CN110282975B - Germanium selenide target material and preparation method thereof - Google Patents
Germanium selenide target material and preparation method thereof Download PDFInfo
- Publication number
- CN110282975B CN110282975B CN201910610004.4A CN201910610004A CN110282975B CN 110282975 B CN110282975 B CN 110282975B CN 201910610004 A CN201910610004 A CN 201910610004A CN 110282975 B CN110282975 B CN 110282975B
- Authority
- CN
- China
- Prior art keywords
- germanium
- selenium
- block
- heating
- vacuum
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to the technical field of photoelectric material production, in particular to a germanium selenide target material and a preparation method thereof. The preparation method comprises the following steps: A) heating the germanium block to 980-1050 ℃, and preserving heat to obtain germanium liquid; B) heating the selenium block to 230-250 ℃, keeping the temperature, melting the selenium block, and dripping the melted selenium block into the germanium liquid to obtain mixed molten liquid; C) heating the mixed smelting liquid at 980-1050 ℃ for 30-60 min, and cooling to obtain selenium-germanium alloy; D) ball-milling the selenium-germanium alloy, and sintering the obtained selenium-germanium powder through vacuum hot pressing to obtain a germanium selenide target material; steps a), B) and C) are carried out under vacuum. According to the invention, the selenium-germanium alloy is prepared by adopting a vacuum dropping method, the selenium-germanium powder is obtained by ball milling, and then the germanium selenide target material is prepared by adopting a vacuum hot pressing method.
Description
Technical Field
The invention relates to the technical field of photoelectric material production, in particular to a germanium selenide target material and a preparation method thereof.
Background
Germanium selenide is mostly applied to the field of photoelectric detection in the IVA group and VIA group compound semiconductors of the periodic table. The commonly used method for preparing the semiconductor compound target material generally adopts a powder metallurgy method. The method needs to uniformly mix the elementary substance powder or directly sinter the compound powder. The melting point of germanium is 938.5 ℃, the melting point of selenium is 221 ℃, and the difference of the melting points is too large, so if germanium powder and selenium powder are directly used for preparing a germanium selenide target material, the sintering temperature is too low, the density of the target material is poor, and therefore, the germanium selenide powder needs to be synthesized.
The Chinese patent with the application number of 201610793216.7 discloses a preparation method of germanium selenide powder, which is prepared by heating and insulating germanium powder and selenium powder under the vacuum condition and then crushing under the protection of argon. The preparation method has the following defects: 1. germanium and selenium need to be prepared into powder and then mixed uniformly, and the powder is easy to oxidize due to the fact that the specific surface of the powder is relatively large; 2. argon protection is needed in the process, and the energy consumption is high; 3. the process is complicated, and the steps of milling, briquetting and the like are needed, so that the pollution is easily caused.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a germanium selenide target and a preparation method thereof, wherein the germanium selenide target prepared by the preparation method or the device provided by the present invention has high density and small difference with the theoretical selenium content.
The invention provides a preparation method of a germanium selenide target material, which comprises the following steps:
A) heating the germanium block to 980-1050 ℃, and preserving heat to obtain germanium liquid;
B) heating the selenium block to 230-250 ℃, keeping the temperature, melting the selenium block, and dripping the melted selenium block into the germanium liquid to obtain mixed molten liquid;
C) heating the mixed smelting liquid at 980-1050 ℃ for 30-60 min, and cooling to obtain selenium-germanium alloy;
D) ball-milling the selenium-germanium alloy, and sintering the obtained selenium-germanium powder in a vacuum hot pressing manner to obtain a germanium selenide target material;
steps a), B) and C) are carried out under vacuum.
Preferably, the molar ratio of the germanium block to the selenium block is 1: 1.01-1.015.
Preferably, in the step A), the heat preservation time is 25-30 min.
Preferably, in the step B), the heating rate is 10-15 ℃/min;
the heat preservation time is 30-90 min.
Preferably, in step C), the cooling is natural cooling; the temperature after cooling is room temperature.
Preferably, the preparation device of the selenium germanium alloy comprises:
a box body;
a melt crucible disposed in the housing, the germanium block being heated in the melt crucible;
a quartz funnel disposed in the housing, the selenium cake being heated in the quartz funnel;
the quartz funnel is arranged above the melting crucible, so that the melting liquid in the quartz funnel is dripped into the melting crucible;
a first heating device for heating the melt crucible;
and the second heating device is used for heating the quartz funnel.
Preferably, the aperture of the quartz funnel is 0.8-1.2 mm.
Preferably, in the step D), the ball-milling ratio of balls to materials is 2: 1;
the ball milling time is 3-6 h.
Preferably, in the step D), the temperature of the vacuum hot-pressing sintering is 550-580 ℃; the pressure of the vacuum hot-pressing sintering is 35-55 MPa; the time for vacuum hot-pressing sintering is 90-120 min; the vacuum degree of the vacuum hot-pressing sintering is less than 5 Pa.
The invention also provides the germanium selenide target prepared by the preparation method.
The invention provides a preparation method of a germanium selenide target material, which comprises the following steps: A) heating the germanium block to 980-1050 ℃, and preserving heat to obtain germanium liquid; B) heating the selenium block to 230-250 ℃, keeping the temperature, melting the selenium block, and dripping the melted selenium block into the germanium liquid to obtain mixed molten liquid; C) heating the mixed smelting liquid at 980-1050 ℃ for 30-60 min, and cooling to obtain selenium-germanium alloy; D) ball-milling the selenium-germanium alloy, and sintering the obtained selenium-germanium powder in a vacuum hot pressing manner to obtain a germanium selenide target material; steps a), B) and C) are carried out under vacuum. The invention adopts a vacuum dripping method to prepare the selenium-germanium alloy, so that the germanium block and the selenium block are respectively melted at different temperatures, wherein the selenium block is in a low-temperature section, and the increase of the volatilization amount of selenium caused by high vapor pressure is avoided. And then ball milling is carried out to obtain selenium-germanium powder, and then a vacuum hot pressing method is applied to prepare the germanium selenide target material, wherein the prepared germanium selenide target material has higher density and smaller content difference with the theoretical selenium content. In addition, the preparation method provided by the invention is simple, has high production efficiency, does not introduce impurities, and has small selenium volatilization amount.
Experimental results show that the selenium content in the germanium selenide target material prepared by the invention is close to the theoretical proportion, the difference with the theoretical selenium content is less than 0.3%, and the relative density of the germanium selenide target material is more than 96%.
Drawings
Fig. 1 is a schematic structural diagram of a selenium-germanium alloy preparation apparatus provided in an embodiment of the present application.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preparation method of a germanium selenide target material, which comprises the following steps:
A) heating the germanium block to 980-1050 ℃, and preserving heat to obtain germanium liquid;
B) heating the selenium block to 230-250 ℃, preserving heat, melting the selenium block, and dripping the melted selenium block into the germanium liquid to obtain mixed smelting liquid;
C) heating the mixed smelting liquid at 980-1050 ℃ for 30-60 min, and cooling to obtain selenium-germanium alloy;
D) ball-milling the selenium-germanium alloy, and sintering the obtained selenium-germanium powder in a vacuum hot pressing manner to obtain a germanium selenide target material;
steps a), B) and C) are carried out under vacuum.
The raw materials used by the preparation method provided by the invention are germanium blocks and selenium blocks. The present invention is not particularly limited with respect to the purity of the germanium block and the selenium block. The source of the germanium block and the selenium block is not particularly limited, and the germanium block and the selenium block can be generally commercially available. In certain embodiments of the invention, the molar ratio of the germanium chunks to the selenium chunks is 1: 1.01 to 1.02. In certain embodiments, the molar ratio of the germanium chunks to the selenium chunks is 1: 1.01, 1: 1.012 or 1: 1.015.
according to the method, the germanium block is heated to 980-1050 ℃, and the germanium liquid is obtained after heat preservation.
The present invention is not limited to a particular heating rate for heating the germanium block, as is known to those skilled in the art.
In the invention, the germanium block is heated to 980-1050 ℃. In certain embodiments of the invention, the germanium block is heated to 1050 ℃, 1000 ℃, or 980 ℃.
In some embodiments of the invention, the time for the heat preservation is 25-30 min. In certain embodiments, the incubation time is 25min or 30 min.
In some embodiments of the invention, the germanium block is heated in a melt crucible to obtain a germanium liquid.
And after obtaining germanium liquid, heating the selenium block to 230-250 ℃, preserving heat, melting the selenium block, and dripping the selenium block into the germanium liquid to obtain mixed smelting liquid.
In the invention, the selenium block is heated to 230-250 ℃. In certain embodiments of the invention, the selenium cake is heated to 230 ℃, 240 ℃ or 250 ℃.
In some embodiments of the present invention, the heating rate of the heating selenium block is 10-15 ℃/min. In certain embodiments, the heating rate is 15 ℃/min, 12 ℃/min, or 10 ℃/min.
In some embodiments of the invention, the selenium block is heated to 230-250 ℃ and then kept for 30-90 min. In certain embodiments, the incubation time is 60min, 90min, or 30 min. After the heat preservation, the selenium block can be completely melted and dripped into the germanium liquid to obtain mixed smelting liquid.
In some embodiments of the present invention, the selenium block is heated in a quartz funnel to obtain selenium liquid, and the selenium liquid is dropped into the melting crucible through the quartz funnel to obtain a mixed melting liquid.
And heating the mixed smelting liquid at 980-1050 ℃ for 30-60 min, and cooling to obtain the selenium-germanium alloy.
The heating temperature of the mixed smelting liquid is equal to the temperature of the heated germanium blocks and ranges from 980 ℃ to 1050 ℃. In certain embodiments of the invention, the mixed smelt is heated at 1050 ℃, 1000 ℃, or 980 ℃. The heating time of the mixed smelting liquid is 30-60 min. In certain embodiments of the invention, the heating time of the mixed melt is 40min, 30min or 50 min.
In certain embodiments of the present invention, the cooling is natural cooling, and the temperature after cooling is room temperature.
In the present invention, steps A), B) and C) are carried out under vacuum. Specifically, it is preferable that: before the step A) is started, vacuumizing the system to ensure that the vacuum degree of the system is less than 3 Pa. In certain embodiments, the vacuum of the system is 2Pa or 2.5 Pa.
In some embodiments of the present invention, the device for preparing the selenium-germanium alloy is a vacuum dripping device. Preferably comprising:
a box body;
a melt crucible disposed in the housing, the germanium block being heated in the melt crucible;
a quartz funnel disposed in the housing, the selenium cake being heated in the quartz funnel;
the quartz funnel is arranged above the melting crucible, so that the melting liquid in the quartz funnel is dripped into the melting crucible;
a first heating device for heating the melt crucible;
and the second heating device is used for heating the quartz funnel.
The preparation device of the selenium-germanium alloy is shown in figure 1. Fig. 1 is a schematic structural diagram of a selenium-germanium alloy preparation apparatus provided in an embodiment of the present invention. Wherein, 1 is a box body, 1-2 is a box cover, 2 is a melting crucible, 3 is a quartz funnel, 4 is a first heating device, and 5 is a second heating device.
In some embodiments of the invention, the box body is preferably made of quartz plates with the thickness of 3-5 mm through welding. The box is preferably cubical. In one embodiment of the present invention, the box body 1 has a rectangular parallelepiped shape, and includes a box body 1-1 and a box cover 1-2, as shown in fig. 1.
In some embodiments of the invention, the tank body and tank lid are sealed by vacuum flanges. The present invention is not particularly limited in kind of the vacuum flange, and may be generally commercially available.
In an embodiment of the present invention, the preparation apparatus further includes a vacuum pump for providing a vacuum environment to the box body. The connection mode of the vacuum pump and the box body is not particularly limited, and the vacuum environment can be provided for the box body. In one embodiment of the present invention, a vacuum port is disposed on a cover of the box body, and the vacuum port is connected to the vacuum pump. The vacuum pump of the present invention is not particularly limited in kind, and may be generally commercially available.
When the operation is started, the box cover is opened, the germanium block is placed in the melting crucible, the selenium block is placed in the quartz funnel, the box cover is closed, a vacuum flange is sleeved between the box body and the box cover, and the box is vacuumized.
The preparation device of the selenium-germanium alloy also comprises a melting crucible 2. A melt crucible is disposed in the housing, and the germanium block is heated in the melt crucible. The invention has no special limitation on the type and size of the melting crucible, and can contain the required mixed melting liquid.
The preparation device of the selenium-germanium alloy also comprises a quartz funnel 3. The quartz funnel is arranged in the box body, and the selenium block is heated in the quartz funnel. The size of the quartz funnel is not particularly limited, and in some embodiments, the diameter of the quartz funnel is 0.8-1.2 mm. In certain embodiments, the quartz funnel has an aperture of 0.8mm, 1mm, or 1.2 mm.
In the invention, the quartz funnel is arranged above the melting crucible, so that the molten liquid in the quartz funnel is dripped into the melting crucible.
The size of the box body is not particularly limited, and in some embodiments, the vertical distance between the melting crucible and the quartz funnel is 50-70 cm. In some embodiments, the frit crucible is located 65cm from the quartz funnel.
The preparation device of the selenium-germanium alloy also comprises a first heating device. The first heating device is used for heating the melting crucible. The present invention is not limited to a particular location for installing the first heating device, and the frit crucible can be heated. In some embodiments of the invention, the first heating means is provided on an outer wall of an upper portion of the cabinet. The first heating device is not limited in structure, and the frit crucible can be heated to a desired temperature by a heating device known to those skilled in the art. In some embodiments of the present invention, the first heating device is a commercially available high temperature heating furnace, and specifically may be a high temperature heating furnace manufactured by high-density pent electronics equipment limited.
The preparation device of the selenium-germanium alloy also comprises a second heating device. The second heating device is used for heating the quartz funnel. The installation position of the second heating device is not particularly limited, and the quartz funnel can be heated. In some embodiments of the invention, the second heating means is provided on an outer wall of a lower portion of the cabinet. The second heating device is not limited in structure, and the quartz funnel can be heated to a desired temperature by a heating device known to those skilled in the art. In some embodiments of the present invention, the second heating device is a commercially available low-temperature heating furnace, and specifically, may be a low-temperature heating furnace manufactured by high-density compact electronics limited.
In the specific operation, heating the germanium block in the melting crucible to 980-1050 ℃ by a first heating device, and preserving heat to obtain germanium liquid; heating the selenium block in the quartz funnel to 230-250 ℃ by using a second heating device, preserving heat, melting the selenium block, and dripping the selenium block into a melt crucible through the quartz funnel to obtain a mixed melt in the melt crucible; and finally, heating the mixed smelting solution for 30-60 min at 980-1050 ℃ by using a second heating device, and cooling to obtain the selenium-germanium alloy. According to the invention, the vacuum dripping device is adopted to prepare the selenium-germanium alloy, so that the germanium block and the selenium block are respectively melted at different temperatures, wherein the selenium block is in a low-temperature section, and the increase of the volatilization amount of selenium caused by high vapor pressure is avoided.
After the selenium-germanium alloy is obtained, ball milling is carried out on the selenium-germanium alloy, and the obtained selenium-germanium powder is sintered through vacuum hot pressing to obtain the germanium selenide target material.
The method of ball milling is not particularly limited in the present invention, and a ball milling method known to those skilled in the art may be used. In some embodiments of the invention, the ball-milling has a ball-to-material ratio of 2-3: 1. in certain embodiments, the ball-milled balls have a ball-to-feed ratio of 2: 1.
in some embodiments of the invention, the ball milling time is 3-6 h. In certain embodiments, the ball milling time is 5h, 6h, or 3 h.
In certain embodiments of the invention, the ball milling is performed in a roller ball mill.
In some embodiments of the invention, the temperature of the vacuum hot-pressing sintering is 550-580 ℃; the pressure of the vacuum hot-pressing sintering is 35-55 MPa; the vacuum hot-pressing sintering time is 90-120 min; the vacuum degree of the vacuum hot-pressing sintering is less than 5 Pa.
In certain embodiments, the temperature of the vacuum hot press sintering is 580 ℃, 560 ℃, or 550 ℃; the pressure of the vacuum hot-pressing sintering is 35MPa, 55MPa or 50 MPa; the time of the vacuum hot-pressing sintering is 120min or 100 min; the vacuum degree of the vacuum hot-pressing sintering is 4.5Pa, 4Pa or 3 Pa.
In certain embodiments of the invention, the vacuum hot press sintering is performed in a hot press furnace. Specifically, it is preferable that: and (3) loading the ball-milled selenium-germanium powder into a graphite die, and then placing the graphite die into a hot pressing furnace for vacuum hot pressing sintering.
The invention also provides the germanium selenide target prepared by the preparation method. The germanium selenide target provided by the invention has higher density and smaller content difference with theoretical selenium.
Experimental results show that the selenium content of the germanium selenide target material prepared by the invention is close to the theoretical proportion, the difference with the theoretical selenium content is less than 0.3%, and the relative density of the germanium selenide target material is more than 96%.
The invention provides a preparation method of a germanium selenide target material, which comprises the following steps: A) heating the germanium block to 980-1050 ℃, and preserving heat to obtain germanium liquid; B) heating the selenium block to 230-250 ℃, preserving heat, melting the selenium block, and dripping the melted selenium block into the germanium liquid to obtain mixed smelting liquid; C) heating the mixed smelting liquid at 980-1050 ℃ for 30-60 min, and cooling to obtain selenium-germanium alloy; D) ball-milling the selenium-germanium alloy, and sintering the obtained selenium-germanium powder in a vacuum hot pressing manner to obtain a germanium selenide target material; steps a), B) and C) are carried out under vacuum. The invention adopts a vacuum dripping method to prepare the selenium-germanium alloy, so that the germanium block and the selenium block are respectively melted at different temperatures, wherein the selenium block is in a low-temperature section, and the increase of the volatilization amount of selenium caused by high vapor pressure is avoided. And then ball milling is carried out to obtain selenium-germanium powder, and then a vacuum hot pressing method is applied to prepare the germanium selenide target material, wherein the prepared germanium selenide target material has higher density and smaller content difference with the theoretical selenium content. In addition, the preparation method provided by the invention is simple, has high production efficiency, does not introduce impurities, and has small selenium volatilization amount.
Experimental results show that the selenium content of the germanium selenide target material prepared by the invention is close to the theoretical proportion, the difference with the theoretical selenium content is less than 0.3%, and the relative density of the germanium selenide target material is more than 96%.
In order to further illustrate the present invention, the following will describe in detail a germanium selenide target and a method for preparing the same with reference to the following examples, which should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all generally commercially available.
Example 1
Preparing the selenium-germanium alloy by using a preparation device shown in figure 1:
rectangular box body: a vacuum-pumping port is arranged on the box cover of the box body and is connected with a vacuum pump;
a melt crucible disposed in the housing, the germanium block being heated in the melt crucible;
a quartz funnel (the aperture of the quartz funnel is 0.8mm) arranged in the box body, wherein the selenium block is heated in the quartz funnel;
the quartz funnel is arranged above the melting crucible, so that the melting liquid in the quartz funnel is dripped into the melting crucible; the vertical distance between the melting crucible and the quartz funnel is 65 cm.
A first heating device (i.e., a high temperature heating furnace) for heating the melt crucible; the first heating device is arranged on the outer wall of the upper part of the box body;
a second heating device (i.e. a low-temperature heating furnace) for heating the quartz funnel; the second heating device is arranged on the outer wall of the lower part of the box body.
The specific operation is as follows:
opening a box cover, placing a germanium block in a melting crucible, placing a selenium block in a quartz funnel, closing the box cover, sleeving a vacuum flange between a box body and the box cover, and vacuumizing to the vacuum degree of 2 Pa. The molar ratio of the germanium blocks to the selenium blocks is 1: 1.01.
starting a first heating device, heating to 1050 ℃, and keeping the temperature for 25min to obtain germanium liquid; and then starting a second heating device, heating to 230 ℃ at the speed of 15 ℃/min, preserving heat for 60min, melting the selenium block, and dripping the selenium block into the germanium liquid to obtain a mixed smelting liquid.
And closing the second heating device, heating the mixed smelting liquid at 1050 ℃ for 60min by the first heating device, then closing the first heating device, and naturally cooling the mixed smelting liquid to room temperature along with the furnace to obtain the selenium-germanium alloy.
Ball milling the selenium-germanium alloy (ball-to-material ratio of ball milling is 2: 1) for 5h to obtain selenium-germanium powder;
and (3) loading the selenium-germanium powder into a graphite die, and then placing the graphite die into a hot pressing furnace for vacuum hot pressing sintering to obtain the germanium selenide target. The temperature of the vacuum hot-pressing sintering is 580 ℃, the pressure of the vacuum hot-pressing sintering is 35MPa, the time of the vacuum hot-pressing sintering is 120min, and the vacuum degree of the vacuum hot-pressing sintering is 4.5 Pa.
And (3) testing the selenium content in the germanium selenide target by adopting a titration method, and testing the density of the germanium selenide target by adopting a drainage method.
The experimental result shows that the selenium content in the germanium selenide target material in the embodiment is 52.10 wt%, which is different from the theoretical selenium content (52.09 wt%) by 0.02%; the relative density of the germanium selenide target material is 97.2%.
Example 2
The preparation device shown in figure 1 is adopted to prepare the selenium-germanium alloy, and the difference from the embodiment 1 is that: the aperture of the quartz funnel is 1 mm.
The specific operation is as follows:
opening a box cover, placing a germanium block in a melting crucible, placing a selenium block in a quartz funnel, closing the box cover, sleeving a vacuum flange between a box body and the box cover, and vacuumizing to the vacuum degree of 2.5 Pa. The molar ratio of the germanium blocks to the selenium blocks is 1: 1.012.
starting a first heating device, heating to 1000 ℃, and preserving heat for 30min to obtain germanium liquid; and then starting a second heating device, heating to 240 ℃ at the speed of 12 ℃/min, preserving heat for 90min, melting the selenium block, and dripping the selenium block into the germanium solution to obtain a mixed smelting solution.
And closing the second heating device, heating the mixed smelting liquid for 30min at 1000 ℃ by using the first heating device, then closing the first heating device, and naturally cooling the mixed smelting liquid to room temperature along with the furnace to obtain the selenium-germanium alloy.
Ball milling the selenium-germanium alloy (ball-to-material ratio of ball milling is 2: 1) for 6h to obtain selenium-germanium powder;
and (3) loading the selenium-germanium powder into a graphite die, and then placing the graphite die into a hot pressing furnace for vacuum hot pressing sintering to obtain the germanium selenide target. The temperature of the vacuum hot-pressing sintering is 560 ℃, the pressure of the vacuum hot-pressing sintering is 55MPa, the time of the vacuum hot-pressing sintering is 100min, and the vacuum degree of the vacuum hot-pressing sintering is 4 Pa.
And (3) testing the selenium content in the germanium selenide target by adopting a titration method, and testing the density of the germanium selenide target by adopting a drainage method.
The experimental result shows that the selenium content in the germanium selenide target material in the embodiment is 51.95 wt%, which is 0.27% different from the theoretical selenium content; the relative density of the germanium selenide target is 96.8%.
Example 3
The preparation device shown in figure 1 is adopted to prepare the selenium-germanium alloy, and the difference from the embodiment 1 is that: the aperture of the quartz funnel is 1.2 mm.
The specific operation is as follows:
opening a box cover, placing a germanium block in a melting crucible, placing a selenium block in a quartz funnel, closing the box cover, sleeving a vacuum flange between a box body and the box cover, and vacuumizing to the vacuum degree of 2 Pa. The molar ratio of the germanium blocks to the selenium blocks is 1: 1.015.
starting a first heating device, heating to 980 ℃, and preserving heat for 30min to obtain germanium liquid; and then starting a second heating device, heating to 250 ℃ at a speed of 10 ℃/min, preserving heat for 30min, melting the selenium block, and dripping the selenium block into the germanium solution to obtain a mixed smelting solution.
And closing the second heating device, heating the mixed smelting liquid for 50min at 980 ℃ by using the first heating device, then closing the first heating device, and naturally cooling the mixed smelting liquid to room temperature along with the furnace to obtain the selenium-germanium alloy.
Ball milling the selenium-germanium alloy (ball-to-material ratio of ball milling is 2: 1) for 3h to obtain selenium-germanium powder;
and (3) loading the selenium-germanium powder into a graphite die, and then placing the graphite die into a hot pressing furnace for vacuum hot pressing sintering to obtain the germanium selenide target. The temperature of the vacuum hot-pressing sintering is 550 ℃, the pressure of the vacuum hot-pressing sintering is 50MPa, the time of the vacuum hot-pressing sintering is 100min, and the vacuum degree of the vacuum hot-pressing sintering is 3 Pa.
And (3) testing the selenium content in the germanium selenide target by adopting a titration method, and testing the density of the germanium selenide target by adopting a drainage method.
The experimental result shows that the selenium content in the germanium selenide target material in the embodiment is 52.13 wt%, which is 0.08% different from the theoretical selenium content; the relative density of the germanium selenide target material is 96.5%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A preparation method of a germanium selenide target is characterized by comprising the following steps:
A) heating the germanium block to 980-1050 ℃, and preserving heat to obtain germanium liquid;
B) heating the selenium block to 230-250 ℃, keeping the temperature, melting the selenium block, and dripping the melted selenium block into the germanium liquid to obtain mixed molten liquid;
C) heating the mixed smelting liquid at 980-1050 ℃ for 30-60 min, and cooling to obtain selenium-germanium alloy;
before the step A), vacuumizing the system to enable the vacuum degree of the system to be less than 3 Pa;
the preparation device of the selenium-germanium alloy comprises:
a box body; the box body comprises a box body 1-1 and a box cover 1-2; the box body 1-1 and the box cover 1-2 are sealed through vacuum flanges;
a melt crucible disposed in the housing, the germanium block being heated in the melt crucible;
a quartz funnel disposed in the housing, the selenium cake being heated in the quartz funnel;
the quartz funnel is arranged above the melting crucible, so that the melting liquid in the quartz funnel is dripped into the melting crucible;
the vertical distance between the melting crucible and the quartz funnel is 50-70 cm;
a first heating device for heating the melt crucible;
the second heating device is used for heating the quartz funnel;
the vacuum pump is used for providing a vacuum environment for the box body;
when the operation is started, the box cover 1-2 is opened, the germanium block is placed in the melting crucible, the selenium block is placed in the quartz funnel, the box cover 1-2 is closed, a vacuum flange is sleeved between the box body 1-1 and the box cover 1-2, and the box is vacuumized;
D) ball-milling the selenium-germanium alloy, and sintering the obtained selenium-germanium powder in a vacuum hot pressing manner to obtain a germanium selenide target material;
steps a), B) and C) are carried out under vacuum.
2. The method of claim 1, wherein the molar ratio of the germanium block to the selenium block is 1: 1.01-1.015.
3. The preparation method according to claim 1, wherein in the step A), the heat preservation time is 25-30 min.
4. The preparation method according to claim 1, wherein in the step B), the heating rate is 10-15 ℃/min;
the heat preservation time is 30-90 min.
5. The method according to claim 1, wherein in step C), the cooling is natural cooling; the temperature after cooling is room temperature.
6. The method according to claim 1, wherein the quartz funnel has a pore size of 0.8 to 1.2 mm.
7. The preparation method according to claim 1, wherein in the step D), the ball-milling has a ball-to-material ratio of 2: 1;
the ball milling time is 3-6 h.
8. The preparation method of claim 1, wherein in the step D), the temperature of the vacuum hot-pressing sintering is 550-580 ℃; the pressure of the vacuum hot-pressing sintering is 35-55 MPa; the vacuum hot-pressing sintering time is 90-120 min; the vacuum degree of the vacuum hot-pressing sintering is less than 5 Pa.
9. A germanium selenide target prepared by the preparation method of any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910610004.4A CN110282975B (en) | 2019-07-08 | 2019-07-08 | Germanium selenide target material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910610004.4A CN110282975B (en) | 2019-07-08 | 2019-07-08 | Germanium selenide target material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110282975A CN110282975A (en) | 2019-09-27 |
| CN110282975B true CN110282975B (en) | 2022-07-01 |
Family
ID=68020899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910610004.4A Active CN110282975B (en) | 2019-07-08 | 2019-07-08 | Germanium selenide target material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110282975B (en) |
Family Cites Families (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1018460B (en) * | 1988-04-30 | 1992-09-30 | 大冶钢厂 | Process for adding selenium to melten steel |
| CN1034199C (en) * | 1994-08-20 | 1997-03-05 | 浙江大学 | Method for production of semi-conductor thermoelectric device and its material and apparatus thereof |
| US6874335B2 (en) * | 2002-04-12 | 2005-04-05 | Micron Technology, Inc. | Large scale synthesis of germanium selenide glass and germanium selenide glass compounds |
| US7389029B2 (en) * | 2003-07-03 | 2008-06-17 | Applied Research And Photonics, Inc. | Photonic waveguide structures for chip-scale photonic integrated circuits |
| US8309163B2 (en) * | 2004-02-19 | 2012-11-13 | Nanosolar, Inc. | High-throughput printing of semiconductor precursor layer by use of chalcogen-containing vapor and inter-metallic material |
| US7277313B2 (en) * | 2005-08-31 | 2007-10-02 | Micron Technology, Inc. | Resistance variable memory element with threshold device and method of forming the same |
| WO2007037796A2 (en) * | 2005-09-19 | 2007-04-05 | Honeywell International Inc. | Chalcogenide pvd components and methods of formation |
| CN101205577B (en) * | 2006-12-18 | 2010-08-25 | 广东凤铝铝业有限公司 | Manufacturing technology of leadless easy-cutting aluminium alloy |
| CN101217178B (en) * | 2007-12-26 | 2010-12-29 | 中国科学院上海硅酸盐研究所 | A preparation method for antimonide molybdenum base thermoelectric material |
| CN101469384B (en) * | 2007-12-28 | 2011-11-16 | 比亚迪股份有限公司 | Brass alloy material and preparation thereof |
| CN201176454Y (en) * | 2008-04-03 | 2009-01-07 | 东北大学 | Smelting furnace |
| CN101660065A (en) * | 2008-08-26 | 2010-03-03 | 天津松岩铝制品有限公司 | Method for smelting aluminum-magnesium alloy |
| FR2943340B1 (en) * | 2009-03-18 | 2011-04-22 | Centre Nat Rech Scient | PROCESS FOR THE PREPARATION OF A THIN THIN PININCE LAYER |
| WO2011010724A1 (en) * | 2009-07-23 | 2011-01-27 | 住友電気工業株式会社 | Method and device for manufacturing semiconductor crystal, and semiconductor crystal |
| CN102051513B (en) * | 2010-11-04 | 2012-03-21 | 宁波工程学院 | Metal selenide thermoelectric material for intermediate temperate and preparation process thereof |
| CN102071329B (en) * | 2010-11-25 | 2012-04-25 | 清远先导材料有限公司 | Method for preparing copper-indium-gallium-selenium alloy |
| CN102092690A (en) * | 2010-12-03 | 2011-06-15 | 无锡润鹏复合新材料有限公司 | Method for preparing tungsten diselenide nano sheets |
| CN102382995A (en) * | 2011-10-17 | 2012-03-21 | 苏州新金相金属材料有限公司 | Preparation process of intermediate alloy containing volatile element |
| CN103449385B (en) * | 2012-05-28 | 2015-04-01 | 广东先导稀材股份有限公司 | Preparation method of cuprous selenide |
| CN102912185B (en) * | 2012-10-16 | 2016-05-04 | 常州大学 | A kind of environment protection type high-strength automatic steel bismuth zircaloy |
| CN102849693B (en) * | 2012-10-22 | 2014-04-02 | 四川大学 | High-temperature liquid-phase synthesis method of cadmium telluride powder |
| CN103320750B (en) * | 2013-06-21 | 2015-04-01 | 成都先锋材料有限公司 | Method for producing sputtering target material of germanium-antimony-tellurium compound phase change material |
| CN103343238B (en) * | 2013-07-22 | 2014-11-12 | 上海交通大学 | Zone melting and directional solidifying method used for volatile element alloy |
| CN103484699B (en) * | 2013-09-10 | 2016-01-06 | 中南大学 | A kind of sealing of the Mg-based master alloy containing low melting point metal element melting and casting method |
| CN104086177B (en) * | 2014-07-29 | 2016-02-03 | 西北有色金属研究院 | A kind of preparation method of FeSe base superconductor |
| CN104860272A (en) * | 2015-05-12 | 2015-08-26 | 武汉理工大学 | New method for quick preparation of high-purity cadmium telluride powder |
| CN105293451B (en) * | 2015-11-06 | 2018-02-06 | 成都先锋材料有限公司 | Nonequilibrium state chalcogenide, film and preparation method thereof |
| CN105568010A (en) * | 2015-12-31 | 2016-05-11 | 包头稀土研究院 | Preparation method of low-melting-point metal alloy |
| CN105967152B (en) * | 2016-05-17 | 2018-01-12 | 广东省稀有金属研究所 | A kind of method and apparatus for preparing high-purity anaerobic granules of selenium |
| CN106348258A (en) * | 2016-08-31 | 2017-01-25 | 洛阳师范学院 | Preparation method of germanium diselenide powder |
| CN106430120A (en) * | 2016-08-31 | 2017-02-22 | 洛阳师范学院 | Method for preparing germanium selenide powder |
| CN107793154B (en) * | 2016-09-07 | 2020-06-19 | 武汉理工大学 | Ultra-fast preparation of Cu2Method for Se/BiCuSeO block composite thermoelectric material |
| CN107299272B (en) * | 2017-05-10 | 2018-09-14 | 西安建筑科技大学 | A kind of smelting technology of bismuth-containing free cutting stainless steel |
| CN109371371A (en) * | 2018-12-10 | 2019-02-22 | 有研工程技术研究院有限公司 | A kind of preparation method of selenium arsenic germanium multi-component Alloy Sputtering target |
| CN109877335B (en) * | 2019-03-12 | 2022-02-22 | 先导薄膜材料（广东）有限公司 | Preparation method of copper indium gallium selenide powder |
| CN110055435B (en) * | 2019-04-28 | 2020-08-14 | 先导薄膜材料（广东）有限公司 | Preparation method of selenium-copper alloy |
| CN110128143B (en) * | 2019-06-25 | 2022-07-15 | 先导薄膜材料（广东）有限公司 | Cadmium selenide target material and preparation method thereof |
-
2019
- 2019-07-08 CN CN201910610004.4A patent/CN110282975B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110282975A (en) | 2019-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103232161B (en) | A kind of preparation method of Ge-Sb-Se system IR glass and equipment | |
| CN105441884B (en) | A kind of preparation method of molybdenum niobium alloy sputtering target material | |
| CN105693248B (en) | A kind of cadmium sulfide target preparation method and device | |
| CN101381085B (en) | Rapid preparation method of LaB6 polycrystalline bulk cathode material | |
| CN106424637A (en) | Massive amorphous alloy high-vacuum die casting forming equipment and process | |
| CN102343437A (en) | Method for manufacturing tungsten target material | |
| CN103785838A (en) | Chromium target production method | |
| CN102994787A (en) | Method for vacuum melting of silver cadmium alloy ingot | |
| CN106643126B (en) | Intermittent positive pressure sintering device and method for tantalum anode block | |
| CN110282975B (en) | Germanium selenide target material and preparation method thereof | |
| CN104616880B (en) | A kind of method for producing Sintered NdFeB magnet | |
| CN102328917B (en) | The two-step synthesis method of selenium gallium indium Copper thin film solar cell material | |
| CN112592173A (en) | Preparation method of ITO (indium tin oxide) sintered target material | |
| CN207231204U (en) | A kind of Vacuum Magnetic sinters quenching stove | |
| CN207726961U (en) | A kind of 3D bend glass hot-bending machines using vacuum displacement technology | |
| CN205927110U (en) | Sintered nd -Fe -B open -type sintering magazine | |
| CN212357345U (en) | Purification device for purifying indium from ITO waste target | |
| CN104561913B (en) | A kind of low-resistivity CIGS quaternary alloy sputtering target material and preparation method thereof | |
| CN210435361U (en) | Sintering furnace | |
| CN2567535Y (en) | Neodymium-iron-boron permanent-magnet material multifunction vacuum fritting furnace | |
| CN103451377A (en) | Amorphous parent metal smelting method and amorphous parent metal smelting device | |
| CN211041866U (en) | Smelting furnace observation window device | |
| CN209893921U (en) | Pit furnace | |
| CN105689699B (en) | A kind of process units and technique for producing hypoxemia dusty material | |
| CN219824312U (en) | Titanium sponge vacuum distillation device capable of controlling chlorine element |
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 |