A high-throughput synthesis device and method for infrared nonlinear optical crystal materials

Abstract

The present invention discloses a high-throughput synthesis device and method for infrared nonlinear optical crystal materials, the device comprises a base and a stainless steel pressure-resistant shell mounted on the base, the stainless steel pressure-resistant shell has a hollow water-cooling cavity, the left and right ends of the stainless steel pressure-resistant shell are sealed by high-pressure flanges, and the high-pressure flanges have an air-filling valve; a silicon carbide furnace is installed inside the stainless steel pressure-resistant shell, and a plurality of quartz crucibles are placed in the cavity of the silicon carbide furnace; a heating device for heating the silicon carbide furnace is installed between the stainless steel pressure-resistant shell and the silicon carbide furnace; a heat insulation component is installed between the heating device and the stainless steel pressure-resistant shell; and a pressure protection device is installed on the stainless steel pressure-resistant shell. The device provided by the present invention can realize high-throughput synthesis of high-purity, high-dose infrared nonlinear crystal materials, and significantly improve production efficiency.

Description

Technical Field

[0001] The invention belongs to the field of preparation of infrared nonlinear optical crystals, and in particular relates to a high-throughput synthesis device and method for infrared nonlinear optical crystal materials. Background Art

[0002] Through laser frequency conversion technology, infrared nonlinear optical crystals can down-convert near-infrared lasers to achieve medium- and long-wave infrared laser tuning output; lasers in this band are of great application value in many fields such as infrared countermeasures, infrared remote sensing, laser medical treatment, and toxic gas monitoring. The preparation of high-quality crystals and the exploration of new infrared nonlinear optical materials are of great research significance and practical value.

[0003] Infrared nonlinear optical crystal materials are mainly P and S compound semiconductors with low phonon energy. Such materials are easy to decompose, volatilize and oxidize at high temperatures, and have very high requirements for the preparation environment and process. Since the saturated vapor pressure of P and S elements is very high under high temperature conditions, P and S compounds are prone to problems such as component deviation and crucible explosion. The single temperature zone method has a small single synthesis dose, low purity, and the safety of the synthesis cannot be guaranteed.

[0004] A Chinese patent (application number: CN201410640085.X) discloses a loading device and a loading method for dual-temperature zone synthesis of multi-component polycrystalline materials. The device reacts with metal raw materials in the high-temperature zone by low-temperature gas phase transport of P and S single substances to solve the problem of quartz crucible explosion. Since the reaction synthesis space is very large, the component deviation is serious, the purity of the raw materials is reduced, and it is difficult to achieve a single large dose of raw materials and the simultaneous synthesis of multiple P and S compounds.

[0005] A Chinese patent (application number: CN202010310756.1) discloses a high-temperature and high-pressure synthesis method and equipment for sulfur and phosphide optoelectronic functional crystals. A high-temperature and high-pressure nickel-based furnace equipment is used to balance the pressure difference between the inside and outside of the crucible by applying external pressure, thereby reducing the synthesis space, solving the problem of crucible explosion, and improving the purity of synthetic raw materials and the single-tube synthesis dosage. However, this method uses a nickel-based alloy tube as a pressure container, and the working temperature of the nickel-based furnace tube is only below 1150°C, so it is impossible to synthesize raw materials with higher melting points; moreover, the inner diameter of the furnace tube is greatly limited, and it is impossible to achieve high-throughput synthesis of P and S compounds.

[0006] At present, the existing single-temperature zone method, double-temperature zone horizontal vapor transport method and high-temperature and high-pressure method for synthesizing infrared nonlinear optical crystal materials have problems such as small single synthesis dose, low purity and efficiency, and cannot achieve high-throughput preparation of infrared nonlinear optical crystal materials. Summary of the invention

[0007] In view of the deficiencies in the prior art, the object of the present invention is to provide an apparatus and method for high-throughput synthesis of infrared nonlinear optical crystal materials, so as to achieve high-throughput synthesis of high-purity, large-dose infrared nonlinear crystal materials.

[0008] To achieve the above object, the technical solution adopted by the present invention is:

[0009] The first object of the present invention is to provide a high-throughput synthesis device for infrared nonlinear optical crystal materials, comprising a base and a stainless steel pressure-resistant shell mounted on the base, the stainless steel pressure-resistant shell having a hollow water-cooling cavity, the stainless steel pressure-resistant shell having a water inlet and a water outlet connected to the water-cooling cavity, cooling water is circulated into the water-cooling cavity through the water inlet and the water outlet to achieve water-cooling circulation cooling of the stainless steel pressure-resistant shell; the left and right ends of the stainless steel pressure-resistant shell are sealed by a high-pressure flange, and the high-pressure flange has an inflation valve; a silicon carbide furnace chamber is installed inside the stainless steel pressure-resistant shell, and a plurality of quartz crucibles are placed in the cavity of the silicon carbide furnace chamber; a heating device for heating the silicon carbide furnace chamber is installed between the stainless steel pressure-resistant shell and the silicon carbide furnace chamber; an insulation component is installed between the heating device and the stainless steel pressure-resistant shell; and a pressure protection device is installed on the stainless steel pressure-resistant shell.

[0010] In a further solution, the heating device is a dual-temperature zone heating device, including a heating assembly symmetrically arranged on the left and right; the heating assembly includes a heating element, a thermocouple and a high-voltage electrode lead; the heating element is installed on the outer peripheral side of the silicon carbide furnace, and the heating element is connected to the outside of the stainless steel pressure-resistant shell through the high-voltage electrode lead. Furthermore, the heating element is a resistance wire, tungsten wire, molybdenum wire, silicon carbon rod, silicon molybdenum rod or graphite. It should be noted that in addition to the dual-temperature zone heating device, single temperature zone and multi-temperature zone can be used to realize the heating function of this equipment.

[0011] In a further embodiment, the thermal insulation assembly includes a metal reflective screen for high temperature thermal insulation and a ceramic fiber thermal insulation module for low temperature thermal insulation.

[0012] In a further solution, the pressure protection device includes a pressure instrument, a pressure transmitter and a solenoid valve installed on a stainless steel pressure-resistant shell. The solenoid valve is used for pressure relief; the pressure transmitter is connected to the pressure instrument to measure and display the pressure value in the cavity; the solenoid valve, pressure transmitter and pressure instrument cooperate to achieve overpressure protection in the cavity.

[0013] In a further solution, a knife-edge flange is installed on the high-pressure flange, and the role of the knife-edge flange is mainly to facilitate loading.

[0014] The second object of the present invention is to provide a method for high-throughput synthesis of infrared nonlinear optical crystal materials, which is accomplished by using the high-throughput synthesis equipment for infrared nonlinear optical crystal materials described in the first object, and comprises the following steps:

[0015] Step 1: Weigh the required raw materials according to the chemical measurement and add the raw materials into a quartz crucible;

[0016] Step 2: Evacuate the loaded quartz crucible to 10 -3 After Pa, the crucible is sealed by hydrogen-oxygen flame; steps 1 and 2 are repeated to seal multiple loaded quartz crucibles;

[0017] Step 3: Place multiple sealed quartz crucibles into the silicon carbide furnace chamber, install the knife-edge flange, and ensure that the silicon carbide furnace chamber is airtight;

[0018] Step 4: Use a vacuum pump to evacuate the silicon carbide furnace, fill it with an appropriate amount of protective gas, and then evacuate again; repeat the gas washing three times and fill it with 4MPa protective gas; preferably, the protective gas is nitrogen or inert gas;

[0019] Step 5: Use a heating device to heat the silicon carbide furnace, and after the reaction raw materials react in the quartz crucible to generate the target product, cool down to room temperature.

[0020] Step 6: Reduce the pressure in the silicon carbide furnace to atmospheric pressure and take out the synthetic material.

[0021] The beneficial effects of the present invention are:

[0022] The equipment provided by the present invention adopts a stainless steel pressure-resistant shell with a water-cooling chamber as a pressure container, and its internal effective space is significantly increased, which can improve the operating temperature and pressure of the equipment while ensuring safety; and because the internal effective space is large, multiple crucibles can be placed at the same time for batch production, thereby improving production efficiency; the equipment provided by the present invention can balance the vapor pressure of P and S elements in the crucible by applying pressure outside the sealed quartz crucible, prevent the crucible from exploding, and has good safety. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 A schematic diagram of the structure of a high-throughput synthesis device for infrared nonlinear optical crystal materials provided by the present invention;

[0024] Figure numerals: 1-base, 2-stainless steel pressure-resistant shell, 3-water-cooling chamber, 4-water inlet, 5-water outlet, 6-high-pressure flange, 7-charging valve, 8-knife-edge flange, 9-silicon carbide furnace, 10-quartz crucible, 11-heating element, 12-thermocouple, 13-high-voltage electrode lead, 14-metal reflection screen, 15-ceramic fiber insulation module, 16-pressure instrument, 17-pressure transmitter, 18-solenoid valve. DETAILED DESCRIPTION

[0025] The present invention is further described below in conjunction with embodiments and drawings so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.

[0026] It should be noted that the terms "connection", "installation" and the like in the present invention all indicate that two interconnected parts are fixed together, generally by welding, screws and the like. The orientations or positional relationships indicated by the terms "left", "right", "top", "bottom", "inside", "outside", "upper", "lower", etc. are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation of the present invention. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0027] Example 1

[0028] refer to Figure 1 A high-throughput synthesis device for infrared nonlinear optical crystal materials comprises a base 1 and a stainless steel pressure-resistant shell 2 mounted on the base 1, the stainless steel pressure-resistant shell 2 having a hollow water-cooling chamber 3, the stainless steel pressure-resistant shell 2 having a water inlet 4 and a water outlet 5 connected to the water-cooling chamber 3, cooling water is circulated into the water-cooling chamber 3 through the water inlet 4 and the water outlet 5 to achieve water-cooling circulation cooling of the stainless steel pressure-resistant shell 2; the left and right ends of the stainless steel pressure-resistant shell 2 are sealed by a high-pressure flange 6, the high-pressure flange 6 has an air charging valve 7, and a knife-edge flange 8 is also installed on the high-pressure flange 6 for the convenience of loading. A silicon carbide furnace 9 is installed inside the stainless steel pressure-resistant shell 2, and a plurality of quartz crucibles 10 are placed in the cavity of the silicon carbide furnace 9; a heating device for heating the silicon carbide furnace 9 is installed between the stainless steel pressure-resistant shell 2 and the silicon carbide furnace 9, and preferably, the heating device is a dual-temperature zone heating device, including a heating assembly symmetrically arranged on the left and right; the heating assembly includes a heating element 11, a thermocouple 12 and a high-voltage electrode lead 13; the heating element 11 is installed on the outer peripheral side of the silicon carbide furnace 9, and the heating element 11 is connected to the outside of the stainless steel pressure-resistant shell 2 through the high-voltage electrode lead 13. Further, the heating element 11 is a resistance wire, a tungsten wire, a molybdenum wire, a silicon carbon rod, a silicon molybdenum rod or graphite. A heat insulation assembly is installed between the heating device and the stainless steel pressure-resistant shell 2, and the heat insulation assembly includes a metal reflective screen 14 for high-temperature heat insulation and a ceramic fiber insulation module 15 for low-temperature heat insulation. A pressure protection device is installed on the stainless steel pressure-resistant shell 2, and the pressure protection device includes a pressure instrument 16, a pressure transmitter 17 and a solenoid valve 18 installed on the stainless steel pressure-resistant shell 2. The solenoid valve is used for pressure relief; the pressure transmitter is connected to the pressure instrument to measure and display the pressure value in the cavity; the solenoid valve, pressure transmitter and pressure instrument cooperate to achieve overpressure protection in the cavity.

[0029] Example 2

[0030] A high-throughput synthesis method of infrared nonlinear optical crystal materials (taking CdSe as an example) comprises the following steps:

[0031] Step 1: Weigh a total of about 500 grams of high-purity Cd and Se according to the stoichiometric ratio, and place them in a quartz crucible with a carbon film coated on the inner wall; the crucible dimensions are 40 mm in inner diameter, 3 mm in wall thickness, and 260 mm in length.

[0032] Step 2: Evacuate the loaded quartz crucible to 10 -3 After Pa, it was sealed by hydrogen-oxygen flame; steps one and two were repeated to package 10 tubes of 400 grams of CdSe synthetic raw materials.

[0033] Step 3: Place the sealed 10-tube quartz crucible into the silicon carbide furnace, install the knife-edge flange, and tighten the screws to ensure good air tightness in the furnace.

[0034] Step 4: Use a vacuum pump to evacuate the furnace and fill it with an appropriate amount of high-purity argon gas, then evacuate again. Repeat the gas washing three times and fill it with 0.5MPa high-purity argon gas.

[0035] Step 5: Heat the heating element to 1290℃ at a rate of 10℃ / min; when the pressure in the furnace reaches 1MPa, the solenoid valve automatically releases the pressure; keep the temperature constant for 900min to fully melt the synthetic raw materials. Finally, reduce the heating elements to room temperature at the same time at a rate of 30℃ / min.

[0036] Step 6: Open the pressure relief valve to reduce the pressure in the furnace to atmospheric pressure; open the flange cover and take out the synthetic material.

[0037] Example 3

[0038] A high-throughput synthesis method for a variety of infrared nonlinear optical crystal materials comprises the following steps:

[0039] Step 1: According to the stoichiometric ratio, weigh and load the raw materials required for synthesizing ZnGeP2, AgGaS2, AgGaGeS4, AgGaSe2, BaGa4Se7, BaGa4Se7, BaGa2GeSe6, BaGa4S7, BaGa2GeS6, Ba2Ga2GeSe8, and Sn2P2S6 into ten quartz crucibles respectively. The crucible dimensions are 30 mm in inner diameter, 3 mm in wall thickness, and 260 mm in length.

[0040] Step 2: Evacuate the loaded quartz crucible to 10 -3 After Pa, it is sealed with hydrogen-oxygen flame.

[0041] Step 3: Place the sealed 10-tube quartz crucible into the silicon carbide furnace, install the knife-edge flange, and tighten the screws to ensure good air tightness in the furnace.

[0042] Step 4: Use a vacuum pump to evacuate the furnace and fill it with an appropriate amount of high-purity argon gas, then evacuate again. Repeat the gas washing three times and fill it with 4MPa high-purity argon gas.

[0043] Step 5: Heat the heating element to 1070℃ at a rate of 10℃ / min; when the pressure in the furnace reaches 8MPa, the solenoid valve automatically releases the pressure; keep the temperature constant for 900min to fully melt the synthetic raw materials. Finally, reduce the heating elements to room temperature at the same time at a rate of 30℃ / min.

[0044] Step 6: Open the pressure relief valve to reduce the pressure in the furnace to atmospheric pressure; open the flange cover and take out the synthetic material.

[0045] Obviously, the described embodiments are only some embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Claims

1. A high-throughput synthesis device for infrared nonlinear optical crystal materials, characterized in that: It comprises a base and a stainless steel pressure-resistant shell mounted on the base, the stainless steel pressure-resistant shell having a hollow water-cooling cavity, the stainless steel pressure-resistant shell having a water inlet and a water outlet connected to the water-cooling cavity; the left and right ends of the stainless steel pressure-resistant shell are sealed by high-pressure flanges, the high-pressure flanges having a charging valve; a silicon carbide furnace chamber is installed inside the stainless steel pressure-resistant shell, and a plurality of quartz crucibles are placed in the cavity of the silicon carbide furnace chamber; a heating device for heating the silicon carbide furnace chamber is installed between the stainless steel pressure-resistant shell and the silicon carbide furnace chamber; a heat insulation component is installed between the heating device and the stainless steel pressure-resistant shell; a pressure protection device is installed on the stainless steel pressure-resistant shell; The heating device is a dual-temperature zone heating device, including a heating assembly symmetrically arranged on the left and right; the heating assembly includes a heating element, a thermocouple and a high-voltage electrode lead; the heating element is installed on the outer peripheral side of the silicon carbide furnace, and the heating element is connected to the outside of the stainless steel pressure-resistant shell through the high-voltage electrode lead; The pressure protection device comprises a pressure instrument, a pressure transmitter and a solenoid valve which are installed on a stainless steel pressure-resistant shell.

2. The high-throughput synthesis device for infrared nonlinear optical crystal materials according to claim 1, characterized in that: The heating element is a resistance wire, a tungsten wire, a molybdenum wire, a silicon carbon rod, a silicon molybdenum rod or graphite.

3. The high-throughput synthesis device for infrared nonlinear optical crystal materials according to claim 1, characterized in that: The heat insulation component comprises a metal reflective screen for high-temperature heat insulation and a ceramic fiber heat insulation module for low-temperature heat insulation.

4. The high-throughput synthesis device for infrared nonlinear optical crystal materials according to any one of claims 1 to 3, characterized in that: A knife-edge flange is mounted on the high-pressure flange.

5. A high-throughput synthesis method for infrared nonlinear optical crystal materials, characterized in that: The method is completed by using the high-throughput synthesis device for infrared nonlinear optical crystal materials as described in any one of claims 1 to 4, and comprises the following steps: Step 1: Weigh the required raw materials according to the chemical measurement and add the raw materials into a quartz crucible; Step 2: Evacuate the loaded quartz crucible to 10 -3 After Pa, the crucible is sealed by hydrogen-oxygen flame; steps 1 and 2 are repeated to seal multiple loaded quartz crucibles; Step 3: Place multiple sealed quartz crucibles into the silicon carbide furnace chamber, install the knife-edge flange, and ensure that the silicon carbide furnace chamber is airtight; Step 4: Use a vacuum pump to evacuate the silicon carbide furnace chamber, fill it with an appropriate amount of protective gas, and then evacuate it again; repeat the gas washing three times and fill it with protective gas; Step 5: Heat the silicon carbide furnace with a heating device, and after the reaction raw materials react in the quartz crucible to generate the target product, cool down to room temperature; Step 6: Reduce the pressure in the silicon carbide furnace to atmospheric pressure and take out the synthetic material.

6. The high-throughput synthesis method of infrared nonlinear optical crystal materials according to claim 5, characterized in that: The protective gas is nitrogen or an inert gas.

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