CN111379014A - Crystal growth fluxing agent and crystal growth method - Google Patents

Crystal growth fluxing agent and crystal growth method Download PDF

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CN111379014A
CN111379014A CN202010380449.0A CN202010380449A CN111379014A CN 111379014 A CN111379014 A CN 111379014A CN 202010380449 A CN202010380449 A CN 202010380449A CN 111379014 A CN111379014 A CN 111379014A
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crystal
crystal growth
temperature
growth
fluxing agent
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张彦
王占勇
徐家跃
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Shanghai Institute of Technology
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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
    • 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
    • C30B29/12—Halides
    • 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
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/02—Heat treatment

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

Abstract

The invention discloses a fluxing agent for crystal growth and a crystal growth method. The crystal is Pb17O8Cl18The fluxing agent system comprises PbO, metal halide M 'X and metal halide M' X2And Bi2O3At least one of; m 'is Li, Na or K, M' is Mg, Ca, Ba, Sr or Pb, and X is F or Cl. The crystal growth method comprises the following steps: mixing and melting a polycrystalline raw material and a fluxing agent; starting seeding above a melt temperature saturation point, stabilizing the melt temperature at the saturation point, and starting crystal growth; and (4) growing the crystal to a required size, lifting the seed rod crystal to be separated from the liquid level, and annealing in a weak oxidizing atmosphere. The invention fully takes care of the orientation of crystal growth, effectively improves the stability of crystal growth, reduces the volatilization of a solution and the viscosity of a system in the growth process, and solves the problem of crystal growthThe problems of needle-like growth and easy cracking and color change of the grown crystal, large size of the grown crystal and high optical quality.

Description

Crystal growth fluxing agent and crystal growth method
Technical Field
The invention relates to a method for growing single crystals, in particular to mid-infrared nonlinear optical Pb17O8Cl18Flux for crystal growth and a crystal growth method.
Background
Pb17O8Cl18The crystal is a novel mid-infrared nonlinear optical crystal with high laser damage threshold discovered in 2015. The method has the advantages of large nonlinear optical coefficient, high laser damage threshold, wide light transmission range, stable physical and chemical properties and the like. Compared with other mid-infrared nonlinear optical crystals, Pb17O8Cl18The crystal has good growth habit, can grow in an open system, and greatly reduces the difficulty of the traditional infrared frequency doubling crystal in the closed system. Pb17O8Cl18The crystal can realize the output of the middle and far infrared laser to the visible light or the near infrared laser through the laser frequency conversion, and has wide application prospect in the field of high-power laser frequency conversion because the crystal has a high light damage resistance threshold. Journal of the American chemical Association (J.Am.chem.Soc.2015, 137,8360-8363 in the United states]Report Pb17O8Cl18The structure of a crystal belonging to the orthorhombic system, the space group being Fmm2, being a biaxial crystal, the unit cell parameters of which
Figure BDA0002481850420000011
Figure BDA0002481850420000012
Each unit cell containing 3 Pb17O8Cl18Chemical formula (I). Due to Pb17O8Cl18The crystal is a homoconstituent molten compound, and the prior report adopts a spontaneous nucleation method to carry out crystal growth, but the grown crystal is partially transparent, and a large number of macroscopic inclusions are arranged in the crystal, so that the grown crystal is easy to crack and can not meet the physical property test easily. Therefore, the invention preferably adopts a new suitable fluxing agent to carry out the mid-infrared nonlinear optical crystal Pb by adopting a fused salt top seed crystal method17O8Cl18The growth of (2).
Disclosure of Invention
The technical problem to be solved by the invention is as follows: providing a Pb17O8Cl18Flux for crystal growth and method for crystal growth to improve crystal growthLong system stability, increased crystallization temperature range for crystal growth, reduced high temperature solution viscosity and volatility, improved crystal needle growth habit, and large-size and high-quality Pb17O8Cl18And (4) crystals.
In order to solve the problems, the invention adopts the following technical scheme:
pb17O8Cl18A flux for crystal growth, characterized in that the flux system comprises PbO, metal halides M 'X, metal halides M' X2And Bi2O3At least one of; the metal halide M 'X and the metal halide M' X2Wherein M 'is Li, Na or K, M' is Mg, Ca, Ba, Sr or Pb, and X is F or Cl.
Preferably, said Pb is17O8Cl18Is prepared by the reaction of a Pb-containing compound, an O-containing compound and a Cl-containing compound.
The invention also provides a method for preparing the Pb by using the Pb17O8Cl18The crystal growth method of the fluxing agent for crystal growth is characterized in that the fluxing agent is grown by adopting a molten salt top seed crystal method, and comprises the following steps:
step 1): pre-synthesis of Pb17O8Cl18Polycrystalline raw materials;
step 2): adopting platinum crucible or alumina ceramic as container, pre-synthesizing Pb17O8Cl18Uniformly mixing a polycrystalline raw material and the fluxing agent, heating until the raw material is completely melted, and keeping at a constant temperature;
step 3): starting seeding at 1-10 ℃ above the saturation point of the melt temperature, keeping the temperature for 5-300 minutes, and starting crystal growth when the melt temperature is stabilized at the saturation point;
step 4): growing the crystal to a required size, lifting the seed rod crystal to separate from the liquid level, reducing the temperature to room temperature at a speed of less than 50 ℃/h, and annealing in a weak oxidizing atmosphere to obtain Pb17O8Cl18And (4) crystals.
Preferably, the amount of the fluxing agent in the step 2) is Pb17O8Cl185-75 mol% of polycrystalline raw material; pb17O8Cl18The temperature for completely melting the polycrystalline raw material into high-temperature solution is 515-600 ℃; the constant temperature time is 24 h.
Preferably, the melt temperature saturation point in the step 3) is 510-550 ℃.
Preferably, the process parameters of the crystal growth in the step 4) are as follows: the cooling rate is 0.01-2 ℃/day, the rotating speed is 1-50 rpm, the pulling speed is 0-100 mm/day,
preferably, the weakly oxidizing atmosphere in the step 4) is air, or a mixture of any one or more of nitrogen, hydrogen, carbon monoxide, carbon dioxide and alkane gases, or a mixture of the aforementioned gases with oxygen and/or inert gases.
The invention also provides Pb prepared by the crystal growth method17O8Cl18The crystal is applied to infrared nonlinear optical crystals.
Preferably, the Pb is17O8Cl18The crystal converts visible light or near infrared laser into 3-8 mu m and 8-14 mu m band mid-infrared laser output through laser frequency down conversion.
Pb provided by the invention17O8Cl18Fused salt top seeded method of crystals using metal halides M 'X, M' X2PbO and Bi2O3Of (2) a cosolvent system of (a). Compared with the prior art, the method has the beneficial effects that:
1) can effectively reduce the volatilization of the melt, improve the stability of the system in the crystal growth process, prevent the formation of mixed crystals and dendrites and improve the growth speed of the crystals.
2) The viscosity of the solution can be obviously reduced, and the lower viscosity is beneficial to solute transportation and is beneficial to growing high-quality crystals.
3) Pb in the present flux system17O8Cl18The crystallization temperature range of the crystal is wider, a proper saturation point is convenient to find, mixed crystals and dendritic crystals are prevented from being generated, and large-size crystals are easy to grow.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
Example 1
Weighing PbO and PbCl according to stoichiometric ratio2And the mixture is fully ground and evenly mixed and then transferred into an alumina ceramic crucible. The mixture was sintered in a muffle furnace at 420 ℃ for 24 hours. After cooling to room temperature, the product obtained was ground again and transferred to an alumina ceramic crucible and sintered at 480 ℃ for 24 hours in a muffle furnace. Naturally cooling to room temperature and taking out to obtain Pb17O8Cl18Polycrystalline feedstock. Adding Pb17O8Cl18Polycrystalline raw material and fluxing agent PbCl2、LiF2Mixing uniformly according to a molar ratio of 65:35, grinding and uniformly mixing the weighed raw materials, directly melting the raw materials in a platinum crucible with the diameter of 100mm × 75mm, putting the crucible filled with the molten material into a molten salt furnace, sealing an opening at the top of the furnace by using a heat-insulating material, leaving a small hole for a seed rod to go in and out at the position of the top of the furnace corresponding to the center of the crucible, heating to 530 ℃, completely melting the molten material, preserving heat for 24 hours at the temperature to fully and uniformly melt the molten material, searching the saturation temperature of crystal growth by using a crystal washing trial method to be 521 ℃, cooling the high-temperature solution to 526 ℃ (the saturation temperature is 5 ℃ higher than the temperature of Pb, and carrying out crystal washing trial culture on the high-temperature solution17O8Cl18The seed crystal is fixed at the lower end of a seed crystal rod by a platinum wire, the seed crystal is slowly led into a growth furnace from a small hole at the top of the furnace, the lower end of the seed crystal is extended into the liquid level by about 1mm, the seed crystal rotates at the speed of 25 revolutions per minute, the temperature is immediately reduced to 521 ℃ after the seed crystal is kept at the constant temperature for 240 minutes, and then the temperature is reduced at the speed of 0.3 ℃/day to carry out crystal growth. In the growth process, the rotation speed of the seed crystal is reduced along with the gradual growth of the crystal. After the crystal growth is finished, the crystal is separated from the liquid level, the temperature is reduced to room temperature at the speed of 15 ℃/h, and Pb is obtained by annealing in the air17O8Cl18And (4) crystals.
Example 2
Using stoichiometric ratio of PbO and PbCl2Mixing the powders, placing into an alumina ceramic crucible, covering, placing in a muffle furnace, maintaining at 470 deg.C for 48 hr, and naturally coolingTaking out the mixture after the temperature is reduced to room temperature, and fully grinding the mixture to obtain Pb17O8Cl18Polycrystalline feedstock. Adding Pb17O8Cl18Polycrystalline feedstock and PbF2、PbCl2Uniformly mixing the materials according to a molar ratio of 55:45, grinding and uniformly mixing the weighed materials, then putting the ground POC polycrystalline material into a platinum crucible with the diameter of 100mm and the diameter of × 75mm, putting the crucible into a molten salt furnace, covering the upper opening cover of the crucible, controlling the furnace temperature to be 575 ℃, completely melting the materials, keeping the temperature for 18 hours to ensure that the high-temperature solution is completely uniform, searching the saturation temperature of crystal growth to be 512 ℃ by using a crystal washing and testing method, cooling the high-temperature solution to 520 ℃ (higher than the saturation temperature of 8 ℃), and adding Pb into the solution17O8Cl18The seed crystal is fixed at the lower end of a seed crystal rod by a platinum wire, the seed crystal is slowly led into a growth furnace from a small hole at the top of the furnace, the lower end of the seed crystal is extended into the liquid level for about 1mm, the seed crystal rotates at the speed of 45 revolutions per minute, the temperature is immediately reduced to 512 ℃ after the seed crystal is kept at the constant temperature for 120 minutes, then the temperature is reduced at the speed of 0.3 ℃/day, and the crystal growth is carried out at the pulling speed of 0.1mm per day. In the growth process, the rotation speed of the seed crystal is reduced along with the gradual growth of the crystal. After the crystal growth is finished, pulling the crystal away from the liquid level, reducing the temperature to room temperature at the speed of 40 ℃/h, and annealing in the air atmosphere to obtain Pb17O8Cl18And (4) crystals.

Claims (9)

1. A flux for crystal growth, the crystal being Pb17O8Cl18Characterized in that the fluxing agent system comprises PbO, metal halide M 'X, metal halide M' X2And Bi2O3At least one of; the metal halide M 'X and the metal halide M' X2Wherein M 'is Li, Na or K, M' is Mg, Ca, Ba, Sr or Pb, and X is F or Cl.
2. The flux for crystal growth of claim 1, wherein said Pb17O8Cl18Is prepared by the reaction of a Pb-containing compound, an O-containing compound and a Cl-containing compound.
3. A crystal growth method using the flux for crystal growth according to claim 1 or 2, characterized by growing by a molten salt top seed method, comprising the steps of:
step 1): pre-synthesis of Pb17O8Cl18Polycrystalline raw materials;
step 2): adopting platinum crucible or alumina ceramic as container, pre-synthesizing Pb17O8Cl18Uniformly mixing a polycrystalline raw material and the fluxing agent, heating until the raw material is completely melted, and keeping at a constant temperature;
step 3): starting seeding at 1-10 ℃ above the saturation point of the melt temperature, keeping the temperature for 5-300 minutes, and starting crystal growth when the melt temperature is stabilized at the saturation point;
step 4): growing the crystal to a required size, lifting the seed rod crystal to separate from the liquid level, reducing the temperature to room temperature at a speed of less than 50 ℃/h, and annealing in a weak oxidizing atmosphere to obtain Pb17O8Cl18And (4) crystals.
4. The crystal growth method according to claim 3, wherein the amount of the flux used in the step 2) is Pb17O8Cl185-75 mol% of polycrystalline raw material; pb17O8Cl18The temperature for completely melting the polycrystalline raw material into high-temperature solution is 515-600 ℃; the constant temperature time is 24 h.
5. The crystal growth method of claim 3, wherein the melt temperature saturation point in step 3) is 510-550 ℃.
6. The crystal growth method of claim 3, wherein the process parameters of the crystal growth in the step 4) are as follows: the cooling rate is 0.01-2 ℃/day, the rotating speed is 1-50 rpm, and the pulling speed is 0-100 mm/day.
7. The crystal growth method according to claim 3, wherein the weakly oxidizing atmosphere in step 4) is air, or a mixture of any one or more of nitrogen, hydrogen, carbon monoxide, carbon dioxide and an alkane gas, or a mixture of the foregoing gases with oxygen and/or an inert gas.
8. Pb produced by the crystal growth method as set forth in any one of claims 3 to 717O8Cl18The crystal is applied to infrared nonlinear optical crystals.
9. Use according to claim 8, wherein said Pb is17O8Cl18The crystal converts visible light or near infrared laser into 3-8 mu m and 8-14 mu m band mid-infrared laser output through laser frequency down conversion.
CN202010380449.0A 2020-05-08 2020-05-08 Crystal growth fluxing agent and crystal growth method Pending CN111379014A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114250514A (en) * 2021-12-15 2022-03-29 上海应用技术大学 Fluxing agent for beta-gallium oxide crystal growth and crystal growth method based on same

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CN101245490A (en) * 2007-02-15 2008-08-20 中国科学院理化技术研究所 CsLiB6O10Flux growth method of crystal
CN101775652A (en) * 2010-02-08 2010-07-14 中国科学院理化技术研究所 K3Al2(PO4)3Preparation and use of nonlinear optical crystal
CN103173860A (en) * 2011-12-21 2013-06-26 中国科学院理化技术研究所 K3YB6O12Compound, K3YB6O12Nonlinear optical crystal and its preparation method and use
CN110685006A (en) * 2019-10-31 2020-01-14 上海应用技术大学 Intermediate infrared nonlinear optical crystal POC and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101245490A (en) * 2007-02-15 2008-08-20 中国科学院理化技术研究所 CsLiB6O10Flux growth method of crystal
CN101775652A (en) * 2010-02-08 2010-07-14 中国科学院理化技术研究所 K3Al2(PO4)3Preparation and use of nonlinear optical crystal
CN103173860A (en) * 2011-12-21 2013-06-26 中国科学院理化技术研究所 K3YB6O12Compound, K3YB6O12Nonlinear optical crystal and its preparation method and use
CN110685006A (en) * 2019-10-31 2020-01-14 上海应用技术大学 Intermediate infrared nonlinear optical crystal POC and preparation method thereof

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Title
HUI ZHANG: "Pb17O8Cl18：A promising IR Nonlinear optical material with large laser damage threshold synthesized in an open system", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114250514A (en) * 2021-12-15 2022-03-29 上海应用技术大学 Fluxing agent for beta-gallium oxide crystal growth and crystal growth method based on same
CN114250514B (en) * 2021-12-15 2023-08-04 上海应用技术大学 Flux for beta-gallium trioxide crystal growth and crystal growth method based on flux

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