CN108642558B - Annular ladder base and system for spontaneous nucleation growth of organic crystals - Google Patents
Annular ladder base and system for spontaneous nucleation growth of organic crystals Download PDFInfo
- Publication number
- CN108642558B CN108642558B CN201810702636.9A CN201810702636A CN108642558B CN 108642558 B CN108642558 B CN 108642558B CN 201810702636 A CN201810702636 A CN 201810702636A CN 108642558 B CN108642558 B CN 108642558B
- Authority
- CN
- China
- Prior art keywords
- crystal
- water bath
- growth
- cylinder
- annular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 202
- 238000010899 nucleation Methods 0.000 title claims abstract description 31
- 230000006911 nucleation Effects 0.000 title claims abstract description 31
- 230000002269 spontaneous effect Effects 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 41
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Substances CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000012774 insulation material Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 23
- 239000007864 aqueous solution Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 10
- 230000001276 controlling effect Effects 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 17
- 239000004698 Polyethylene Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910007709 ZnTe Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- UWWWTJSYTIOUPP-UHFFFAOYSA-N N,N-dimethyl-4-[2-(2-methylpyridin-4-yl)ethenyl]aniline 4-methylbenzenesulfonic acid Chemical compound C1(=CC=C(C=C1)S(=O)(=O)O)C.CN(C1=CC=C(C=CC2=CC(=NC=C2)C)C=C1)C UWWWTJSYTIOUPP-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000001268 conjugating effect Effects 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005338 frosted glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003911 water pollution Methods 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
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/08—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by cooling of the solution
-
- 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
- C30B29/54—Organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
An annular ladder base and a system for spontaneous nucleation growth of organic crystals are provided, wherein the annular ladder base is provided with an annular ladder groove, the annular ladder groove is formed by multi-stage annular L-shaped grooves in a ladder distribution mode, and the annular ladder groove can be arranged at the bottom of a crystal cultivating bottle in a covering mode and is used for spontaneous nucleation crystal nuclei to naturally fall into the annular L-shaped grooves; the organic crystal spontaneous nucleation growth system comprises a water bath circulation device, a temperature control device and a crystal growth device, wherein the water bath circulation device comprises a water bath circulation cylinder and a circulation pump, so that aqueous solution in the water bath circulation cylinder is circulated, the temperature control device is used for regulating and controlling the temperature of the aqueous solution in the water bath circulation cylinder, the crystal growth device comprises a crystal growing bottle and an annular stepped base arranged at the inner bottom of the crystal growing bottle, and the crystal growing bottle is arranged in the water bath circulation cylinder. The invention can effectively control the nucleation position of the crystal nucleus, effectively avoid the problem of crystal adhesion in the crystal nucleus growth process, maintain the temperature stability of the aqueous solution and improve the crystal yield.
Description
Technical Field
The invention belongs to the technical field of crystal growth equipment, and particularly relates to an annular ladder base and an annular ladder system for spontaneous nucleation growth of organic crystals.
Background
4- (4-dimethylaminostyryl) picoline p-toluenesulfonate (DAST) crystal is an organic photoelectric crystal material with high second order nonlinearity coefficient and low dielectric constant, the crystal consists of p-toluenesulfonic acid anions with negative charges and pyridine cations with positive charges, a pyridine group in a molecule is used as an electron acceptor, a sulfonic acid group is used as an electron donor, and a C=C double bond is used for conjugating two pi bonds, so that the crystal is of a typical D-pi-A structure. Under the action of an external optical field, the charge of the DAST crystal can be transferred from one end of the molecule to the other end, so that the nonlinear polarization rate of the DAST molecule is increased. Research shows that the larger the electron donor-acceptor strength is, the larger the intramolecular charge transfer degree is, and the corresponding microscopic second-order polarizability is also larger. DAST crystals are stacked in a macroscopical crystal mode with non-central symmetry, and belong to monoclinic system, biaxial crystal, space group Cc, point group M, Z=4 and lattice constantβ= 92.24 °. The DAST crystal has good second-order nonlinear coefficient (χ) due to the structural characteristics (2) =2020±220 pm/v@1318nm) and low dielectric constant (ε 1 =5.2±0.4), the crystal electro-optic coefficient at 820nm wavelength is γ 11 The frequency doubling effect of the crystal is 1000 times that of urea, which is 1-2 orders of magnitude larger than the corresponding value of ZnTe crystal, and is 400+ -150 pm/V. DAST crystal is an organic nonlinear crystal with excellent performance and is also an organic crystal material for generating THz radiation, and the generated energy is 6 times that of ZnTe crystal in the frequency range of 7-20THz, liTaO 3 185 times of the crystal is 42 times larger than high-quality GaAs and InP, and has wide development prospect in the field of terahertz radiation and detection based on DAST crystal difference frequency.
Currently, DAST crystal growth methods mainly include: spontaneous nucleation: the spontaneous nucleation method is to obtain the driving force required by crystal growth through slow cooling of the solution to carry out the crystal growth, the prepared high-purity DAST crystal raw material is put into a crystal growth bottle, then the temperature is controlled to be slowly reduced, and the crystal slowly crystallizes in the solution and gradually grows into a large crystal. The method has simple structure and easy operation, and can be used for mass production, but the nucleation position of the crystal nucleus can not be controlled in the crystal growth process, so that the crystals are easily adhered together in the crystal nucleus growth process to form mixed crystals, and the crystal yield is lower. (II) swash plate method: the inclined plate method is to add polytetrafluoroethylene inclined plate with V-shaped grooves into a crystal cultivating bottle on the basis of a spontaneous nucleation method, and the main purpose is to control the crystal growth posture, when crystal nuclei appear in solution, the crystal nuclei can slide into the inclined plate grooves and grow in a standing manner, so that the problem of crystal nucleus adhesion can be avoided to a certain extent, but the V-shaped groove inclined plate cannot be perfectly matched with a circular crystal cultivating bottle, so that the crystal carrying effective area for growing crystals is smaller, the number of the V-shaped grooves is limited, the number of the once-used grown crystals is small, and the production efficiency is low. Because the V-shaped groove inclined plate can not completely cover the bottom of the crystal growing bottle, not all crystal nuclei can slide down into the grooves in the actual crystal growing process, and part of crystal nuclei slide down to the bottom of the crystal growing bottle, and the crystal nuclei grow up and adhere to each other to form mixed crystals. And (III) seed crystal method: the DAST crystal is prepared by a seed crystal method, a seed crystal rod made of polytetrafluoroethylene is added into a crystal growing bottle, the top of the seed crystal is adhered with a seed crystal with better quality, DAST crystal solution is allowed to grow along the surface of the seed crystal in a directional manner, the problem of crystal adhesion is solved, and crystals with larger sizes are grown. However, the DAST crystal grown by the seed crystal method has strict temperature control and high requirement on environmental stability, and the seed crystal is easy to fall off in the crystal growth process. All three methods can prepare DAST crystals, but each method has advantages and disadvantages, and cannot be used for high-quality and large-size batch crystal growth. Meanwhile, most of the water bath heating devices of the three methods are side heating, so that uneven water temperature heating is easy to cause, temperature difference exists, water solution is static solution in a crystal growth cylinder, water pollution is easy to be caused after long-time placement, and certain influence is caused on the stability of the crystal growth environment.
Disclosure of Invention
Accordingly, it is a primary object of the present invention to provide an annular step base and system for spontaneous nucleation growth of organic crystals, in order to at least partially solve at least one of the above-mentioned technical problems.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
as one aspect of the invention, an annular step base for spontaneous nucleation growth of organic crystals is provided, which can be arranged at the inner bottom of a crystal growing bottle in a covering manner, and is provided with an annular step groove, wherein the annular step groove is formed by n-level annular L-shaped grooves in a step distribution, n is more than or equal to 2, the bottom surface of each level of annular L-shaped groove is parallel to the bottom of the crystal growing bottle, and the side surface of each level of annular L-shaped groove forms an angle of 90 degrees with the bottom of the crystal growing bottle.
The width of the bottom surface and the height of the side surface of the annular L-shaped groove at each stage are 5mm.
The annular step base is made of polytetrafluoroethylene materials.
As still another aspect of the present invention, there is provided an organic crystal spontaneous nucleation growth system comprising a water bath circulation device, a temperature control device and a crystal growth device, wherein:
the water bath circulation device comprises a water bath circulation cylinder and a circulation pump which are connected, and the circulation pump is used for circulating the water solution in the water bath circulation cylinder;
the temperature control device comprises a heating rod, a temperature sensor, a temperature controller and a temperature feedback processor, wherein:
the heating rod and the temperature sensor are respectively arranged in the water bath circulation cylinder;
the temperature feedback processor is connected to the temperature sensor and used for collecting and processing data of the temperature sensor;
the temperature controller is connected to the temperature feedback processor and used for controlling the heating rod according to the processing result of the temperature feedback processor;
the crystal growth device comprises a crystal growing bottle and the annular step base, wherein the annular step base is arranged at the inner bottom of the crystal growing bottle in a covering mode, and the crystal growing bottle is arranged in the water bath circulation cylinder.
The water bath circulation cylinder comprises a water bath growth cylinder and a water bath heating cylinder, wherein the water bath growth cylinder is internally provided with the crystal growing bottle and a temperature sensor; the water bath heating cylinder is internally provided with the heating rod and the temperature sensor, the water bath growth cylinder and the water bath heating cylinder are connected through a circulating pipeline, and the circulating pump is arranged on the circulating pipeline.
The water bath circulation cylinder further comprises a crystal growth furnace, the water bath growth cylinder is arranged in the crystal growth furnace, and a heat insulation material is arranged between the water bath growth cylinder and the crystal growth furnace.
Wherein the crystal growth furnace is made of stainless steel materials.
The circulating pipeline is made of glass materials, and the heat-insulating materials are coated on the circulating pipeline.
The side surface of the crystal growing bottle is cylindrical, and the side surface of the annular step base is also cylindrical.
Wherein, the crystal cultivating bottle and the water bath circulating cylinder are made of glass materials.
As a further aspect of the invention there is provided the use of an organic crystal spontaneous nucleation growth system as described above in the preparation of an organic nonlinear optical crystal, in particular in the preparation of a DAST crystal.
Based on the technical scheme, the invention has the beneficial effects that:
(1) On the basis of the existing organic crystal spontaneous nucleation growth device, an annular step base with annular step grooves is placed at the bottom of a crystal growing bottle, the annular step grooves are formed by the step distribution of n-level annular L-shaped grooves, the problem that the rectangular V-shaped groove sloping plate base is incompletely matched with a circular crystal growing bottle is effectively solved, the nucleation position of a crystal nucleus can be effectively controlled, and the problem of crystal adhesion in the crystal nucleus growth process is effectively avoided.
(2) Compared with the V-shaped groove sloping plate base, the number of the annular L-shaped grooves can be more, batch organic crystal growth can be carried out at one time, and the crystal productivity is improved.
(3) And a water bath circulation device is arranged, so that the temperature stability of the aqueous solution is kept, the crystal yield is improved, and high-quality organic crystals are obtained.
(4) The whole organic crystal spontaneous nucleation growth system has simple structure and easy operation, and can be widely applied to the field of organic nonlinear optical crystal preparation.
Drawings
FIG. 1 is a diagram showing the structure of a spontaneous nucleation growth system for organic crystals according to the present invention;
FIG. 2 is a schematic view of the annular step base structure of the present invention;
FIG. 3 is a schematic diagram of a spontaneous nucleation growth process of DAST crystals according to an embodiment of the present invention.
In the drawings, the reference numerals specifically have the following meanings:
1-a crystal growth furnace; 2-a thermocouple; 3-a water bath growth cylinder;
4-crystal cultivating bottle; 5-an annular step base; 6-a circulating pump;
7-a water outlet pipe; 8-heating the cylinder in a water bath; 9-an annular heating rod;
10-a temperature controller; 11 temperature feedback processor.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
The invention provides an annular ladder base and a system for spontaneous nucleation and growth of organic crystals, which can effectively control nucleation positions of crystal nuclei, avoid the problem of crystal adhesion in the process of crystal nucleus growth and improve crystal productivity; further, by the design of the water bath circulation device, the temperature of the aqueous solution is kept stable, high-quality and large-size crystals can be obtained, and the yield of the crystals is improved.
As shown in fig. 2, the annular step base for spontaneous nucleation and growth of organic crystals can be arranged at the inner bottom of a crystal raising bottle 4 in a covering manner, and is provided with an annular step groove, wherein the annular step groove is formed by n-level annular L-shaped grooves in a step distribution, n is more than or equal to 2, the bottom surface of each level of annular L-shaped groove is parallel to the bottom of the crystal raising bottle, and the side surface of each level of annular L-shaped groove forms an angle of 90 degrees with the bottom of the crystal raising bottle so as to be matched with the crystal raising bottle, and the vertical growth of seed crystals is facilitated. The width of the bottom surface and the height of the side surface of each stage of annular L-shaped groove can be designed according to practical requirements, for example, the width and the height of the side surface of each stage of annular L-shaped groove can be set to be 4-6 mm, and particularly, for example, the width and the height of the side surface of each stage of annular L-shaped groove are set to be 5mm; the number of the annular L-shaped grooves, namely the n value, can be adjusted according to the size of the crystal growing bottle, and compared with the V-shaped groove sloping plate base, the number of the annular L-shaped grooves can be more, so that batch organic crystal growth can be carried out at one time, and the crystal productivity is improved.
As shown in FIG. 1, the organic crystal spontaneous nucleation growth system of the invention specifically comprises a water bath circulation device, a temperature control device and a crystal growth device, so that the problem of crystal nucleus adhesion can be effectively avoided, and the stability of the crystal growth environment is improved. The respective apparatus components are described in detail below.
The water bath circulation device comprises a water bath growth cylinder 3, a water bath heating cylinder 8, a circulating pump 6, a water inlet pipe and a water outlet pipe 7, wherein the water bath growth cylinder 3 and the water bath heating cylinder 8 are connected through the water inlet pipe and the water outlet pipe 7, the circulating pump 6 is arranged on the water inlet pipe, the water inlet pipe and the water outlet pipe jointly form a circulating pipeline, the dynamic circulation regulation and control are carried out on the aqueous solution, and as a preferential choice, the circulating pipeline is coated with a heat insulation material, such as polyethylene heat insulation material.
The temperature control device comprises an annular heating rod 9, thermocouples 2, a temperature controller 10 and a temperature feedback processor 11, wherein the annular heating rod 9 is arranged in a water bath heating cylinder 8, the two thermocouples 2 are used as temperature sensors and are respectively arranged in the water bath growing cylinder 3 and the water bath heating cylinder 8, the temperature feedback processor 11 is connected to the two thermocouples 2 for collecting and processing temperature data, the temperature controller 10 is connected to the temperature feedback processor 11 and the heating rod 9, the heating rod 9 is controlled according to the processing result of the temperature feedback processor 11, the instant temperature of the aqueous solution is dynamically monitored, the temperature rising and lowering process of the aqueous solution is dynamically regulated through temperature feedback, for example, if the processing result of the temperature feedback processor 11 shows that the temperature data collected by the two thermocouples 2 is lower than a set value, the temperature controller 10 is used for controlling and improving the heating capacity of the heating rod to raise the temperature of the aqueous solution; otherwise, the temperature controller 10 controls the heating rod to reduce the heating capacity and the temperature of the aqueous solution.
The crystal growth device comprises a crystal growth furnace 1, a crystal growing bottle 4 and an annular stepped base 5, wherein a water bath growth cylinder 3 is arranged in the crystal growth furnace 1, and a heat insulation material, such as polyethylene heat insulation material, is arranged between the water bath growth cylinder 3 and the crystal growth furnace 1; the crystal raising bottle 4 is placed in the water bath growth jar 3; the annular step base 5 is arranged at the inner bottom of the crystal raising bottle 4 in a covering manner, and the structure of the annular step base 5 is as described above. As shown in fig. 3, the organic crystal solution spontaneously nucleates by slowly cooling, the crystal nucleus naturally drops on the annular ladder base, and the problem of crystal adhesion in the crystal nucleus growing process is effectively avoided by increasing the effective area of the crystal-loading inclined plate, and the high-quality organic crystal is finally obtained by natural crystallization and directional growth.
The crystal cultivating bottle 4 is cylindrical, so the annular ladder base is also cylindrical, and is matched with the bottom shape of the crystal cultivating bottle 4, thereby effectively solving the problem that the rectangular V-shaped groove sloping plate base is incompletely matched with the circular crystal cultivating bottle.
The following description of the technical scheme of the present invention further refers to a preferred embodiment of growing high quality DAST crystals by using an organic crystal spontaneous nucleation growth system with reference to the accompanying drawings.
Example 1
Before high-quality DAST crystal growth is realized, the high-purity DAST crystal raw material subjected to three purification methods of filtration, natural recrystallization and slow recrystallization is mixed with methanol solution according to the following ratio of 3.8:100 ml of high-purity DAST growth solution is prepared, the DAST growth solution is put into a crystal cultivating bottle 4 made of glass material, the top is sealed by a frosted glass cover and vacuum grease, and an annular stepped base 5 made of polytetrafluoroethylene is placed at the bottom of the crystal cultivating bottle. The crystal growing bottle 4 containing the high-purity DAST crystal growing solution is placed in the water bath growing cylinder 3 made of glass materials, the water bath growing cylinder 3 with the crystal growing bottle placed inside is placed in the crystal growing furnace 1 made of stainless steel materials, and polyethylene heat insulation materials are embedded in the inner side and the bottom of the furnace wall of the crystal growing furnace 1, so that the heat insulation effect is achieved, and the stability of the crystal growing environment is improved. The top of the water bath growth cylinder 3 is connected with a water bath heating cylinder 8 made of glass materials through a water inlet pipe, a circulating pump 6 is arranged on the water inlet pipe, the bottom of the water bath growth cylinder 3 is connected with the water bath heating cylinder 8 through a water outlet pipe 7, the water outlet pipe and the water inlet pipe are coated with polyethylene heat insulation materials, and an aqueous solution circulates between the water bath growth cylinder 3 and the water bath heating cylinder 8 through controlling the circulating pump 6. The water bath growth jar 3 and the water bath heating jar 8 are simultaneously and vertically provided with the thermocouple 2, the temperature of the aqueous solution is monitored immediately, the water bath growth jar is simultaneously connected with the temperature feedback device 11, the temperature is dynamically collected and regulated, the temperature feedback device 11 is connected with the temperature controller 10, and the temperature controller 10 is used for dynamically regulating and controlling the temperature of the water bath device by controlling the annular heating rod 9 arranged in the water bath growth jar 8.
In the embodiment, the inner diameter of the crystal growing furnace is 40cm, and the height is 60cm; the inner diameter of the water bath growth cylinder is 36cm, and the height is 50cm; the inner diameter of the crystal cultivating bottle is 12cm, and the height is 30cm; the width and the height of each stage of annular L-shaped groove of the annular ladder base are 5mm; the water bath heating cylinder has an inner diameter of 40cm and a height of 60cm.
After the DAST crystal growth solution is subjected to heat treatment through temperature regulation, the temperature of the DAST crystal growth solution is reduced to 1 ℃ below the saturation point temperature, then the DAST crystal growth solution is cooled at the cooling rate of 0.1 ℃/d until spontaneous nucleation crystal nuclei appear, the crystal nuclei naturally fall into the annular L-shaped groove, then the cooling program is regulated, the crystal is slowly crystallized, and the high-quality DAST single crystal with the crystal size of more than 12 multiplied by 1mm is obtained 3 The yield can be improved by about 20% compared with the V-shaped groove crystal.
The present embodiment has been described in detail with reference to the accompanying drawings. It should be noted that, in the drawings or the text of the specification, implementations not shown or described are all forms known to those of ordinary skill in the art, and not described in detail. Furthermore, the above definitions of the elements and methods are not limited to the specific structures, shapes or modes mentioned in the embodiments, and may be modified or replaced simply by one skilled in the art, for example: the integrated water bath circulation cylinder can be used for replacing a split water bath circulation cylinder consisting of the water bath circulation cylinder and the water bath heating cylinder, at the moment, the water inlet and outlet pipe of the circulation pump is connected to the water bath circulation cylinder, so that the water solution in the water bath circulation cylinder can be circulated, and meanwhile, the heating rod and the crystal raising bottle are arranged in the water bath circulation cylinder. It can be appreciated that the split-type water bath circulation cylinder is more stable in temperature control than the integrated water bath circulation cylinder.
In conclusion, the annular stepped base and the water bath circulation system are skillfully designed, the base is perfectly matched with the crystal growing bottle, the effective area of the crystal carrying inclined plate is increased, the nucleation position of the product nucleus is controlled, the temperature stability of the aqueous solution is improved, and the growth of high-quality DAST crystals is carried out. The growth device has the advantages of simple structure, easy operation and controllable nucleation position, can perform batch organic DAST crystal growth, and is widely applied to the field of organic nonlinear optical crystal preparation.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (7)
1. Use of an organic crystal spontaneous nucleation growth system in the preparation of DAST crystals, wherein the organic crystal spontaneous nucleation growth system comprises a water bath circulation device, a temperature control device and a crystal growth device, wherein:
the water bath circulation device comprises a water bath circulation cylinder and a circulation pump which are connected, and the circulation pump is used for circulating the water solution in the water bath circulation cylinder;
the temperature control device comprises a heating rod, a temperature sensor, a temperature controller and a temperature feedback processor, wherein:
the heating rod and the temperature sensor are respectively arranged in the water bath circulation cylinder;
the temperature feedback processor is connected to the temperature sensor and used for collecting and processing data of the temperature sensor;
the temperature controller is connected to the temperature feedback processor and the heating rod and is used for controlling the heating rod according to the processing result of the temperature feedback processor;
the crystal growth device comprises a crystal growth bottle and an annular step base for spontaneous nucleation growth of organic crystals, wherein the annular step base is arranged at the inner bottom of the crystal growth bottle in a covering manner, and the crystal growth bottle is arranged in the water bath circulation cylinder;
the annular step base is provided with an annular step groove which is integrally recessed downwards, the annular step groove is formed by the step distribution of n-level annular L-shaped grooves, n is more than or equal to 2, the bottom surface of each level of annular L-shaped groove is parallel to the bottom of the crystal growing bottle, the side surface of each level of annular L-shaped groove forms a 90-degree angle with the bottom of the crystal growing bottle, and the width of the bottom surface and the height of the side surface of each level of annular L-shaped groove are 4-6 mm.
2. The use of claim 1, wherein the annular stepped base is made of polytetrafluoroethylene material.
3. The use according to claim 1, wherein the water bath circulation cylinder comprises a water bath growth cylinder and a water bath heating cylinder which are connected through a circulation pipeline, wherein the crystal growing bottle is arranged in the water bath growth cylinder, the heating rod is arranged in the water bath heating cylinder, the number of the temperature sensors is two and respectively arranged in the water bath growth cylinder and the water bath heating cylinder, and the circulation pump is arranged on the circulation pipeline.
4. The use according to claim 3, wherein the crystal growing apparatus further comprises a crystal growing furnace, the water bath growth cylinder is disposed in the crystal growing furnace, and a thermal insulation material is disposed between the water bath growth cylinder and the crystal growing furnace.
5. The use according to claim 4, wherein the crystal growth furnace is made of stainless steel material.
6. Use according to claim 3, wherein the circulation duct is made of glass material, coated with a thermal insulation material.
7. Use according to any one of claims 1 to 6, characterized in that:
the crystal cultivating bottle is cylindrical, and the annular step base is cylindrical;
the crystal cultivating bottle and the water bath circulating cylinder are made of glass materials.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810504593 | 2018-05-23 | ||
| CN2018105045933 | 2018-05-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108642558A CN108642558A (en) | 2018-10-12 |
| CN108642558B true CN108642558B (en) | 2023-12-22 |
Family
ID=63750004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810702636.9A Active CN108642558B (en) | 2018-05-23 | 2018-06-29 | Annular ladder base and system for spontaneous nucleation growth of organic crystals |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108642558B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10212192A (en) * | 1997-01-27 | 1998-08-11 | Japan Energy Corp | Method for growing bulk crystal |
| US6200385B1 (en) * | 2000-03-20 | 2001-03-13 | Carl Francis Swinehart | Crucible for growing macrocrystals |
| JP2006027967A (en) * | 2004-07-16 | 2006-02-02 | Ricoh Co Ltd | Apparatus and method for manufacturing substrate with organic crystal |
| CN204918834U (en) * | 2015-09-09 | 2015-12-30 | 重庆文理学院 | Frame is cultivateed with cascaded single crystal in laboratory |
| CN105648519A (en) * | 2016-01-11 | 2016-06-08 | 青岛大学 | Square rectangular-pyramid-bottom DAST (diethylaminosulfurtrifluoride) crystal growth device |
| CN106002498A (en) * | 2016-08-01 | 2016-10-12 | 中国电子科技集团公司第四十六研究所 | Surface grinding process method for organic DAST crystals |
| CN106757346A (en) * | 2016-12-19 | 2017-05-31 | 山东大学 | A kind of method for protecting aqueous solution growth plane of crystal step |
| CN207307237U (en) * | 2017-08-02 | 2018-05-04 | 张源源 | A kind of chemical industry solution crystallizer |
| CN208632691U (en) * | 2018-05-23 | 2019-03-22 | 天津大学 | Ring ladder pedestal and system for organic crystal spontaneous nucleation growth |
-
2018
- 2018-06-29 CN CN201810702636.9A patent/CN108642558B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10212192A (en) * | 1997-01-27 | 1998-08-11 | Japan Energy Corp | Method for growing bulk crystal |
| US6200385B1 (en) * | 2000-03-20 | 2001-03-13 | Carl Francis Swinehart | Crucible for growing macrocrystals |
| JP2006027967A (en) * | 2004-07-16 | 2006-02-02 | Ricoh Co Ltd | Apparatus and method for manufacturing substrate with organic crystal |
| CN204918834U (en) * | 2015-09-09 | 2015-12-30 | 重庆文理学院 | Frame is cultivateed with cascaded single crystal in laboratory |
| CN105648519A (en) * | 2016-01-11 | 2016-06-08 | 青岛大学 | Square rectangular-pyramid-bottom DAST (diethylaminosulfurtrifluoride) crystal growth device |
| CN106002498A (en) * | 2016-08-01 | 2016-10-12 | 中国电子科技集团公司第四十六研究所 | Surface grinding process method for organic DAST crystals |
| CN106757346A (en) * | 2016-12-19 | 2017-05-31 | 山东大学 | A kind of method for protecting aqueous solution growth plane of crystal step |
| CN207307237U (en) * | 2017-08-02 | 2018-05-04 | 张源源 | A kind of chemical industry solution crystallizer |
| CN208632691U (en) * | 2018-05-23 | 2019-03-22 | 天津大学 | Ring ladder pedestal and system for organic crystal spontaneous nucleation growth |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108642558A (en) | 2018-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106381525B (en) | A kind of device of the reduction InP crystal twin based on VGF method | |
| CN107541776A (en) | A kind of growth apparatus and method of large scale gallium oxide single crystal | |
| CN202030861U (en) | Heating device for polycrystalline silicon crystal growing furnace | |
| Balamurugan et al. | Bulk growth of< 1 0 1> KDP crystal by Sankaranarayanan–Ramasamy method and its characterization | |
| CN103882517A (en) | Preparation method of polycrystalline silicon ingot | |
| CN103422162A (en) | Single crystal furnace thermal field structure for square sapphire generation | |
| CN109385662A (en) | The preparation method and class monocrystalline silicon piece of a kind of laying method of seed crystal, class monocrystal silicon | |
| CN104532353A (en) | Chromium-doped zinc selenide monocrystal Bridgman growth device and method | |
| CN108642558B (en) | Annular ladder base and system for spontaneous nucleation growth of organic crystals | |
| CN103422163A (en) | Device and method for growing sapphire single crystals | |
| Kesavan et al. | Numerical investigation of Directional Solidification process for improving multi-crystalline silicon ingot quality for photovoltaic applications | |
| Moskovskih et al. | The low thermal gradient CZ technique as a way of growing of dislocation-free germanium crystals | |
| CN206666673U (en) | A kind of multistation crucible declines stove | |
| CN203530480U (en) | Equipment for growing sapphire single crystals | |
| CN109137080A (en) | Method for growing selenium-gallium-barium crystal | |
| CN103255477A (en) | Molded sapphire crystal growth method and apparatus thereof | |
| CN201158722Y (en) | Thermal field device for gallium arsenide crystal growth | |
| CN208949444U (en) | A kind of growth apparatus of c to sapphire crystal | |
| CN208632691U (en) | Ring ladder pedestal and system for organic crystal spontaneous nucleation growth | |
| CN104120487A (en) | Growth method and growth equipment of platelike sapphire crystals | |
| CN209493651U (en) | Heater is used in a kind of processing of calcium fluoride mono crystal | |
| CN102618935B (en) | Annealing method for infrared nonlinear single crystal of multi-component compound containing easily volatile components | |
| CN102560678B (en) | A kind of method that stray crystal occurs in suppression 4-(4-dimethylaminostyryl) picoline tosilate crystal growing process | |
| US9163326B2 (en) | Crystal growth device | |
| CN109371462A (en) | Epitaxial growth organic metal halide perovskite monocrystal thin films preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TG01 | Patent term adjustment | ||
| TG01 | Patent term adjustment |