CN117535782A - Cs (cell lines) 3 Zn 6 B 9 O 21 Crystal growth fluxing agent and crystal growth method - Google Patents
Cs (cell lines) 3 Zn 6 B 9 O 21 Crystal growth fluxing agent and crystal growth method Download PDFInfo
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- CN117535782A CN117535782A CN202310541412.5A CN202310541412A CN117535782A CN 117535782 A CN117535782 A CN 117535782A CN 202310541412 A CN202310541412 A CN 202310541412A CN 117535782 A CN117535782 A CN 117535782A
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- 239000013078 crystal Substances 0.000 title claims abstract description 108
- 238000002109 crystal growth method Methods 0.000 title description 6
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 230000004907 flux Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000002457 bidirectional effect Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 230000002269 spontaneous effect Effects 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012774 insulation material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- -1 Cesium zinc borate Chemical compound 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
Classifications
-
- 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
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
-
- 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
-
- 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
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/66—Crystals of complex geometrical shape, e.g. tubes, cylinders
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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)
- Physics & Mathematics (AREA)
- Geometry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention provides Cs 3 Zn 6 B 9 O 21 The flux growth method of the crystal adopts Cs 2 O‑B 2 O 3 ‑PbO‑PbF 2 The system is used as fluxing agent, and the mol ratio of the fluxing agent is (0.75-2.5) to (1.5-6) to (0-1.5) to (1-3). The crystal growth temperature is between 660 and 700 ℃, the viscosity and the volatility of the system are low, the mass transfer and the heat transfer are facilitated, the generation of crystal defects is reduced, the stability of a growth system is improved, the spontaneous crystallization is prevented, and the success rate of crystal growth is improved. The fluxing agent system has wide crystallization area and large cooling interval, and can stably grow a series of CZB crystals with large size and high optical quality.
Description
The invention relates to a single crystal growth method, in particular to a Cs 3 Zn 6 B 9 O 21 A crystal growth flux and a crystal growth method.
Technical Field
Background
Beryllium potassium fluoborate (KBE) 2 BO 3 F 2 KBBF) crystal is the only nonlinear optical crystal capable of directly doubling frequency to generate deep ultraviolet laser at present, but the layered growth habit is serious, and the crystal is difficult to grow thick. Meanwhile, KBBF crystal contains a highly toxic element Be, so that the wide application of KBBF crystal is limited. Zhou Jinjie of Tianjin university in 2014 synthesizes a novel ultraviolet nonlinear optical crystal by replacing Be in KBBF with ZnBulk material Cs 3 Zn 6 B 9 O 21 The crystal overcomes the layered growth habit of KBBF.
Cesium zinc borate (Cs) 3 Zn 6 B 9 O 21 CZB) crystals with unit cell parameters of Z=4, belonging to orthorhombic system, space group Cmc2 1 . CZB is an excellent ultraviolet nonlinear optical crystal having a small birefringence [ Δn=0.06 (1064 nm)]The ultraviolet cut-off edge is 359nm, the frequency doubling effect is about 3.3 times of KDP, and the crystal with the largest frequency doubling effect in the KBBF family is discovered at present. Since CZB is a non-homogeneous molten compound, only the flux method can be used for crystal growth. At present, no report is made on the growth of CZB crystals, and a proper flux system is required to be searched for to grow high-quality CZB crystals.
Disclosure of Invention
The invention aims to provide a CZB crystal growth fluxing agent and a crystal growth method, which are used for obtaining high-quality single crystals.
The CZB crystal growth fluxing agent of the invention is Cs 2 O-B 2 O 3 -PbO-PbF 2 A system.
Preferably, wherein Cs 2 O∶B 2 O 3 ∶PbO∶PbF 2 The molar ratio of (0.75-2.5) to (1.5-6) to (0-1.5) to (1-3).
The invention also provides a CZB crystal growth method, which comprises the following steps:
(a) According to Cs 2 O∶ZnO∶B 2 O 3 ∶PbO∶PbF 2 The mol ratio is (1-3) to (1-2) to (2-7) to (0-2) to (1-3) and the materials are evenly mixed, and the temperature is raised to 800-900 ℃ for melting, thus preparing the crystal growth raw material;
(b) After the growth raw materials are completely melted, cooling to 720-770 ℃, stirring at constant temperature for 24-48 h, introducing seed crystals fixed on seed rods to the liquid level at 1-3 ℃ above the saturation point temperature, keeping the temperature for 30-60 min, and cooling to the saturation point temperature;
(c) Taking the saturation point temperature as the initial temperature of cooling, cooling at the speed of 0.1-0.5 ℃/day, and simultaneously rotating the crystal at the speed of 5-20 rpm to enable the crystal to grow;
(d) After the crystal grows to the required size, lifting the seed rod to separate the crystal from the liquid surface, and cooling to room temperature at the speed of 5-20 ℃/h to obtain the CZB crystal.
Preferably, the compound Cs in step (a) 2 Cs for O 2 CO 3 Instead of this.
Preferably, compound B in step (a) 2 O 3 By H 3 BO 3 Instead of this.
Preferably, in the step (a), a platinum crucible is used to hold the uniformly mixed raw materials.
Preferably, the direction of the seed crystal in the step (b) may be any direction.
Preferably, the crystal rotation direction in the step (c) is unidirectional rotation or bidirectional rotation.
Preferably, in the step (c), if the crystal is rotated in two directions, the crystal is rotated in a clockwise and counterclockwise direction alternately, and the crystal is rotated according to the following period: the rotation is sequentially accelerated, rotated at a constant speed, decelerated, and stopped in a first direction, and then sequentially accelerated, rotated at a constant speed, decelerated, and stopped in a second direction opposite to the first direction.
In the above bidirectional rotation, the rotation time in each direction is preferably 1 to 3 minutes, and the interval time between bidirectional rotations is preferably 0.1 to 0.5 minutes.
The crystal growth size is determined according to the crystal growth condition and the crucible size. If the crystal growth condition is good, the crystal is grown continuously, otherwise, the growth is stopped to separate the crystal from the liquid surface; the maximum allowable size of the crystal is generally smaller than the size of the crucible by 1-3 cm, so that the crystal and the crucible are prevented from collision.
The invention has the beneficial effects that:
metal oxide and metal fluoride in nonlinear optical crystal growthCommonly used fluxing agents. In the invention, pbO and PbF are introduced 2 The composite fluxing agent can effectively reduce the viscosity and the volatility of a growth system and improve the stability of the growth system by utilizing the coupling synergistic effect of various raw materials:
(1) The crystal growth temperature is lower, and the range is between 660 and 700 ℃.
(2) The volatility of the growth system is small, so that the stability of the growth system can be improved, spontaneous crystallization is prevented from generating, and the success rate of crystal growth is improved.
(3) The viscosity of the growth system is lower, which is favorable for solute transport and heat transport, improves the crystal growth speed and reduces the generation of crystal defects.
(4) The crystallization area is wide, the cooling interval is large, a series of large-size and completely transparent CZB crystals without inclusion can be stably grown, and if a large-size crucible is used, the growth period is properly prolonged, and crystals with larger sizes can be obtained correspondingly.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
621.25 g Cs 2 CO 3 112.85 g ZnO, 578.76 g H 3 BO 3 232.13 g PbO and 255.01 g PbF 2 Mixing uniformly after grinding in agate grinding, adding phi 100X 100mm in batches 3 The platinum crucible is placed into a muffle furnace to be heated to 800-900 ℃ for melting, cooled after being fully melted, transferred into a three-section resistance wire heating crystal growth furnace, openings on two sides of the furnace top are sealed by covers made of heat insulation materials, a small hole for a seed rod to come in and go out is reserved at the position corresponding to the center of the crucible at the furnace top, the temperature is raised to 760 ℃ at the speed of 60 ℃/h to enable the raw materials to be fully melted, a platinum stirrer is used for stirring for 24 hours at the temperature, and the stirrer is lifted after the high-temperature solution is fully and uniformly mixed. The seed crystal is put in to try to determine the saturation point temperature to be 692 ℃, then the formal seed crystal is put in until the seed crystal contacts the surface of the solution, the crystal growth is carried out, the rotation speed is 15rpm, the temperature is reduced at the speed of 0.1-0.5 ℃/day, the crystal growth is finished after 20 days,the crystals were lifted off the liquid surface and cooled to room temperature at a rate of 5℃per hour to give a size of 20X 18X 15mm 3 Is a transparent single crystal of (a).
Example 2
576.04 g Cs 2 CO 3 143.88 g ZnO, 546.78 g H 3 BO 3 133.76 g PbO and 433.50 g PbF 2 Mixing uniformly after grinding in agate grinding, adding phi 100X 100mm in batches 3 The platinum crucible is placed into a muffle furnace to be heated to 800-900 ℃ for melting, cooled after being fully melted, transferred into a three-section resistance wire heating crystal growth furnace, openings on two sides of the furnace top are sealed by covers made of heat insulation materials, a small hole for a seed rod to come in and go out is reserved at the position corresponding to the center of the crucible at the furnace top, the temperature is raised to 750 ℃ at the speed of 80 ℃/h to enable the raw materials to be fully melted, a platinum stirrer is used for stirring for 36h at the temperature, and the stirrer is lifted after the high-temperature solution is fully and uniformly mixed. Feeding trial seed crystal to determine saturation point temperature to 683 deg.C, feeding formal seed crystal until seed crystal contacts with solution surface, performing crystal growth at rotation speed of 10rpm, cooling at speed of 0.1-0.5 deg.C/day, lifting crystal off liquid surface after 16 days of crystal growth, cooling to room temperature at speed of 10 deg.C/h to obtain crystal with size of 29×25× 20mm 3 Is a transparent single crystal of (a).
Example 3
622.41 g Cs 2 CO 3 124.37 g ZnO, 581.12 g H 3 BO 3 106.41 g PbO and 437.11 g PbF 2 Mixing uniformly after grinding in agate grinding, adding phi 100X 100mm in batches 3 The platinum crucible is placed into a muffle furnace to be heated to 800-900 ℃ for melting, cooled after being fully melted, transferred into a three-section resistance wire heating crystal growth furnace, openings on two sides of the furnace top are sealed by covers made of heat insulation materials, a small hole for a seed rod to come in and go out is reserved at the position corresponding to the center of the crucible at the furnace top, the temperature is raised to 740 ℃ at the speed of 80 ℃/h to enable the raw materials to be fully melted, a platinum stirrer is used for stirring for 48 hours at the temperature, and the stirrer is lifted after the high-temperature solution is fully and uniformly heated. Feeding trial seed crystals to determine the saturation point temperature to be 675 ℃, and then feeding formal seed crystalsUntil the seed crystal contacts the surface of the solution, crystal growth is carried out, the rotation speed is 12rpm, the temperature is reduced at the speed of 0.1-0.5 ℃/day, after 24 days of crystal growth is finished, the crystal is lifted off the liquid surface, the temperature is reduced to room temperature at the speed of 5 ℃/h, and the size of 32 multiplied by 28 multiplied by 24mm is obtained 3 Is a transparent single crystal of (a).
Example 4
604.29 g Cs 2 CO 3 120.75 g ZnO, 564.21 g H 3 BO 3 87.76 g PbO and 388.01 g PbF 2 Mixing uniformly after grinding in agate grinding, adding phi 100X 100mm in batches 3 The platinum crucible is placed into a muffle furnace to be heated to 800-900 ℃ for melting, cooled after being fully melted, transferred into a three-section resistance wire heating crystal growth furnace, openings on two sides of the furnace top are sealed by covers made of heat insulation materials, a small hole for a seed rod to come in and go out is reserved at the position corresponding to the center of the crucible at the furnace top, the temperature is raised to 760 ℃ at the speed of 100 ℃ to enable the raw materials to be fully melted, a platinum stirrer is used for stirring for 24 hours at the temperature, and the stirrer is put out after the high-temperature solution is fully and uniformly. Feeding trial seed crystals to determine the saturation point temperature to be 675 ℃, then feeding formal seed crystals until the seed crystals contact the surface of the solution, carrying out crystal growth, wherein the rotation speed of the seed crystals is 15rpm, reducing the temperature at the speed of 0.1-0.5 ℃/day, after the crystal growth is finished for 32 days, lifting the crystals off the liquid surface, and reducing the temperature to room temperature at the speed of 15 ℃/h to obtain the crystal with the size of 39 multiplied by 28 multiplied by 21mm 3 Is a transparent single crystal of (a).
Example 5
585.20 g Cs 2 CO 3 116.93 g ZnO, 546.39 g H 3 BO 3 94.43 g PbO and 528.48 g PbF 2 Mixing uniformly after grinding in agate grinding, adding phi 100X 100mm in batches 3 Placing the platinum crucible into a muffle furnace, heating to 800-900 ℃ to melt the material fully, cooling down, transferring to a three-section resistance wire heating crystal growth furnace, sealing the openings at two sides of the furnace top by using a cover made of heat insulation material, leaving a small hole for the seed rod to go in and out at the position corresponding to the center of the crucible at the furnace top, heating to 730 ℃ at a speed of 60 ℃/h to melt the raw material completely, and using a platinum stirrer in the furnaceStirring for 36h at the temperature, and taking out the stirrer after the high-temperature solution is sufficiently uniform. Feeding trial seed crystals to determine the saturation point temperature to be 673 ℃, then feeding formal seed crystals until the seed crystals contact the surface of the solution, carrying out crystal growth, wherein the rotation speed of the seed crystals is 10rpm, reducing the temperature at the speed of 0.1-0.5 ℃/day, after the completion of the crystal growth for 27 days, lifting the crystals off the liquid surface, and reducing the temperature to room temperature at the speed of 10 ℃/h to obtain the crystal with the size of 34 multiplied by 30 multiplied by 24mm 3 Is a transparent single crystal of (a).
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and substitutions will now occur to those skilled in the art without departing from the technical principles of the present invention, and these modifications and substitutions should also be considered to be within the scope of the present invention.
Claims (8)
1. Cs (cell lines) 3 Zn 6 B 9 O 21 A crystal growth flux characterized by using Cs 2 O-B 2 O 3 -PbO-PbF 2 The system is used as a fluxing agent;
Cs 2 O∶B 2 O 3 ∶PbO∶PbF 2 the molar ratio of (0.75-2.5) to (1.5-6) to (0-1.5) to (1-3).
2. A method of flux growth of CZB crystals as defined in claim 1, comprising the steps of:
(a) According to Cs 2 O∶ZnO∶B 2 O 3 ∶PbO∶PbF 2 The mol ratio is (1-3) to (1-2) to (2-7) to (0-2) to (1-3) and the materials are evenly mixed, and the temperature is raised to 800-900 ℃ for melting, thus preparing the crystal growth raw material;
(b) After the growth raw materials are completely melted, cooling to 720-770 ℃, stirring at constant temperature for 24-48 h, introducing seed crystals fixed on seed rods to the liquid level at 1-3 ℃ above the saturation point temperature, keeping the temperature for 30-60 min, and cooling to the saturation point temperature;
(c) Taking the saturation point temperature as the initial temperature of cooling, cooling at the speed of 0.1-0.5 ℃/day, and simultaneously rotating the crystal at the speed of 5-20 rpm to enable the crystal to grow;
(d) After the crystal grows to the required size, lifting the seed rod to separate the crystal from the liquid surface, and cooling to room temperature at the speed of 5-20 ℃/h to obtain the CZB crystal.
3. The growth method according to claim 1 or 2, wherein the compound Cs in step (a) 2 Cs for O 2 CO 3 Instead of this.
4. The growth method according to claim 1 or 2, wherein the compound B in the step (a) 2 O 3 By H 3 BO 3 Instead of this.
5. The growth method according to claim 2, wherein the step (a) uses a platinum crucible to hold the uniformly mixed raw materials.
6. A growth method according to claim 2, wherein the direction of the seed crystal in step (b) is an arbitrary direction.
7. The growth method according to claim 2, wherein the crystal rotation direction in the step (c) is unidirectional rotation or bidirectional rotation.
8. The growth method according to claim 2, wherein in the step (c), if the crystal is rotated in both directions, the crystal is rotated in a clockwise and counterclockwise direction alternately, and the crystal is rotated according to the following period: the rotation is sequentially accelerated, rotated at a constant speed, decelerated, and stopped in a first direction, and then sequentially accelerated, rotated at a constant speed, decelerated, and stopped in a second direction opposite to the first direction.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310541412.5A CN117535782A (en) | 2023-05-15 | 2023-05-15 | Cs (cell lines) 3 Zn 6 B 9 O 21 Crystal growth fluxing agent and crystal growth method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310541412.5A CN117535782A (en) | 2023-05-15 | 2023-05-15 | Cs (cell lines) 3 Zn 6 B 9 O 21 Crystal growth fluxing agent and crystal growth method |
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