling of a germanium single crystal according to claim 1, wherein the melting comprises:
(1) Etching and cleaning the high-purity germanium raw material, and drying by adopting nitrogen;
(2) Placing the high-purity germanium raw material and the high-purity seed crystal into a pulling furnace, sealing the pulling furnace, and introducing hydrogen for purging;
(3) Heating power is controlled and the temperature is raised to 1000 ℃, so that the high-purity germanium raw material is completely melted into a melt, the temperature is reduced to 940-970 ℃, the crystal rotation speed is opened by 5-10r/min, the crucible rotation speed is opened by 5-10r/min, and the constant temperature is kept for 30-60min.
3. The method of protecting a quartz crucible during the pulling of a germanium single crystal according to claim 2, wherein the seeding comprises:
slowly inserting the high-purity seed crystal into the melt, adjusting heating power according to the melt interface, waiting for 10-20min to start seeding after a certain width aperture appears, gradually increasing the pulling speed to 20-30mm/h, and simultaneously maintaining the pulling speed for seeding for 20-40min.
4. A method of protecting a quartz crucible during a germanium single crystal pulling process according to claim 3, wherein the shoulder comprises:
the crucible lifting speed is controlled to be 0.5-1mm/h, the uniform cooling is controlled and kept for a certain period of time, so that the crystal diameter is gradually increased to the required crystal size, and the cooling is stopped.
5. The method of protecting a quartz crucible during a germanium single crystal pulling process of claim 4, wherein said controlling the temperature to be lowered uniformly and maintained for a certain period of time comprises:
and uniformly cooling according to the cooling frequency of 100-200w/h and keeping for a certain period of time.
6. The method of protecting a quartz crucible during a germanium single crystal pulling process of claim 4, wherein the constant diameter comprises:
the temperature is controlled according to the crystal diameter, so that the crystal diameter is kept unchanged for a certain period of time.
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