CN111809235A - Method for preparing cadmium telluride or cadmium zinc telluride polycrystal material - Google Patents
Method for preparing cadmium telluride or cadmium zinc telluride polycrystal material Download PDFInfo
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- CN111809235A CN111809235A CN202010932454.8A CN202010932454A CN111809235A CN 111809235 A CN111809235 A CN 111809235A CN 202010932454 A CN202010932454 A CN 202010932454A CN 111809235 A CN111809235 A CN 111809235A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
- C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- 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
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
- C30B29/48—AIIBVI compounds wherein A is Zn, Cd or Hg, and B is S, Se or Te
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Abstract
The invention relates to a preparation method of cadmium telluride or cadmium zinc telluride polycrystal material, which is characterized by comprising the following preparation process flows: 1) cleaning and drying a first crucible, a second crucible which can be loaded into the first crucible and a first cover which covers the first crucible; wherein the first crucible has an annular groove along the outer peripheral wall; the top of the first cover is closed, the bottom of the first cover is opened, and the side wall of the first cover can be inserted into the annular groove; the bottom of the second crucible is provided with a hole; 2) weighing simple substance tellurium and simple substance cadmium according to the ratio of cadmium telluride; or weighing the simple substance tellurium, the simple substance cadmium and the simple substance zinc according to the mixture ratio of the tellurium, the zinc and the cadmium. The preparation method of the invention adopts the liquid seal technology to prevent the volatilization loss of the cadmium vapor, and the first crucible can be repeatedly used, thereby reducing the cost; by reducing the instantaneous reaction quantity of tellurium and cadmium, the intensity of the chemical combination reaction of tellurium and cadmium is reduced, the pressure-resistant requirement on synthesis equipment is reduced, and the equipment cost is reduced.
Description
Technical Field
The invention belongs to the field of preparation of crystal materials, and particularly relates to a synthetic cadmium telluride (CdTe) or cadmium zinc telluride (Cd) 1- x Zn x Te) polycrystalline material.
Background
The cadmium telluride and cadmium zinc telluride crystals are the first choice substrate materials for preparing the mercury cadmium telluride infrared focal plane detector, are ideal semiconductor materials for preparing the nuclear radiation detector, and have wide application in the aspects of preparing thin film solar cells, infrared windows, optical modulators and the like.
In the preparation process of cadmium telluride and cadmium zinc telluride materials, the successful synthesis of the cadmium telluride and cadmium zinc telluride polycrystalline materials by adopting the tellurium simple substance, the cadmium simple substance and the zinc simple substance is a key technology, a quartz crucible vacuum sintering sealing method is usually adopted, after the synthesis is finished, the quartz crucible needs to be broken to take out crystal ingots inside, one quartz crucible needs to be lost every time of synthesis, and the cost is high; on the other hand, the tellurium simple substance and the cadmium simple substance can have violent reaction when being combined, and when the single synthesis amount is slightly large, the problem of explosion of a quartz crucible container can often occur, so that the materials are oxidized and scrapped, and equipment is damaged, thereby causing great economic loss.
Aiming at the difficulty of the existing synthesis process of cadmium telluride and cadmium zinc telluride polycrystal materials, the invention provides a method for synthesizing the cadmium telluride and cadmium zinc telluride polycrystal materials in an industrialized large-scale and low-cost manner.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing cadmium telluride or cadmium zinc telluride polycrystal material, which can enable a tellurium simple substance and a cadmium simple substance to slowly react and is suitable for industrial large-scale and low-cost preparation.
The technical scheme adopted by the invention is as follows: a method for preparing cadmium telluride or cadmium zinc telluride polycrystal materials is characterized by comprising the following preparation process flows:
1) cleaning and drying a first crucible, a second crucible which can be loaded into the first crucible and a first cover which covers the first crucible; wherein the first crucible has an annular groove along the outer peripheral wall; the top of the first cover is closed, the bottom of the first cover is opened, and the side wall of the first cover can be inserted into the annular groove; the bottom of the second crucible is provided with a hole;
2) weighing simple substance tellurium and simple substance cadmium according to the ratio of cadmium telluride; or weighing simple substance tellurium, simple substance cadmium and simple substance zinc according to the ratio of tellurium, zinc and cadmium;
3) loading elemental tellurium or elemental tellurium and elemental zinc into a first crucible, and loading elemental cadmium into a second crucible; placing the second crucible into the first crucible, and ensuring that the bottom of the second crucible is positioned above the melt of all the elemental materials in the first crucible after the elemental materials react to generate cadmium telluride or cadmium zinc telluride;
4) inserting the side wall of the first cover into the annular groove, covering the first crucible, and putting a liquid sealant into the annular groove;
5) placing the first crucible into a third crucible in a synthesis furnace; the synthesis furnace is provided with a plurality of temperature zones;
6) vacuumizing the interior of the synthesis furnace, and then filling inert gas with certain pressure;
7) operating a connecting rod arranged on the synthesis furnace to cover the second cover on the third crucible; the second cover is matched with the third crucible in a mechanical sealing way;
8) firstly, heating the liquid sealant to melt the liquid sealant; heating the lower part of the first crucible to melt the material in the first crucible; finally, heating the second crucible to melt the elemental cadmium in the second crucible;
9) the molten elemental cadmium in the second crucible is slowly dripped into the first crucible through a hole at the bottom of the second crucible and reacts with the melt in the first crucible to generate cadmium telluride or cadmium zinc telluride; continuously heating the lower part of the first crucible while cadmium telluride or cadmium zinc telluride is generated, and keeping a new material in the first crucible in a molten state;
10) after all the elemental materials react to generate cadmium telluride or cadmium zinc telluride, keeping the temperature, and then slowly cooling to the room temperature;
11) exhausting the inert gas in the synthesis furnace, operating the connecting rod to lift the second cover, and taking the first crucible out of the third crucible; and dissolving the liquid sealant in the annular groove, opening the first cover, and taking the cadmium telluride or cadmium zinc telluride crystal ingot out of the first crucible.
Preferably, the inner diameter of the hole at the bottom of the second crucible is 1-10 mm. The pore inner diameter is too large, the flow rate of the molten cadmium is too high, the reaction of tellurium and cadmium is violent, and the risk of tube cracking exists; the inner diameter of the hole is too small, so that molten cadmium is not easy to drip out, and the preparation efficiency is reduced, therefore, the inner diameter of the hole at the bottom of the second crucible is controlled to be 1-10 mm.
Preferably, diboron trioxide is used as the liquid sealant in the step 4). At high temperature, the boron trioxide melts into liquid with higher viscosity, and the cadmium vapor in the second crucible can be prevented from leaking.
Preferably, in the step 7), the second cover and the third crucible are mechanically sealed through thread fit; or the second cover realizes mechanical sealing with the third crucible through the outer conical surface.
Preferably, the degree of vacuum in the first crucible after the vacuum pumping in the step 6) is less than 1 KPa; the used inert gas is nitrogen or argon with the purity of more than 5N, after vacuum pumping, the inert gas with the pressure of 0.08-0.12 MPa is filled, then vacuum pumping and inert gas filling are carried out for 2-10 times, and finally the pressure of the inert gas filling is 0.2-10 MPa. The pressure of the filled gas is too low, so that the loss of cadmium components caused by the volatilization of cadmium vapor can not be effectively prevented; the pressure of the filled gas is too high, the pressure resistance requirement on equipment is increased, and the equipment cost is higher. Therefore, the pressure of the inert gas is controlled to be 0.2-10 MPa.
Preferably, in the step 8), the temperature of the liquid sealant is increased to 450-700 ℃ so that the liquid sealant is melted firstly; then, the temperature of the lower part of the first crucible is increased to 450-990 ℃, so that the material in the first crucible is melted; and finally, raising the temperature of the second crucible to 321-765 ℃ to completely melt the elemental cadmium.
Preferably, in the step 8), a temperature gradient is axially arranged at the lower part of the first crucible, the temperature gradient is 0.5-15 ℃/cm, and the temperature is gradually reduced from the bottom to the top, so that the material in the first crucible is gradually melted from the bottom to the top. The cadmium melt is dripped through the hole at the bottom of the second crucible and then reacts with the melt in the first crucible to generate cadmium telluride or cadmium zinc telluride, heat is generated in the combination reaction process, and the heat can be used for heating unmelted materials at the upper part of the first crucible, so that energy is saved; the temperature gradient of the lower temperature zone of the first crucible is kept to continue rising, so that the material in the first crucible is gradually melted from the bottom of the crucible to the top.
Preferably, in the step 9), while cadmium telluride or cadmium zinc telluride is generated, the temperature of the lower portion of the first crucible is raised to 1092 to 1300 ℃ at a rate of 100 to 500 ℃/h, and the new material in the first crucible is kept in a molten state. The temperature rise rate is too fast, the temperature of the melt is overheated, and energy is wasted; the temperature rise rate is too low to melt the newly generated cadmium telluride or cadmium zinc telluride. Therefore, the temperature rise rate is controlled to be 100-500 ℃/h, and the temperature is controlled to be 1092-1300 ℃ after cadmium telluride or cadmium zinc telluride is generated through all reactions.
Preferably, in the step 10), after all the elemental materials react to generate cadmium telluride or cadmium zinc telluride, the temperature is kept for 0.1 to 100 hours.
Preferably, the first crucible has an upper inner diameter larger than a lower inner diameter of the first crucible, and the second crucible has an outer diameter smaller than the upper inner diameter of the first crucible and larger than the lower inner diameter of the first crucible. The design can fix the second crucible in the first crucible.
Preferably, the first crucible, the second crucible and the first cover are made of quartz, and the third crucible and the second cover are made of graphite; and in the step 1), the first crucible and the second crucible are cleaned and dried, and then are placed into a carbon plating furnace, and a layer of carbon film is plated on the inner surfaces of the first crucible and the second crucible.
The invention has the advantages that: the liquid seal technology is adopted to prevent the volatilization loss of cadmium vapor, the first crucible does not need to be sintered and sealed, and the first crucible can be repeatedly used, so that the cost is reduced; by slowly dripping the cadmium melt into the tellurium melt or the tellurium-zinc melt, the instantaneous reaction quantity of tellurium and cadmium is reduced, the intensity of the chemical combination reaction of tellurium and cadmium is reduced, the pressure-resistant requirement on synthesis equipment is lowered, and the equipment cost is lowered. Therefore, the invention can meet the requirement of preparing cadmium telluride or cadmium zinc telluride polycrystal materials in an industrialized large scale at low cost.
Drawings
Fig. 1 is a schematic structural diagram of an embodiment of the present invention.
Wherein, 1 is a first crucible, 2 is a second crucible, 3 is a first cover, 4 is a thin tube, 11 is an annular groove, 5 is a third crucible, 6 is a second cover, 7 is a vertical pressure synthesis furnace with multiple temperature zones, 71 is a temperature zone I, 72 is a temperature zone II, 73 is a temperature zone III, 74 is a temperature zone IV, 75 is a connecting rod, 8 is cooling water, and 9 is a heat insulation material.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1: 100kg of CdTe crystal material is prepared.
The preparation process flow comprises the following steps:
1) the first crucible 1, the second crucible 2 and the first cover 3 are made of quartz; the first crucible 1 has a ring-shaped groove 11 along the outer peripheral wall, and the lower part of the first crucible 1 has an inner diameter of 300mm, the upper part has an inner diameter of 322mm, the wall thickness is 5mm, and the length is 800 mm; the width of the annular groove 11 is 18mm, the wall thickness is 2.5mm, and the depth is 15 mm; the upper part of the second crucible 2 is cylindrical, the lower part of the second crucible is funnel-shaped, the outer diameter of the cylindrical tube is 320mm, the length of the cylindrical tube is 180mm, the total length of the funnel and the thin tube 4 is 100mm, the wall thickness of the funnel and the thin tube 4 is 3mm, and the inner diameter of the tail end of the thin tube 4 is 8 mm; the top of the first cover 3 is closed, the bottom of the first cover is open, the side wall of the first cover can be inserted into the annular groove 11, and the inner diameter of the first cover 3 is 336mm, the wall thickness of the first cover is 2.5mm, and the length of the first cover is 30 mm; the first crucible 1, the second crucible 2 and the first cover 3 are cleaned and dried. The first crucible 1 and the second crucible 2 are put into a carbon plating furnace, and a carbon film is plated on the inner surfaces of the first crucible 1 and the second crucible 2.
2) The weights of the simple substance tellurium and the simple substance cadmium are respectively 53164.23 g and 46835.77 g by an electronic balance.
3) The method comprises the steps of putting elemental tellurium into a first crucible 1, putting elemental cadmium into a second crucible 2, putting the second crucible 2 into the first crucible 1, and ensuring that the tail end of a thin tube 4 is positioned above a melt generated after all elemental materials react in the first crucible 1 to generate cadmium telluride.
4) The side wall of the first cover 3 is inserted into the annular groove 11, the first crucible 1 is closed, and the boron trioxide liquid sealant is put into the annular groove 11.
5) The first crucible 1 is placed in a third crucible 5 in a synthesis furnace 7, the third crucible 5 is made of graphite in the embodiment, and the synthesis furnace 7 has a four-temperature zone.
6) Vacuumizing the interior of the synthetic furnace 7, filling nitrogen with the purity of 5N and the pressure of about 0.12MPa after the vacuum degree reaches below 1KPa, vacuumizing and inflating for 10 times, and finally filling the nitrogen with the pressure of 10 MPa.
7) The connecting rod 75 arranged on the synthesis furnace 7 is operated to cover the second cover 6 on the third crucible 5; in this embodiment, the second lid 6 is made of graphite, and the second lid 6 and the third crucible 5 are in sealing fit by adopting a threaded structure.
8) The liquid sealant is heated to 600 ℃ by controlling the temperature zone four 74, so that the liquid sealant is melted firstly; forming a gradient temperature field at the lower part of the first crucible 1 by controlling a first temperature zone 71 and a second temperature zone 72, gradually reducing the temperature from the bottom to the top, raising the temperature at the bottom of the first crucible 1 to 460 ℃, and setting the temperature gradient to be 15 ℃/cm, so that the tellurium simple substance at the bottom of the first crucible 1 is firstly melted; and finally, the temperature of the second crucible 2 is raised to 700 ℃ by controlling a third temperature zone 73, so that the cadmium simple substance in the second crucible is melted.
9) The molten elemental cadmium in the second crucible 2 is slowly dropped into the first crucible 1 through the thin tube 4 to react with the tellurium melt to generate cadmium telluride; while cadmium telluride is generated, the lower part of the first crucible 1 is heated to 1100 ℃ at the speed of 100 ℃/h by controlling the first temperature zone 71 and the second temperature zone 72, so that the tellurium simple substance in the first crucible 1 is gradually melted from the bottom of the crucible upwards, and the new material in the first crucible 1 is kept in a molten state.
10) After the cadmium melt in the second crucible 2 is completely dripped into the tellurium melt at the lower part, the chemical combination reaction is completed, the temperature at the lower part of the first crucible 1 is kept at 1100 ℃, the temperature is kept for 10 hours, and then the temperature is slowly reduced to the room temperature.
11) The nitrogen gas in the synthesis furnace 7 is discharged, the connecting rod 75 is operated to lift the second cover 6, and the first crucible 1 is taken out from the third crucible 5; the liquid sealant in the annular groove 11 is dissolved, the first cover 3 is opened, and the cadmium telluride ingot is taken out from the first crucible 1.
Example 2: preparation of 6kg Cd0.96Zn0.04And (5) Te crystal material.
The preparation process flow comprises the following steps:
1) the first crucible 1, the second crucible 2 and the first cover 3 are made of quartz; the first crucible 1 has a ring-shaped groove 11 along the outer peripheral wall, and the lower part of the first crucible 1 has an inner diameter of 90mm, the upper part has an inner diameter of 112mm, the wall thickness is 3mm, and the length is 800 mm; the width of the annular groove 11 is 18mm, the wall thickness is 2.5mm, and the depth is 15 mm; the upper part of the second crucible 2 is cylindrical, the lower part of the second crucible is funnel-shaped, the outer diameter of the cylindrical tube is 110mm, the length of the cylindrical tube is 150mm, the total length of the funnel and the thin tube 4 is 100mm, the wall thickness of the funnel and the thin tube 4 is 2.5mm, and the inner diameter of the tail end of the thin tube 4 is 1 mm; the top of the first cover 3 is closed, the bottom of the first cover is open, the side wall of the first cover can be inserted into the annular groove 11, and the inner diameter of the first cover 3 is 336mm, the wall thickness of the first cover is 2.5mm, and the length of the first cover is 30 mm; cleaning and drying the first crucible 1, the second crucible 2 and the first cover 3; the first crucible 1 and the second crucible 2 are put into a carbon plating furnace, and a carbon film is plated on the inner surfaces of the first crucible 1 and the second crucible 2.
2) The weights of the simple substance tellurium, the simple substance cadmium and the simple substance zinc are respectively 3215.0484 g, 2719.0481 g and 65.9035 g by an electronic balance.
3) The method comprises the steps of putting elemental tellurium and elemental zinc into a first crucible 1, putting elemental cadmium into a second crucible 2, putting the second crucible 2 into the first crucible 1, and ensuring that the tail end of a thin tube 4 is positioned above a melt of all elemental materials in the first crucible 1 after the elemental materials react to generate cadmium zinc telluride.
4) The side wall of the first cover 3 is inserted into the annular groove 11, the first crucible 1 is closed, and the boron trioxide liquid sealant is put into the annular groove 11.
5) The first crucible 1 is placed in a third crucible 5 in a synthesis furnace 7, the third crucible 5 is made of graphite in the embodiment, and the synthesis furnace 7 has a four-temperature zone.
6) Vacuumizing the interior of the synthetic furnace 7, filling argon with the purity of 6N at about 0.08MPa after the vacuum degree reaches below 10Pa, vacuumizing and filling the argon for 3 times, and finally filling the argon at the pressure of 0.2 MPa.
7) The connecting rod 75 arranged on the synthesis furnace 7 is operated to cover the second cover 6 on the third crucible 5; in this embodiment, the second lid 6 is made of graphite, and the second lid 6 and the third crucible 5 are in sealing fit by adopting a threaded structure.
8) The liquid sealant is heated to 500 ℃ by controlling the temperature zone four 74, so that the liquid sealant is melted firstly; forming a gradient temperature field at the lower part of the first crucible 1 by controlling a first temperature zone 71 and a second temperature zone 72, gradually reducing the temperature from the bottom to the top, increasing the temperature at the bottom of the first crucible 1 to 480 ℃, and setting the temperature gradient to be 1 ℃/cm so as to firstly melt the tellurium simple substance and the zinc simple substance at the bottom of the first crucible 1; and finally, the temperature of the second crucible 2 is raised to 340 ℃ by controlling a third temperature zone 73, so that the cadmium simple substance in the second crucible is melted.
9) After the cadmium simple substance in the second crucible 2 is melted, the cadmium simple substance is slowly dripped into the first crucible 1 through the thin tube 4 to react with the tellurium-zinc melt to generate tellurium-zinc-cadmium; when cadmium zinc telluride is generated, the lower part of the first crucible 1 is heated to 1120 ℃ at the speed of 100 ℃/h by controlling the first temperature zone 71 and the second temperature zone 72, so that the tellurium simple substance and the zinc simple substance in the first crucible 1 are gradually melted from the bottom of the crucible upwards, and the new material in the first crucible 1 is kept in a molten state.
10) After the cadmium melt in the second crucible 2 is completely dripped into the tellurium-zinc melt at the lower part, the chemical combination reaction is completed, the temperature at the lower part of the first crucible 1 is kept at 1120 ℃, the temperature is kept for 2h, and then the temperature is slowly reduced to the room temperature.
11) Argon gas in the synthesis furnace 7 is discharged, the connecting rod 75 is operated to lift the second cover 6, and the first crucible 1 is taken out from the third crucible 5; the liquid sealant in the annular groove 11 is dissolved, the first lid 3 is opened, and the cadmium zinc telluride ingot is taken out from the first crucible 1.
Example 3: preparation of 6kg Cd0.9Zn0.1And (5) Te crystal material.
The preparation process flow comprises the following steps:
1) the first crucible 1, the second crucible 2 and the first cover 3 are made of quartz; the first crucible 1 has a ring groove 11 along the outer peripheral wall, the lower inner diameter of the first crucible 1 is 90mm, the upper inner diameter is 112mm, the wall thickness is 3mm, the length is 800mm, and the width of the ring groove 11 is 18mm, the wall thickness is 2.5mm, and the depth is 15 mm. The upper part of the second crucible 2 is cylindrical, the lower part of the second crucible is funnel-shaped, the outer diameter of the cylindrical tube is 110mm, the length of the cylindrical tube is 150mm, the total length of the funnel and the thin tube 4 is 100mm, the wall thickness of the funnel and the thin tube 4 is 2.5mm, and the inner diameter of the tail end of the thin tube 4 is 2 mm; the top of the first cover 3 is closed, the bottom of the first cover is open, the side wall of the first cover can be inserted into the annular groove 11, and the inner diameter of the first cover 3 is 336mm, the wall thickness of the first cover is 2.5mm, and the length of the first cover is 30 mm; cleaning and drying the first crucible 1, the second crucible 2 and the first cover 3; the first crucible 1 and the second crucible 2 are put into a carbon plating furnace, and a carbon film is plated on the inner surfaces of the first crucible 1 and the second crucible 2.
2) The weights of the simple substance tellurium, the simple substance cadmium and the simple substance zinc are respectively 3253.5956 g, 2579.6704 g and 166.7340 g by an electronic balance.
3) The method comprises the steps of putting elemental tellurium and elemental zinc into a first crucible 1, putting elemental cadmium into a second crucible 2, putting the second crucible 2 into the first crucible 1, and ensuring that the tail end of a thin tube 4 is positioned above a melt of all elemental materials in the first crucible 1 after the elemental materials react to generate cadmium zinc telluride.
4) The side wall of the first cover 3 is inserted into the annular groove 11, the first crucible 1 is closed, and the boron trioxide liquid sealant is put into the annular groove 11.
5) The first crucible 1 is placed in a third crucible 5 in a synthesis furnace 7, the third crucible 5 is made of graphite in the embodiment, and the synthesis furnace 7 has a four-temperature zone.
6) Vacuumizing the interior of the synthetic furnace 7, filling nitrogen with the purity of 6N at about 0.1MPa after the vacuum degree reaches below 10Pa, vacuumizing and inflating for 3 times, and finally filling the nitrogen at the pressure of 6 MPa.
7) The connecting rod 75 arranged on the synthesis furnace 7 is operated to cover the second cover 6 on the third crucible 5; in this embodiment, the second lid 6 is made of graphite, and the second lid 6 is hermetically fitted with the third crucible 5 by adopting a conical structure.
8) The liquid sealant is heated to 470 ℃ by controlling the temperature zone four 74, so that the liquid sealant is melted firstly; then, the temperature of the lower part of the first crucible 1 is raised to 490 ℃ by controlling a first temperature zone 71 and a second temperature zone 72 so as to completely melt the tellurium simple substance and the zinc simple substance; finally, the temperature of the second crucible 2 is raised to 340 ℃ by controlling a temperature zone three 73, so that the cadmium simple substance is completely melted.
9) After the cadmium simple substance in the second crucible 2 is melted, the cadmium simple substance is slowly dripped into the first crucible 1 through the thin tube 4 to react with the tellurium-zinc melt to generate tellurium-zinc-cadmium; while cadmium zinc telluride is generated, the lower part of the first crucible 1 is heated to 1125 ℃ at the speed of 500 ℃/h by controlling the first temperature zone 71 and the second temperature zone 72, and a new material in the first crucible 1 is kept in a molten state.
10) After the cadmium melt in the second crucible 2 is completely dripped into the tellurium-zinc melt at the lower part, the chemical combination reaction is finished, the heat is continuously preserved for 3 hours at the temperature of 1125 ℃, and then the temperature is slowly reduced to the room temperature.
11) The nitrogen gas in the synthesis furnace 7 is discharged, the connecting rod 75 is operated to lift the second cover 6, and the first crucible 1 is taken out from the third crucible 5; the liquid sealant in the annular groove 11 is dissolved, the first lid 3 is opened, and the cadmium zinc telluride ingot is taken out from the first crucible 1.
Example 4: preparation of 6kg Cd0.8Zn0.2And (5) Te crystal material.
The preparation process flow comprises the following steps:
1) the first crucible 1 and the first cover 3 are made of quartz, and the second crucible 2 is made of boron nitride; the first crucible 1 is provided with a ring groove 11 along the peripheral wall, the inner diameter of the lower part of the first crucible 1 is 90mm, the inner diameter of the upper part of the first crucible is 112mm, the wall thickness is 3mm, the length is 800mm, the width of the ring groove 11 is 18mm, the wall thickness is 2.5mm, and the depth is 15 mm; the upper part of the second crucible 2 is cylindrical, the lower part of the second crucible is funnel-shaped, the outer diameter of the cylindrical tube is 110mm, the length of the cylindrical tube is 150mm, the total length of the funnel and the thin tube 4 is 100mm, the wall thickness is 1mm, and the inner diameter of the tail end of the thin tube 4 is 2 mm; the top of the first cover 3 is closed, the bottom of the first cover is open, the side wall of the first cover can be inserted into the annular groove 11, and the inner diameter of the first cover 3 is 336mm, the wall thickness of the first cover is 2.5mm, and the length of the first cover is 30 mm; cleaning and drying the first crucible 1, the second crucible 2 and the first cover 3; the first crucible 1 is placed in a carbon plating furnace, and a carbon film is plated on the inner surface of the first crucible 1.
2) The weights of the simple substance tellurium, the simple substance cadmium and the simple substance zinc are respectively 3319.9368 g, 2339.7957 g and 340.2675 g by an electronic balance.
3) The method comprises the steps of putting elemental tellurium and elemental zinc into a first crucible 1, putting elemental cadmium into a second crucible 2, putting the second crucible 2 into the first crucible 1, and ensuring that the tail end of a thin tube 4 is positioned above a melt of all elemental materials in the first crucible 1 after the elemental materials react to generate cadmium zinc telluride.
4) The side wall of the first cover 3 is inserted into the annular groove 11, the first crucible 1 is closed, and the boron trioxide liquid sealant is put into the annular groove 11.
5) Placing the first crucible 1 into a third crucible 5 in a synthesis furnace 7; in this embodiment, the third crucible 5 is made of graphite, and the synthesis furnace 7 has four temperature zones.
6) Vacuumizing the interior of the synthetic furnace 7, filling argon with the purity of 7N at about 0.1MPa after the vacuum degree reaches below 10Pa, vacuumizing and filling the argon for 3 times, and finally filling the argon at the pressure of 5 MPa.
7) The connecting rod 75 arranged on the synthesis furnace 7 is operated to cover the second cover 6 on the third crucible 5; in this embodiment, the second lid 6 is made of graphite, and the second lid 6 is hermetically fitted with the third crucible 5 by adopting a conical structure.
8) The liquid sealing agent is heated to 450 ℃ by controlling the temperature zone four 74, so that the liquid sealing agent is melted firstly; then, the temperature of the lower part of the first crucible 1 is raised to 900 ℃ by controlling a first temperature zone 71 and a second temperature zone 72 so as to completely melt the tellurium simple substance and the zinc simple substance; finally, the temperature of the second crucible 2 is raised to 350 ℃ by controlling a temperature zone three 73, so that the cadmium simple substance is completely melted.
9) After the cadmium simple substance in the second crucible 2 is melted, the cadmium simple substance is slowly dripped into the first crucible 1 through the thin tube 4 to react with the tellurium-zinc melt to generate tellurium-zinc-cadmium; when the cadmium zinc telluride is generated, the lower part of the first crucible 1 is heated to 1135 ℃ at the speed of 200 ℃/h by controlling the first temperature zone 71 and the second temperature zone 72, and a new material in the first crucible 1 is kept in a molten state.
10) After the cadmium melt in the second crucible 2 is completely dripped into the tellurium-zinc melt at the lower part, the chemical combination reaction is finished, the temperature is kept for 4 hours at 1135 ℃, and then the temperature is slowly reduced to the room temperature.
11) Argon gas in the synthesis furnace 7 is discharged, the connecting rod 75 is operated to lift the second cover 6, and the first crucible 1 is taken out from the third crucible 5; the liquid sealant in the annular groove 11 is dissolved, the first lid 3 is opened, and the cadmium zinc telluride ingot is taken out from the first crucible 1.
Claims (10)
1. A method for preparing cadmium telluride or cadmium zinc telluride polycrystal materials is characterized by comprising the following preparation process flows:
1) cleaning and drying a first crucible, a second crucible which can be loaded into the first crucible and a first cover which covers the first crucible; wherein the first crucible has an annular groove along the outer peripheral wall; the top of the first cover is closed, the bottom of the first cover is opened, and the side wall of the first cover can be inserted into the annular groove; the bottom of the second crucible is provided with a hole;
2) weighing simple substance tellurium and simple substance cadmium according to the ratio of cadmium telluride; or weighing simple substance tellurium, simple substance cadmium and simple substance zinc according to the ratio of tellurium, zinc and cadmium;
3) loading elemental tellurium or elemental tellurium and elemental zinc into a first crucible, and loading elemental cadmium into a second crucible; placing the second crucible into the first crucible, and ensuring that the bottom of the second crucible is positioned above the melt of all the elemental materials in the first crucible after the elemental materials react to generate cadmium telluride or cadmium zinc telluride;
4) inserting the side wall of the first cover into the annular groove to cover the first crucible, and putting a liquid sealant into the annular groove;
5) placing the first crucible into a third crucible in a synthesis furnace; the synthesis furnace is provided with a plurality of temperature zones;
6) vacuumizing the interior of the synthesis furnace, and then filling inert gas with certain pressure;
7) operating a connecting rod arranged on the synthesis furnace to cover the second cover on the third crucible; the second cover is matched with the third crucible in a mechanical sealing way;
8) firstly, heating the liquid sealant to melt the liquid sealant; heating the lower part of the first crucible to melt the material in the first crucible; finally, heating the second crucible to melt the elemental cadmium in the second crucible;
9) the molten elemental cadmium in the second crucible is slowly dripped into the first crucible through a hole at the bottom of the second crucible and reacts with the melt in the first crucible to generate cadmium telluride or cadmium zinc telluride; continuously heating the lower part of the first crucible while cadmium telluride or cadmium zinc telluride is generated, and keeping a new material in the first crucible in a molten state;
10) after all the elemental materials react to generate cadmium telluride or cadmium zinc telluride, keeping the temperature, and then slowly cooling to the room temperature;
11) exhausting the inert gas in the synthesis furnace, operating the connecting rod to lift the second cover, and taking the first crucible out of the third crucible; and dissolving the liquid sealant in the annular groove, opening the first cover, and taking the cadmium telluride or cadmium zinc telluride crystal ingot out of the first crucible.
2. The method of preparing a cadmium telluride or cadmium zinc telluride polycrystalline material as set forth in claim 1 wherein: the inner diameter of the hole at the bottom of the second crucible is 1-10 mm.
3. The method of preparing a cadmium telluride or cadmium zinc telluride polycrystalline material as set forth in claim 1 wherein: and in the step 4), boron trioxide is used as a liquid sealant.
4. The method of preparing a cadmium telluride or cadmium zinc telluride polycrystalline material as set forth in claim 1 wherein: in the step 7), the second cover and the third crucible are in threaded fit to realize mechanical sealing; or the second cover realizes mechanical sealing with the third crucible through the outer conical surface.
5. The method of preparing a cadmium telluride or cadmium zinc telluride polycrystalline material as set forth in claim 1 wherein: after vacuumizing in the step 6), ensuring that the vacuum degree in the first crucible is less than 1 KPa; the used inert gas is nitrogen or argon with the purity of more than 5N, after vacuum pumping, the inert gas with the pressure of 0.08-0.12 MPa is filled, then vacuum pumping and inert gas filling are carried out for 2-10 times, and finally the pressure of the inert gas filling is 0.2-10 MPa.
6. The method of preparing a cadmium telluride or cadmium zinc telluride polycrystalline material as set forth in claim 1 wherein: in the step 8), the temperature of the liquid sealant is increased to 450-700 ℃ so that the liquid sealant is melted firstly; then, the temperature of the lower part of the first crucible is increased to 450-990 ℃, so that the material in the first crucible is melted; and finally, raising the temperature of the second crucible to 321-765 ℃ to completely melt the elemental cadmium.
7. The method of preparing a cadmium telluride or cadmium zinc telluride polycrystalline material as set forth in claim 1 wherein: and 8) setting a temperature gradient along the axial direction at the lower part of the first crucible, wherein the temperature gradient is 0.5-15 ℃/cm, and the temperature is gradually reduced from the bottom to the top so that the material in the first crucible is gradually melted from the bottom to the top.
8. The method of preparing a cadmium telluride or cadmium zinc telluride polycrystalline material as set forth in claim 1 wherein: in the step 9), while cadmium telluride or cadmium zinc telluride is generated, the temperature of the lower part of the first crucible is raised to 1092-1300 ℃ at the speed of 100-500 ℃/h, and the new material in the first crucible is kept in a molten state.
9. The method of preparing a cadmium telluride or cadmium zinc telluride polycrystalline material as set forth in claim 1 wherein: the inner diameter of the upper part of the first crucible is larger than the inner diameter of the lower part of the first crucible, and the outer diameter of the second crucible is smaller than the inner diameter of the upper part of the first crucible and larger than the inner diameter of the lower part of the first crucible.
10. A method of preparing a cadmium telluride or cadmium zinc telluride polycrystalline material as set forth in any one of claims 1 to 9 wherein: the first crucible, the second crucible and the first cover are made of quartz materials, and the third crucible and the second cover are made of graphite materials; and in the step 1), the first crucible and the second crucible are cleaned and dried, and then are placed into a carbon plating furnace, and a layer of carbon film is plated on the inner surfaces of the first crucible and the second crucible.
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| CN112647133A (en) * | 2020-12-16 | 2021-04-13 | 武汉高芯科技有限公司 | Cadmium zinc telluride crystal growth method and device |
| CN112680792A (en) * | 2020-12-09 | 2021-04-20 | 清远先导材料有限公司 | Method for purifying cadmium telluride |
| CN116555912A (en) * | 2023-05-29 | 2023-08-08 | 武汉拓材科技有限公司 | Preparation device of cadmium telluride polycrystal material |
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Effective date of registration: 20220922 Address after: Room 101-3, No. 10, Intelligent Digital Industrial Park, Changzhou Science and Education City, No. 18-67, Changwu Middle Road, Wujin District, Changzhou City, Jiangsu Province 213000 Patentee after: Zhongke Hongxin (Changzhou) Sensing Technology Co.,Ltd. Address before: No.399, Chendian Road, Jiulong Avenue, Tiangu Industrial Zone, Jiulonghu Town, Zhenhai District, Ningbo City, Zhejiang Province Patentee before: Ningbo tellurite Photoelectric Technology Co.,Ltd. |
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