CN112410869A - Method for growing crystal pulling body by reversely extracting fluxing agent - Google Patents

Method for growing crystal pulling body by reversely extracting fluxing agent Download PDF

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Publication number
CN112410869A
CN112410869A CN202011354513.4A CN202011354513A CN112410869A CN 112410869 A CN112410869 A CN 112410869A CN 202011354513 A CN202011354513 A CN 202011354513A CN 112410869 A CN112410869 A CN 112410869A
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China
Prior art keywords
growth
material rod
crystal
fluxing agent
speed
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CN202011354513.4A
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Chinese (zh)
Inventor
王坤鹏
张建秀
刘泳
任衍彪
李凤丽
徐本燕
朱雨凤
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Zaozhuang University
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Zaozhuang University
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Priority to CN202011354513.4A priority Critical patent/CN112410869A/en
Publication of CN112410869A publication Critical patent/CN112410869A/en
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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
    • C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
    • C30B13/02—Zone-melting with a solvent, e.g. travelling solvent process
    • 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
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/14—Phosphates
    • 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
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/30—Niobates; Vanadates; Tantalates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention discloses a method for growing a crystal body by reversely extracting a fluxing agent. Preparing a polycrystalline material rod containing a fluxing agent; in an optical floating zone furnace, quickly performing pre-growth at a speed which is about 50% higher than the normal growth speed; when the rapid pre-growth is about to end, namely when only about 0.5cm of the head of the material rod remains, the melting zone is stopped to move for about 1 minute under the condition of unchanged temperature and rotating speed; taking the obtained pre-grown polycrystalline material rod as a melt part, taking the rest material rod head as a seed crystal, starting to move a melting zone in a reverse direction, and reducing the moving speed of the melting zone to 0.5mm/min, namely realizing the growth effect of a TSSG top seed crystal method by adopting an optical floating zone furnace, which is called as a fluxing agent reverse pulling method; in the two completely opposite growth processes, the solid-liquid interface is always kept to be smoothly connected, and the whole process is not interrupted until the growth process is finished. The single crystal prepared by the method has the characteristics of simple process, short period and good stability, and the grown crystal has low defect concentration and high optical quality.

Description

Method for growing crystal pulling body by reversely extracting fluxing agent
Technical Field
The invention relates to a growth technology of a fluxing agent reverse-extraction crystal pulling body, belonging to the technical field of functional crystal materials.
Background
The optical floating zone method is one of the commonly used crystal growth techniques at present, and has the advantages of no crucible, no pollution, high growth speed and the like, but only can grow the uniformly molten crystal, and for the non-uniformly molten material, a high-temperature solution method is generally adopted, namely, a fluxing agent is added to reduce the melting point of the material, but the high-temperature solution method has complex process and high cost, and chemical raw materials need to be melted in a precious metal crucible at high temperature, so the pollution is easy to occur.
In order to overcome the difficulties in the prior art, the invention combines the advantages of an optical floating zone technology and a high-temperature liquid crystal growth technology, and provides a fluxing agent reverse-extraction crystal growth technology which has no crucible, no pollution, high growth speed and capability of growing inconsistent molten materials.
Disclosure of Invention
The invention aims to provide a method for growing a crystal body by reversely extracting a fluxing agent, so as to solve the technical problem.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for growing a crystal body by flux back-lifting is characterized by comprising the following steps:
1) preparing a polycrystalline material rod containing a fluxing agent;
2) in the optical floating zone furnace, the pre-growth is carried out rapidly at a speed about 30-60% higher than the normal growth speed;
3) when the rapid pre-growth is about to end, namely when only about 0.5-1.2cm of the head of the material rod remains, stopping the movement of the melting zone for about 1-3 minutes under the condition of unchanged temperature and rotating speed;
4) taking the pre-grown polycrystalline material rod obtained in the step 3 as a melt part, taking the rest material rod head as a seed crystal, starting to move a melting zone in a reverse direction, reducing the moving speed of the melting zone to 0.15-0.5 mm/min, and finishing crystal growth after 5-9 hours, namely, realizing the growth effect of a TSSG top seed crystal method by adopting an optical floating zone furnace, namely, the method is called a fluxing agent reverse pulling method;
5) in the two completely opposite growth processes of the steps 2 and 4, the solid-liquid interface is always kept to be smoothly connected, and the whole process is not interrupted until the growth process is finished.
The specific method of the step 1 is as follows: fully grinding the raw materials configured according to the molar ratio in an agate crucible for 20-40 minutes, transferring the uniformly mixed raw materials into a ceramic crucible, putting the ceramic crucible into a sintering furnace, and adding 170-210 materials oCSintering for 12-24 hours to make about 5-8cm of initial charge bar.
The invention has the beneficial effects that: the invention is suitable for the growth of the consistent melting crystal and the growth of the inconsistent melting crystal, and particularly solves the problems of crucible pollution, high cost and the like in the growth process of the inconsistent melting crystal. The single crystal prepared by the method has the characteristics of simple process, short period and good stability, and the grown crystal has low defect concentration and high optical quality.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
And preparing LiSrBaPO4 crystals. Using BaCO3, SrCO3, Li2CO3, and NH4H2PO4 as starting materials, according to the chemical equation:
Li2CO3 + 2SrCO3 + 2BaCO3 + NH4H2PO4 → 2LiSrBaPO4 + 5CO2↑ + 3H2O↑；
placing the raw materials configured according to the molar ratio into an agate crucible, grinding for 30 minutes, transferring the uniformly mixed raw materials into a ceramic crucible, placing the ceramic crucible into a sintering furnace, and placing the ceramic crucible into a 180 DEG sintering furnaceoC, sintering for 24 hours, taking out the sintered material, fully mixing and grinding the sintered material with the fluxing agent LiF, and manufacturing an initial material rod of 8 cm. Mounting the material rod in an optical floating zone furnace, and quickly pre-growing at a speed which is about 50% higher than the normal growth speed; stopping the melting zone when the rapid pre-growth is about to end, namely the head of the material rod is only left about 0.5cm, and the temperature and the rotating speed are not changedMoving for about 1 minute; taking the pre-grown polycrystalline material rod as a melt part, taking the rest material rod head as seed crystals, starting to move a melting zone in a reverse direction, reducing the moving speed of the melting zone to 0.2mm/min, finishing the crystal growth after 5 hours, and finally obtaining LiSrBaPO4 crystals with the diameter of 0.8cm and the length of 6 cm.
Example 2:
and preparing LiSrVO4 crystals. Using SrCO3, Li2CO3, and NH4VO3 as starting materials, according to the chemical equation:
Li2CO3 + 2SrCO3 + NH4VO3→ 2LiSrVO4+ 3CO2↑ + 2H2O↑；
placing the raw materials configured according to the molar ratio into an agate crucible, grinding for 20 minutes, transferring the uniformly mixed raw materials into a ceramic crucible, placing the ceramic crucible into a sintering furnace at 210 DEGoC, sintering for 12 hours, taking out the sintered material, fully mixing and grinding the sintered material with the fluxing agent LiF, and manufacturing an initial material rod of 8 cm. Mounting the material rod in an optical floating zone furnace, and quickly pre-growing at a speed which is about 30% higher than the normal growth speed; when the rapid pre-growth is about to end, namely when only about 0.5cm of the head of the material rod remains, the melting zone is stopped to move for about 1 minute under the condition of unchanged temperature and rotating speed; and taking the pre-grown polycrystalline material rod as a melt part, taking the rest material rod head as seed crystals, starting to reversely move a melting zone, reducing the moving speed of the melting zone to 0.3mm/min, finishing the crystal growth after 8 hours, and finally obtaining LiSrVO4 crystals with the diameter of 0.7cm and the length of 15 cm.
Example 3
Preparation of LiBa (BO3) 0.5 (VO4)0.5 crystal. Using BaCO3, Li2CO3, H2BO3 and NH4VO3 as starting materials, according to the chemical equation:
Li2CO3 + 2BaCO3 + H2BO3 + NH4VO3→ 2LiBa(BO3) 0.5 (VO4)0.5+ 3CO2↑ + 3H2O↑；
placing the raw materials configured according to the molar ratio into an agate crucible, grinding for 40 minutes, transferring the uniformly mixed raw materials into a ceramic crucible, placing the ceramic crucible into a sintering furnace and placing the ceramic crucible into a 170 DEG sintering furnaceoC, sintering for 24 hours, taking out the sintered material, fully mixing and grinding the sintered material with the fluxing agent LiF, and manufacturing an initial material rod of 5 cm. The material bar is arranged in an optical floating zone furnace and rapidly grows at a speed which is about 50 percent higher than the normal growth speedPre-growing; when the rapid pre-growth is about to end, namely when only about 0.5cm of the head of the material rod remains, the melting zone is stopped to move for about 1 minute under the condition of unchanged temperature and rotating speed; the pre-grown polycrystalline material rod is used as a melt part, the rest material rod head is used as a seed crystal, a melting zone starts to move reversely, the moving speed of the melting zone is reduced to 0.15mm/min, the crystal growth is finished after 9 hours, and finally LiBa (BO3) 0.5 (VO4)0.5 crystal with the diameter of 0.9cm and the length of 8cm is obtained.
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.

Claims (2)

1. A method for growing a crystal body by flux back-lifting is characterized by comprising the following steps:
1) preparing a polycrystalline material rod containing a fluxing agent;
2) in the optical floating zone furnace, the pre-growth is carried out rapidly at a speed about 30-60% higher than the normal growth speed;
3) when the rapid pre-growth is about to end, namely when only about 0.5-1.2cm of the head of the material rod remains, stopping the movement of the melting zone for about 1-3 minutes under the condition of unchanged temperature and rotating speed;
4) taking the pre-grown polycrystalline material rod obtained in the step 3 as a melt part, taking the rest material rod head as a seed crystal, starting to move a melting zone in a reverse direction, reducing the moving speed of the melting zone to 0.15-0.5 mm/min, and finishing crystal growth after 5-9 hours, namely, realizing the growth effect of a TSSG top seed crystal method by adopting an optical floating zone furnace, namely, the method is called a fluxing agent reverse pulling method;
5) in the two completely opposite growth processes of the steps 2 and 4, the solid-liquid interface is always kept to be smoothly connected, and the whole process is not interrupted until the growth process is finished.
2. A method of growing a flux-backed crystal as set forth in claim 1, wherein said method comprisesThe specific method of the step 1 is as follows: fully grinding the raw materials configured according to the molar ratio in an agate crucible for 20-40 minutes, transferring the uniformly mixed raw materials into a ceramic crucible, putting the ceramic crucible into a sintering furnace, and adding 170-210 materials oCSintering for 12-24 hours to make about 5-8cm of initial charge bar.
CN202011354513.4A 2020-11-27 2020-11-27 Method for growing crystal pulling body by reversely extracting fluxing agent Pending CN112410869A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6039802A (en) * 1997-03-12 2000-03-21 Murata Manufacturing Co., Ltd. Single crystal growth method
CN101363131A (en) * 2008-09-19 2009-02-11 山东大学 Top seed solution growth reentrance technology in fluxing agent growth method
CN102011188A (en) * 2010-12-08 2011-04-13 上海大学 Method for growing RFeO3 photomagnetic function crystal by secondary melting method
CN102061522A (en) * 2010-11-05 2011-05-18 北京工业大学 Two-step preparation method of large Al2O3-based crystal
CN107955963A (en) * 2017-12-18 2018-04-24 中国科学院上海硅酸盐研究所 A kind of La of float-zone method growth doping various concentrations Ta2Ti2O7The method of monocrystalline

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6039802A (en) * 1997-03-12 2000-03-21 Murata Manufacturing Co., Ltd. Single crystal growth method
CN101363131A (en) * 2008-09-19 2009-02-11 山东大学 Top seed solution growth reentrance technology in fluxing agent growth method
CN102061522A (en) * 2010-11-05 2011-05-18 北京工业大学 Two-step preparation method of large Al2O3-based crystal
CN102011188A (en) * 2010-12-08 2011-04-13 上海大学 Method for growing RFeO3 photomagnetic function crystal by secondary melting method
CN107955963A (en) * 2017-12-18 2018-04-24 中国科学院上海硅酸盐研究所 A kind of La of float-zone method growth doping various concentrations Ta2Ti2O7The method of monocrystalline

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张克立等编: "《无机合成化学 第2版》", 31 January 2012 *

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