CN109930203B - BaGa4Se7Apparatus and method for synthesizing polycrystal - Google Patents
BaGa4Se7Apparatus and method for synthesizing polycrystal Download PDFInfo
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Abstract
The invention discloses a BaGa4Se7The polycrystalline synthesis device comprises a gas phase transmission quartz tube (1), a boron nitride boat (2) and a quartz small tube (3); the gas phase transmission quartz tube (1) is a quartz tube with one closed end, an annular groove (4) is formed by sinking the middle tube wall of the quartz tube into the quartz tube and divides the gas phase transmission quartz tube into two parts, wherein a transition region and a high-temperature region are sequentially arranged from the annular groove to the closed end, and a low-temperature region is arranged from the annular groove to the open end; the boron nitride boat is used for containing high-purity barium simple substances and gallium simple substances and is placed in a high-temperature area of the gas-phase transmission quartz tube (1); the quartz small tube is used for containing a selenium simple substance and is placed in a low-temperature area of the gas-phase transmission quartz tube (1), one end of the quartz small tube is closed, and a small hole (5) is formed in the closed end of the quartz small tube. The invention synthesizes BaGa through the gas phase transmission reaction of selenium steam4Se7Polycrystal, the yield is more than 99 percent, and 200g of high-purity polycrystal raw material can be synthesized in one time.
Description
Technical Field
The invention belongs to the field of preparation of ternary compound semiconductor materials, and particularly relates to BaGa4Se7Disclosed are a polycrystal synthesis device and a polycrystal synthesis method.
Background
The middle and far infrared laser has important application in the fields of environmental monitoring, medical operation, laser radar, space communication and the like. The non-linear frequency conversion method is a main method for generating middle and far infrared laser. The all-solid-state laser system using the infrared nonlinear optical crystal as a key core component has the advantages of high power, wide tuning, small volume, light weight, convenience in maintenance and the like. BaGa4Se7Is a novel infrared nonlinear optical crystal discovered in recent years, and the nonlinear optical effect of the novel infrared nonlinear optical crystal is large (d)1124pm/V), high laser damage threshold (557 MW/cm)2) High transmittance within the range of 1-14 μm, doubleLarge refraction (Δ n)>0.06) is the only crystal which can realize the output of the broadband laser with 2-14 mu m by using the common light source with 1-2 mu m for pumping at present, and has unique advantages.
Currently, BaGa is synthesized4Se7The method for preparing the polycrystalline raw material is mainly a single-temperature-zone direct synthesis method. The single temperature zone method only needs to set a constant temperature zone, and has simple process and convenient operation. The high-purity barium simple substance, the gallium simple substance and the selenium simple substance are taken as raw materials and directly generated by chemical combination reaction in a quartz tube at the high temperature of more than 1000 ℃. At the temperature, the vapor pressure of selenium is very high, the quartz tube is corroded by the added active metal barium, the reaction activity of liquid metal Ga is low, the quartz tube is frequently cracked and exploded, the amount of single synthesis is controlled within 50g, the reaction repeatability is poor, and the component deviation is easy to generate BaGa2Se4The impurity phase is deposited on the inner wall of the quartz tube, which causes the yield reduction and brings extra pollution in the processes of batching, packaging, transferring and the like. All of these constraints large-scale high-purity single-phase BaGa4Se7Obtaining polycrystalline raw materials which cannot satisfy BaGa4Se7Single crystal growth and device fabrication.
Disclosure of Invention
The invention aims to overcome the existing BaGa4Se7The defects in the polycrystalline synthesis technology are that the synthetic BaGa is provided4Se7The polycrystalline device and the synthesis method can avoid the cracking and explosion of a reaction container caused by the combined action of the corrosion of the active metal barium on a quartz tube at high temperature and the high vapor pressure of selenium, solve the problem of low reaction activity of liquid metal Ga and synthesize more than 200g of high-purity BaGa in one time4Se7Polycrystalline feedstock.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
BaGa4Se7The polycrystalline synthesis device comprises a gas phase transmission quartz tube 1, a boron nitride boat 2 and a quartz small tube 3;
the gas phase transmission quartz tube 1 is a quartz tube with one closed end, an annular groove 4 is formed by sinking the middle tube wall of the quartz tube into the tube, the annular groove divides the gas phase transmission quartz tube into two parts, wherein the annular groove is a transition region and a high temperature region from the closed end to the open end in sequence, and the annular groove is a low temperature region from the open end to the closed end;
the boron nitride boat is used for containing high-purity barium simple substances and gallium simple substances and is placed in a high-temperature area of the gas-phase transmission quartz tube 1;
the quartz small tube is used for containing a selenium simple substance and is placed in a low-temperature area of the gas phase transmission quartz tube (1), one end of the quartz small tube is closed, and a small hole 5 is formed in the closed end of the quartz small tube.
Preferably, the length of the gas phase transmission quartz tube is 950-1150mm, the inner diameter is 34-38mm, the wall thickness is 2-3mm, and the depth of the annular groove is 2-3 mm.
Preferably, the length of the quartz small tube is 220 mm and 280mm, the inner diameter is 28-30mm, the wall thickness is 2-3mm, and the diameter of the small hole is 2-3 mm.
The invention also provides BaGa based on the polycrystal synthesis device4Se7A method of polycrystalline synthesis, the method comprising the steps of:
1) taking high-purity (more than or equal to 6N) barium simple substance, gallium simple substance and selenium simple substance as raw materials, wherein the molar ratio of the ingredients is barium: gallium: 1 to 4:7 of selenium, and additionally adding 1 to 3 percent of selenium simple substance in excess;
2) cleaning the gas-phase transmission quartz tube, the boron nitride boat and the quartz tube, drying and removing the water vapor inside;
3) mixing the elementary barium and the elementary gallium in a molar ratio of 1:4, putting the mixture into a boron nitride boat, and putting the boron nitride boat at the closed end of a gas phase transmission quartz tube; weighing a selenium simple substance, putting the selenium simple substance into a quartz small tube, and putting the quartz small tube into the other end of the gas phase transmission quartz tube; the gas phase transmission quartz tube is pumped to high vacuum to 10-4Pa～10-6Pa, sealing with oxyhydrogen flame, and placing into a horizontal double-temperature-zone synthesis furnace, wherein a boron nitride boat containing barium and gallium is located in a high-temperature zone, a quartz tubule containing selenium is located in a low-temperature zone, and a transition zone is arranged between the two zones;
4) firstly, the temperature of the high temperature zone is raised to 900-950 ℃, and simultaneously the temperature of the low temperature zone is raised to 500-600 ℃, and the temperature is kept 60 ℃80 hours; then keeping the temperature of the high temperature zone unchanged, raising the temperature of the low temperature zone to be 30-50 ℃ higher than that of the high temperature zone, and preserving the heat for 10-30 hours; finally, both ends are cooled to room temperature at the speed of 1-10 ℃/hour to obtain BaGa4Se7And (4) polycrystallization.
According to the characteristics of physicochemical properties of raw materials of a simple substance barium, a simple substance gallium and a simple substance selenium, considering the adverse factors that active metal barium has a strong corrosion effect on a quartz tube at high temperature, the vapor pressure of the simple substance selenium increases along with a temperature index, liquid metal gallium has low reaction activity and the like, the invention designs and adopts a dual-temperature-zone gas phase transmission method for synthesis, so that the simple substance barium and the simple substance gallium firstly react in a high-temperature-zone boron nitride boat to form alloy, the simple substance selenium is contained in a low-temperature-zone quartz tubule, and the synthesis is completed by utilizing the transmission of selenium vapor. The molar ratio of the ingredients is barium: gallium: 1 to 4:7 of selenium, and additionally adding 1 to 3 percent of excessive selenium simple substance, wherein the synthesis process comprises the following steps:
1) soaking a gas phase transmission quartz tube and a boron nitride boat and a quartz tube for containing materials in aqua regia, then repeatedly cleaning the quartz tube and the boron nitride boat and the quartz tube with cleaning liquid until the quartz tube and the boron nitride boat and the quartz tube are clean, and drying the cleaned crucible; completely removing the water vapor inside the reactor;
the gas phase transmission quartz tube is a quartz tube with one closed end, the length is 1050mm, the inner diameter is 36mm, the wall thickness is 2mm, two sides of the middle part of the quartz tube are provided with annular grooves, and the depth of each annular groove is 2 mm; the boron nitride boat is used for containing high-purity barium and gallium; the quartz small tube is used for containing selenium, and the bottom of the closed end of the quartz small tube is provided with a small hole with the diameter of 2mm, so that the mixing of the elementary substances of barium, gallium and selenium in the charging and heating processes can be prevented, and the transmission of selenium steam in the reaction is allowed;
2) cleaning barium simple substance by dilute acid to remove an oxide layer on the surface, mixing the barium simple substance and the gallium simple substance according to the molar ratio of 1:4, putting the mixture into the boron nitride boat, and putting the boron nitride boat at the closed end of the gas phase transmission quartz tube; weighing a proper amount of selenium simple substance, putting the selenium simple substance into a quartz small tube, and putting the quartz small tube into the other end of the gas phase transmission quartz tube; the gas phase transmission quartz tube is vacuumized to 10-4Pa～10-6Pa, sealing with oxyhydrogen flame, putting into horizontal double-temperature-zone synthesis furnace, and placing the boat containing barium and gallium inThe high temperature area, the quartz tubule filled with selenium is positioned in the low temperature area, and a transition area is arranged between the high temperature area and the low temperature area;
3) firstly, raising the temperature of a high-temperature area to 900-950 ℃, simultaneously raising the temperature of a low-temperature area to 500-600 ℃, and preserving the heat for 60-80 hours; then keeping the temperature of the high-temperature area unchanged, raising the temperature of the low-temperature area to be 30-50 ℃ higher than that of the high-temperature area, and preserving the heat for 20 hours; finally, the temperature of both ends is reduced to room temperature at the speed of 5 ℃/hour to obtain BaGa4Se7And (4) polycrystallization.
BaGa synthesized by the invention4Se7Is a middle and far infrared nonlinear optical crystal with excellent performance. The invention aims to solve the problem of BaGa4Se7The problems of easy tube explosion, deviation of stoichiometry, poor repeatability and the like caused by factors such as corrosion of active metal barium to a quartz tube, low reaction activity of liquid metal gallium, large vapor pressure of non-metallic element selenium and the like in the synthesis of polycrystalline raw materials. The yield of the designed double-temperature-zone gas phase transmission synthesis method is more than 99 percent, and 200g of high-purity polycrystalline raw material can be synthesized once.
The invention has the following beneficial effects:
1. the simple substance of barium and the simple substance of gallium are reacted in the boron nitride boat in the high temperature area to form alloy, so that the corrosion of active metal barium to the quartz tube can be avoided, and the reaction activity of liquid metal gallium can be increased. The selenium simple substance is placed in a quartz small tube in a low-temperature area, and synthesis is completed by utilizing transmission of selenium steam, so that explosion of a reaction container caused by too large selenium steam pressure when the temperature is too high can be avoided.
2. The annular grooves are formed in two sides of the middle of the gas-phase transmission quartz tube, the depth of each annular groove is 2mm, the small quartz tube used for containing the elemental selenium is provided with a small hole with the diameter of 2mm at the bottom of the closed end, and the designs can prevent the elemental barium, the gallium and the elemental selenium from being mixed in the charging process and the temperature rising process and allow the transmission of selenium steam during reaction.
3. BaGa of the invention4Se7The polycrystalline raw material is synthesized by adopting a dual-temperature-zone method, the elementary barium and the elementary gallium are placed in a high-temperature zone at the initial stage of reaction, the elementary selenium is placed in a low-temperature zone, and selenium steam is transmitted from the low-temperature zone to the high-temperature zone through gas phase transmission to react and generateThe temperature of one end for selenium release is increased to be higher than that of one end for barium and gallium, and the selenium is conveyed to a high-temperature area completely to generate a product. The temperature trend is also kept in the cooling process, namely the temperature of one end for placing the selenium is always higher than that of one end for generating the product, so that the steam can be ensured to be totally condensed in a product area, the composition of the product meets the stoichiometric ratio, and the yield is improved.
Drawings
FIG. 1 is BaGa4Se7The structure schematic diagram of the synthesis device by the dual-temperature zone method;
FIG. 2 is a diagram of BaGa obtained4Se7A polycrystalline feedstock map;
FIG. 3 is the BaGa obtained4Se7Analyzing the purity of the polycrystalline raw material;
reference numerals: 1. a gas phase transmission quartz tube; 2. a boron nitride boat; 3. a quartz tubule; 4. an annular groove; 5. and (4) a small hole.
Detailed Description
The invention is described in further detail below with reference to the figures and the detailed description.
Example 1
As shown in FIG. 1, a BaGa4Se7The polycrystalline synthesis device comprises a gas phase transmission quartz tube 1, a boron nitride boat 2 and a quartz small tube 3;
the gas phase transmission quartz tube 1 is a quartz tube with one closed end, an annular groove 4 is formed by sinking the middle tube wall of the quartz tube into the tube, the annular groove divides the gas phase transmission quartz tube into two parts, wherein the annular groove is a transition region and a high temperature region from the closed end to the open end in sequence, and the annular groove is a low temperature region from the open end to the closed end;
the boron nitride boat is used for containing high-purity barium simple substances and gallium simple substances and is placed in a high-temperature area of the gas-phase transmission quartz tube 1;
the quartz small tube is used for containing a selenium simple substance and is placed in a low-temperature area of the gas phase transmission quartz tube (1), one end of the quartz small tube is closed, and a small hole 5 is formed in the closed end of the quartz small tube.
The length 1050mm of gaseous phase transmission quartz capsule, internal diameter 36mm, wall thickness 2mm, the degree of depth of annular groove is 2 mm.
The quartz small tube has the length of 250mm, the inner diameter of 30mm, the wall thickness of 2mm and the diameter of the small hole of 2 mm.
Example 2
In this embodiment, the synthesis apparatus described in embodiment 1 is adopted, the adopted raw materials barium (Ba), gallium (Ga), and selenium (Se) are all 6N grade, and when the raw materials are mixed, the molar ratio of each raw material is barium: gallium: selenium is 1:4:7, properly selenium-rich (excessive 1% -3%) according to the proportion: 35.082 g of barium, 71.252 g of gallium and 142.617 g of selenium. The synthesis process comprises the following steps:
1. cleaning and drying reaction vessel
Soaking and washing the inner walls of the gas phase transmission quartz tube, the boron nitride boat and the quartz tubule with tap water, then soaking in aqua regia for 24 hours, then washing to neutrality with tap water, placing in an ultrasonic cleaning tank for oscillation cleaning for 30 minutes, repeatedly washing with deionized water, then cleaning with high-purity alcohol, and placing in an oven at 100 ℃ for drying for later use.
2. Charging
Firstly, putting weighed barium and gallium into a boron nitride boat, putting the boat into the closed end of a gas phase transmission quartz tube, then putting weighed selenium into a small quartz tube, putting the small quartz tube into the other end of the gas phase transmission quartz tube, enabling the small quartz tube and the small boron nitride boat to be separated by 400mm, and vacuumizing to 10 mm after the loading is finished-4Pa～10-6And Pa, sealing the gas-phase transmission quartz tube by using oxyhydrogen flame.
3. Synthesis of
Placing the gas phase transmission quartz tube filled with raw materials and sealed into a horizontally placed double-temperature-zone reaction furnace in a way that a boron nitride boat is positioned in a high-temperature zone and a quartz small tube is positioned in a low-temperature zone, as shown in figure 1; raising the temperature of a high-temperature area of the synthesis furnace to 900 ℃ at a speed of 2 ℃/min, raising the temperature of a low-temperature area to 600 ℃ at a speed of 1 ℃/min, conveying selenium from a low-temperature section end to a high-temperature end in a gas phase form to react with the barium-gallium alloy, and preserving the heat for 80 hours; the temperature of the low temperature end of the tube furnace is increased to 950 ℃ at the rate of 2 ℃/minute, and the boron nitride boat is maintainedKeeping the temperature of the two ends unchanged, and cooling the two ends to the room temperature at the speed of 5 ℃/min after keeping the temperature for 20 hours. 248g of BaGa are obtained4Se7Polycrystalline raw material, yield greater than 99%.
BaGa synthesized in this example4Se7The high purity, single phase polycrystalline material is shown in FIG. 2, and the XRD analysis is shown in FIG. 3. As can be seen from fig. 3, the product purity is greater than 99%.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. BaGa4Se7The polycrystalline synthesis device is characterized by comprising a gas phase transmission quartz tube (1), a boron nitride boat (2) and a quartz small tube (3);
the gas phase transmission quartz tube (1) is a quartz tube with one closed end, an annular groove (4) is formed by sinking the middle tube wall of the quartz tube into the quartz tube and divides the gas phase transmission quartz tube into two parts, wherein a transition region and a high-temperature region are sequentially arranged from the annular groove to the closed end, and a low-temperature region is arranged from the annular groove to the open end;
the boron nitride boat is used for containing high-purity barium simple substances and gallium simple substances and is placed in a high-temperature area of the gas-phase transmission quartz tube (1);
the quartz small tube is used for containing a selenium simple substance and is placed in a low-temperature area of the gas phase transmission quartz tube (1), one end of the quartz small tube is closed, and a small hole (5) is formed in the closed end of the quartz small tube;
the closed end of the small quartz tube is arranged at the position of the annular groove, and the open end of the small quartz tube is arranged at the open end of the gas phase transmission quartz tube.
2. BaGa according to claim 14Se7Is characterized in thatThe length of the gas phase transmission quartz tube is 950-1150mm, the inner diameter is 34-38mm, the wall thickness is 2-3mm, and the depth of the annular groove is 2-3 mm.
3. BaGa according to claim 14Se7The polycrystalline synthesis device is characterized in that the length of the quartz tubule is 220-280mm, the inner diameter is 28-30mm, the wall thickness is 2-3mm, and the diameter of the small hole is 2-3 mm.
4. BaGa based on the polycrystal synthesis apparatus according to any one of claims 1 to 34Se7A method of polycrystalline synthesis, the method comprising the steps of:
1) taking a barium simple substance, a gallium simple substance and a selenium simple substance with the purity of more than or equal to 6N as raw materials, wherein the molar ratio of the ingredients is barium: gallium: 1 to 4:7 of selenium, and additionally adding 1 to 3 percent of selenium simple substance in excess;
2) cleaning the gas-phase transmission quartz tube, the boron nitride boat and the quartz tube, drying and removing the water vapor inside;
3) mixing the elementary barium and the elementary gallium in a molar ratio of 1:4, putting the mixture into a boron nitride boat, and putting the boron nitride boat at the closed end of a gas phase transmission quartz tube; weighing a selenium simple substance, putting the selenium simple substance into a quartz small tube, and putting the quartz small tube into the other end of the gas phase transmission quartz tube; the gas phase transmission quartz tube is pumped to high vacuum to 10-4Pa～10-6Pa, sealing with oxyhydrogen flame, and placing into a horizontal double-temperature-zone synthesis furnace, wherein a boron nitride boat containing barium and gallium is located in a high-temperature zone, a quartz tubule containing selenium is located in a low-temperature zone, and a transition zone is arranged between the two zones;
4) firstly, raising the temperature of a high-temperature area to 900-950 ℃, simultaneously raising the temperature of a low-temperature area to 500-600 ℃, and preserving heat for 60-80 hours; then keeping the temperature of the high-temperature area unchanged, raising the temperature of the low-temperature area to be 30-50 ℃ higher than that of the high-temperature area, and preserving the heat for 10-30 hours; finally, both ends are cooled to room temperature at the speed of 1-10 ℃/hour to obtain BaGa4Se7And (4) polycrystallization.
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| CN111041559B (en) * | 2019-12-13 | 2021-07-20 | 四川大学 | Synthetic container and synthetic method of quaternary sulfur lithium compound polycrystal |
| CN116240633A (en) * | 2020-12-14 | 2023-06-09 | 天津理工大学 | Compound orthorhombic selenium gallium barium and orthorhombic selenium gallium barium nonlinear optical crystal, preparation method and application thereof |
| CN116240634A (en) * | 2020-12-14 | 2023-06-09 | 天津理工大学 | Compound monoclinic phase selenium gallium barium and monoclinic phase selenium gallium barium nonlinear optical crystal, preparation method and application thereof |
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