WO2013178036A1 - Bismuth selenide preparation method - Google Patents

Bismuth selenide preparation method Download PDF

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Publication number
WO2013178036A1
WO2013178036A1 PCT/CN2013/076189 CN2013076189W WO2013178036A1 WO 2013178036 A1 WO2013178036 A1 WO 2013178036A1 CN 2013076189 W CN2013076189 W CN 2013076189W WO 2013178036 A1 WO2013178036 A1 WO 2013178036A1
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Prior art keywords
quartz tube
bismuth
selenium
graphite boat
synthesis furnace
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PCT/CN2013/076189
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French (fr)
Chinese (zh)
Inventor
胡智向
卢金生
文崇斌
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广东先导稀材股份有限公司
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Publication of WO2013178036A1 publication Critical patent/WO2013178036A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals

Definitions

  • the invention relates to a preparation method of a synthetic material, in particular to a preparation method of triselenization diterpene. Background technique
  • the triselenization diterpene formula Bi 2 Se 3 atomic weight 654.4, melting point 710 ° C, density 6. 82 g / cm 3 , black or dark blue solid, with semiconductor properties. It is a good substitute for cadmium selenide and lead selenide. It is mainly used in semiconductors, optoelectronic devices, thermoelectric cooling semiconductors, Bi 2 Se 3 films, etc.
  • One object of the present invention is to provide a process for the preparation of bis(Selenide) ruthenium which is non-toxic during the preparation process.
  • Another object of the present invention is to provide a process for preparing triselenosedin which can reduce contamination.
  • a further object of the present invention is to provide a process for the preparation of bis-selenide diterpene which requires low equipment and low cost.
  • the present invention provides a method for preparing triselenization diterpene, comprising the steps of: mixing selenium powder and niobium powder in a prescribed molar ratio to obtain a mixture in which selenium is excessive; Inside the graphite boat; the graphite boat with the mixture is placed in the quartz tube; the quartz tube is placed In the horizontal synthesis furnace; an inert gas is introduced into the quartz tube; under the protection of the inert gas, the horizontal synthesis furnace is heated to a temperature above the melting point of the triselenization bismuth, so that the selenium bismuth and the synthesis reaction are carried out to obtain the selenization ⁇ ; After the synthesis reaction, the horizontal synthesis furnace was cooled to room temperature to obtain a tri-selenide crystal.
  • the reaction since the reaction is protected by an inert gas, it is non-toxic in the preparation process and the quality of the obtained product is good.
  • the dust collecting hood since the dust collecting hood is used, the volatilization of the selenium vapor can be reduced and the volatile selenium particles can be recovered, and the pollution can be reduced.
  • the preparation method of the triselenization diterpene since the graphite boat, the quartz tube, the horizontal synthesis heating furnace, and the like are used, the preparation method has low requirements on equipment and low cost.
  • the preparation method of the triselenization diterpene comprises the steps of: mixing the niobium powder and the selenium powder in a prescribed molar ratio to obtain a mixture, wherein the selenium is excessive; the mixture is charged into the graphite boat; The graphite boat is placed in a quartz tube; the quartz tube is placed in a horizontal synthesis furnace; an inert gas is introduced into the quartz tube; and under the protection of an inert gas, the horizontal synthesis furnace is heated and heated to a temperature above the melting point of the triselenization bismuth, so that The selenium telluride is subjected to a synthesis reaction to obtain a trisethanized diterpene compound; after the synthesis reaction, the horizontal synthesis furnace is cooled to room temperature to obtain a trisethanized crystal.
  • the purity of the selenium powder is 4 to 5 N
  • the particle size of the selenium powder is 50 to 300 ⁇
  • the purity of the niobium powder is 4 to 5 ⁇
  • the particle size of the tantalum powder is 50-150 ⁇ m.
  • the graphite boat is
  • the quartz tube is a 4N high purity quartz tube.
  • the inert gas is nitrogen or argon.
  • the flow rate is 0. 1 ⁇ 0. 5m 3 /h, and the access time is 10 ⁇ 30min.
  • the horizontal synthesis furnace is heated and heated to: heating at a heating rate of 10 to 15 ° C /rnin, heating to 750 to 850 ° C and holding Q . 5 ⁇ 2h.
  • the horizontal synthesis furnace is cooled to room temperature to naturally cool to room temperature.
  • the method further comprises the steps of:
  • a dust collecting hood is placed on the nozzle of the quartz tube after the graphite boat containing the mixture is placed in the quartz tube and before the quartz tube is placed in the horizontal synthesis furnace.
  • the dust collecting hood is a filter bag of a silicone oil fiberglass cloth.
  • the graphite boat is a 5N high-purity graphite boat
  • the quartz tube is a 4N high-purity quartz tube.
  • 5N tantalum powder with a particle size of 75 ⁇ m and 5N selenium powder with a particle size of 50 ⁇ m were mixed with 500g of a ratio of 2: 3. 12 to obtain a mixture; the mixture was placed in a graphite boat.
  • the graphite boat is placed in a quartz tube; the quartz tube is placed in a horizontal synthesis furnace; nitrogen gas is introduced into the quartz tube, the flow rate is 0.
  • the horizontal synthesis furnace is made to 15
  • the heating rate of °C /min is heated to 850 ° C, and incubated at 850 ° C for 0.5 h to form a tri-selenide compound; after the end of the heat, the horizontal synthesis furnace is naturally cooled to room temperature;
  • the quartz tube was taken out, and the graphite boat was taken out from the quartz tube, and finally the obtained selenite crystal was taken out from the graphite boat.
  • 4 ⁇ ⁇ powder with a particle size of 150 ⁇ and 4 ⁇ selenium powder with a particle size of 200 ⁇ m are mixed with 1000g of a ratio of 2: 3. 08 to obtain a mixture; the mixture is loaded into a graphite boat, Put the graphite boat into the quartz tube; place the quartz tube in the horizontal synthesis furnace; pass nitrogen gas into the quartz tube, the flow rate is 0.
  • the synthesis furnace is heated to 80 CTC at a heating rate of 13 ° C /min, and insulated at 800 Torr for 1.2 h to form a trisethanide compound; after the end of the heat preservation, the horizontal synthesis furnace is naturally cooled to room temperature; the nitrogen gas is stopped; The quartz tube was taken out, and the graphite boat was taken out from the quartz tube, and finally the obtained selenite crystal was taken out from the graphite boat.
  • 5N tantalum powder with a particle size of 50 ⁇ m and 4N selenium powder with a particle size of 300 ⁇ m are mixed with 1200g of a ratio of 2: 3. 05 to obtain a mixture; the mixture is loaded into a graphite boat, The graphite boat is placed in a quartz tube; the quartz tube is placed in a horizontal synthesis furnace; nitrogen gas is introduced into the quartz tube, the flow rate is 0.
  • ImVh and the introduction time is 30 minutes; then, under the protection of nitrogen gas, the horizontal synthesis furnace is made 10 Heating at a heating rate of °C /min to 750 ° C, and holding at 750 ° C for 2 h to form After the heat preservation, the horizontal synthesis furnace is cooled to room temperature; the nitrogen gas is stopped; the quartz tube is taken out, the graphite boat is taken out from the quartz tube, and finally the selenization is taken out from the graphite boat. Two crystals.
  • the triselenium difluoride crystal was detected by inductively coupled plasma mass spectrometry (ICP-MS) (manufacturer of PE company, model: DRC-I I ).
  • the test conditions of the device are: temperature 18 °C -28 °C, relative humidity is 30-70%, cleanliness is 1000.
  • Detection principle Inductively coupled plasma mass spectrometer detection method: After the element is subjected to high-temperature ionization by plasma, it enters the mass analyzer in the form of positive charge, and is received by the detector according to the difference of mass/charge ratio to generate a signal. The signal generated by the element to be tested and the reference material of the reference substance are worth the element content to be tested.
  • Table 1 shows the test results of Examples 1-3.
  • Example 1 Example 2
  • Example 3 Impurity element ⁇

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Silicon Compounds (AREA)

Abstract

Provided is a bismuth selenide preparation method, comprising the steps of: mixing selenium powder with bismuth powder in a specified molar ratio to obtain a mixture with excessive selenium; filling the mixture in a graphite boat; placing the graphite boat filled with the mixture in a quartz tube; placing the quartz tube in a horizontal synthesis furnace; aerating an inert gas into the quartz tube; under the protection of the inert gas, heating up the horizontal synthesis furnace above the melting point of the bismuth selenide, such that the selenium conducts a synthesis reaction with the bismuth to give the bismuth selenide; after the synthesis reaction, cooling the horizontal synthesis furnace to room temperature to obtain bismuth selenide crystals. The present invention has low cost, good product quality, no toxicity, and no contaminants, as well as low requirement for equipment.

Description

三硒化二锡的制备方法  Method for preparing tri-selenide di-tin
技术领域 Technical field
本发明涉及一种合成材料的制备方法， 尤其涉及一种三硒化二铋的制备 方法。 背景技术  The invention relates to a preparation method of a synthetic material, in particular to a preparation method of triselenization diterpene. Background technique
三硒化二铋分子式 Bi2Se3， 原子量 654. 8，熔点 710°C，密度 6. 82 g/cm3, 黑色或深兰色固体，具有半导体特性。是较好的替代硒化镉和硒化铅的物质， 主要用于半导体、 光电器件、 温差致冷半导体、 Bi2Se3 薄膜等。 The triselenization diterpene formula Bi 2 Se 3 , atomic weight 654.4, melting point 710 ° C, density 6. 82 g / cm 3 , black or dark blue solid, with semiconductor properties. It is a good substitute for cadmium selenide and lead selenide. It is mainly used in semiconductors, optoelectronic devices, thermoelectric cooling semiconductors, Bi 2 Se 3 films, etc.
尽管业界对三硒化二铋的制备工艺有一定开发， 但是依然需要进行工艺 开发， 以实现制备工艺对设备要求低、 成本低、 产品质量好、 无毒害、 污染 物少等。 发明内容  Although the industry has certain developments in the preparation process of triselenization diterpenoids, process development is still required to achieve low requirements on equipment, low cost, good product quality, no toxicity, and less pollution. Summary of the invention
本发明的一个目的在于提供一种三硒化二铋的制备方法， 其在制备 过程中无毒害。  SUMMARY OF THE INVENTION One object of the present invention is to provide a process for the preparation of bis(Selenide) ruthenium which is non-toxic during the preparation process.
本发明的另一目的在于提供一种三硒化二铋的制备方法， 其可减少 污染。  Another object of the present invention is to provide a process for preparing triselenosedin which can reduce contamination.
本发明的再一目的在于提供一种三硒化二铋的制备方法， 其对设备 要求低、 成本低。  A further object of the present invention is to provide a process for the preparation of bis-selenide diterpene which requires low equipment and low cost.
本发明的还一目的在于提供一种三硒化二铋的制备方法， 其可获得 的产品的质量好。  It is still another object of the present invention to provide a process for the preparation of bis-selenide diterpene which is of good quality.
为了实现本发明的目的， 本发明提供一种三硒化二铋的制备方法， 包括步骤： 将硒粉和铋粉按规定摩尔比混合， 以获得混料， 其中硒过量； 将混料装入石墨舟内； 装有混料的石墨舟放入石英管内； 将石英管置于 水平合成炉内； 向石英管内通入惰性气体； 在惰性气体保护下， 使得水 平合成炉加热升温至三硒化二铋的熔点以上， 以使硒铋和进行合成反应， 以获得三硒化二铋； 在合成反应之后， 使水平合成炉降温至室温， 以获 得三硒化二铋晶体。 In order to achieve the object of the present invention, the present invention provides a method for preparing triselenization diterpene, comprising the steps of: mixing selenium powder and niobium powder in a prescribed molar ratio to obtain a mixture in which selenium is excessive; Inside the graphite boat; the graphite boat with the mixture is placed in the quartz tube; the quartz tube is placed In the horizontal synthesis furnace; an inert gas is introduced into the quartz tube; under the protection of the inert gas, the horizontal synthesis furnace is heated to a temperature above the melting point of the triselenization bismuth, so that the selenium bismuth and the synthesis reaction are carried out to obtain the selenization铋; After the synthesis reaction, the horizontal synthesis furnace was cooled to room temperature to obtain a tri-selenide crystal.
本发明的有益效果如下。  The beneficial effects of the present invention are as follows.
根据本发明所述的三硒化二铋的制备方法， 由于反应采用惰性气体 保护， 其在制备过程中无毒害且可获得的产品质量好。  According to the preparation method of the diselenide disulphide according to the present invention, since the reaction is protected by an inert gas, it is non-toxic in the preparation process and the quality of the obtained product is good.
根据本发明所述的三硒化二铋的制备方法， 由于采用收尘罩， 可减 少硒蒸汽的挥发并可回收挥发的硒微粒， 并起到减少污染的作用。  According to the preparation method of the triselenization diterpene according to the present invention, since the dust collecting hood is used, the volatilization of the selenium vapor can be reduced and the volatile selenium particles can be recovered, and the pollution can be reduced.
根据本发明所述的三硒化二铋的制备方法， 由于采用石墨舟、 石英 管、 水平合成加热炉等， 所述制备方法其对设备要求低、 成本低。  According to the preparation method of the triselenization diterpene according to the present invention, since the graphite boat, the quartz tube, the horizontal synthesis heating furnace, and the like are used, the preparation method has low requirements on equipment and low cost.
具体实 式 Specific form
下面首先说明根据本发明的三硒化二铋的制备方法。  Next, the preparation method of the triselenization diterpene according to the present invention will be described first.
根据本发明的三硒化二铋的制备方法， 包括步骤： 将铋粉和硒粉按 规定摩尔比混合， 以获得混料， 其中硒过量； 将混料装入石墨舟内； 装 有混料的石墨舟放入石英管内； 将石英管置于水平合成炉内； 向石英管 内通入惰性气体； 在惰性气体保护下， 使水平合成炉加热升温至三硒化 二铋的熔点以上， 以使硒铋和进行合成反应， 以获得三硒化二铋化合物； 在合成反应之后， 使水平合成炉降温至室温， 以获得三硒化二铋晶体。  The preparation method of the triselenization diterpene according to the present invention comprises the steps of: mixing the niobium powder and the selenium powder in a prescribed molar ratio to obtain a mixture, wherein the selenium is excessive; the mixture is charged into the graphite boat; The graphite boat is placed in a quartz tube; the quartz tube is placed in a horizontal synthesis furnace; an inert gas is introduced into the quartz tube; and under the protection of an inert gas, the horizontal synthesis furnace is heated and heated to a temperature above the melting point of the triselenization bismuth, so that The selenium telluride is subjected to a synthesis reaction to obtain a trisethanized diterpene compound; after the synthesis reaction, the horizontal synthesis furnace is cooled to room temperature to obtain a trisethanized crystal.
在根据本发明所述的三硒化二铋的制备方法中， 优选地， 硒粉的纯 度为 4〜5N， 硒粉的粒径为 50~ 300 μ πι; 铋粉的纯度为 4〜5Ν， 铋粉的粒 径为 50—150 μ m。 In the method for preparing the bismuth selenide according to the present invention, preferably, the purity of the selenium powder is 4 to 5 N, the particle size of the selenium powder is 50 to 300 μππ ; and the purity of the niobium powder is 4 to 5 Ν. The particle size of the tantalum powder is 50-150 μm.
在根据本发明所述的三硒化二铋的制备方法中， 优选地， 规定摩尔 比为铋：硒 =2 : (3. 05〜3. 12)。 在根据本发明所述的三硒化二铋的制备方法中， 优选地， 石墨舟为In the preparation method of the bismuth selenide according to the present invention, preferably, the predetermined molar ratio is 铋: selenium = 2: (3. 05~3. 12). In the method for preparing a bismuth selenide according to the present invention, preferably, the graphite boat is
5N高纯石墨舟。 5N high purity graphite boat.
在根据本发明所述的三硒化二铋的制备方法中， 优选地， 石英管为 4N高纯石英管。  In the method for producing bismuth selenide according to the present invention, preferably, the quartz tube is a 4N high purity quartz tube.
在根据本发明所述的三硒化二铋的制备方法中， 优选地， 惰性气体 为氮气或氩气。  In the method for producing bismuth selenide according to the present invention, preferably, the inert gas is nitrogen or argon.
在根据本发明所述的三硒化二铋的制备方法中， 优选地， 向石英管 内通入惰性气体时， 流量为 0. 1〜0. 5m3/h， 通入时间为 10〜30min。 In the method of the present invention, the flow rate is 0. 1~0. 5m 3 /h, and the access time is 10~30min.
在根据本发明所述的三硒化二铋的制备方法中， 优选地， 使水平合 成炉加热升温为： 加热升温速率为 10〜15 °C /rnin， 加热至 750〜850 °C并 保温 Q. 5〜2h。  In the preparation method of the bismuth selenide according to the present invention, preferably, the horizontal synthesis furnace is heated and heated to: heating at a heating rate of 10 to 15 ° C /rnin, heating to 750 to 850 ° C and holding Q . 5~2h.
在根据本发明所述的三硒化二铋的制备方法中， 优选地， 使水平合 成炉降温至室温为自然降温至室温。  In the method for producing bismuth selenide according to the present invention, preferably, the horizontal synthesis furnace is cooled to room temperature to naturally cool to room temperature.
在根据本发明所述的三硒化二铋的制备方法中， 优选地， 还包括步 骤：  In the method for preparing a bis-selenide diterpene according to the present invention, preferably, the method further comprises the steps of:
在装有混料的石墨舟放入石英管内之后且在将石英管置于水平合成 炉内之前， 在石英管的管口上设置收尘罩。  A dust collecting hood is placed on the nozzle of the quartz tube after the graphite boat containing the mixture is placed in the quartz tube and before the quartz tube is placed in the horizontal synthesis furnace.
在根据本发明所述的三硒化二铋的制备方法中， 优选地， 所述收尘 罩为硅油玻纤布的过滤袋。  In the method for producing bismuth selenide according to the present invention, preferably, the dust collecting hood is a filter bag of a silicone oil fiberglass cloth.
下面说明本发明所述的三硒化二铋的制备方法的实施例。  Next, an embodiment of the preparation method of the triselenization diterpene according to the present invention will be described.
在下面的实施例 1-3 中， 石墨舟为 5N高纯石墨舟， 石英管为 4N高 纯石英管在装有混料的石墨舟放入石英管内之后且在将石英管置于水平 合成炉内之前在石英管的管口上将设置收尘罩， 收尘罩为硅油玻纤布的 过滤袋 实施例 1 In the following Examples 1-3, the graphite boat is a 5N high-purity graphite boat, and the quartz tube is a 4N high-purity quartz tube. After the graphite boat loaded with the mixture is placed in the quartz tube and the quartz tube is placed in the horizontal synthesis furnace A dust collecting hood will be placed on the nozzle of the quartz tube before, and the dust collecting hood is a filter bag of silicone oil fiberglass cloth. Example 1
将粒径 75 μ m的 5N铋粉和粒径为 50 μ m的 5N硒粉按摩尔比 2： 3. 12 的配比配料 500g混合， 以获得混料； 将混料装入石墨舟内， 将石墨舟放 入石英管内； 将石英管置于水平合成炉内； 向石英管内通入氮气， 流量 为 0. 5m7h且通入时间为 lOmin; 之后在氮气气体保护下， 使水平合成炉 以 15°C /min的升温速率加热升温至 850°C， 在 850°C保温 0. 5h， 以形成 三硒化二铋化合物； 保温结束后， 使使水平合成炉自然降温至室温； 停 止通氮气； 取出石英管， 再从石英管中取出石墨舟， 最后从石墨舟中取 出获得的三硒化二铋晶体。  5N tantalum powder with a particle size of 75 μm and 5N selenium powder with a particle size of 50 μm were mixed with 500g of a ratio of 2: 3. 12 to obtain a mixture; the mixture was placed in a graphite boat. The graphite boat is placed in a quartz tube; the quartz tube is placed in a horizontal synthesis furnace; nitrogen gas is introduced into the quartz tube, the flow rate is 0. 5m7h and the introduction time is lOmin; then, under the protection of nitrogen gas, the horizontal synthesis furnace is made to 15 The heating rate of °C /min is heated to 850 ° C, and incubated at 850 ° C for 0.5 h to form a tri-selenide compound; after the end of the heat, the horizontal synthesis furnace is naturally cooled to room temperature; The quartz tube was taken out, and the graphite boat was taken out from the quartz tube, and finally the obtained selenite crystal was taken out from the graphite boat.
实施例 2  Example 2
将粒径 150 μ ΐϋ 的 4Ν 铋粉和粒径为 200 μ ιη 的 4Ν 硒粉按摩尔比 2 : 3. 08 的配比配料 1000g 混合， 以获得混料； 将混料装入石墨舟内， 将石墨舟放入石英管内； 将石英管置于水平合成炉内； 向石英管内通入 氮气， 流量为 0. 3ii]3/h且通入时间为 15min; 之后在氮气气体保护下， 使 水平合成炉以 13 °C /min 的升温速率加热升温至 80CTC， 在 800Ό保温 1. 2h， 以形成三硒化二铋化合物； 保温结束后， 使使水平合成炉自然降 温至室温； 停止通氮气； 取出石英管， 再从石英管中取出石墨舟， 最后 从石墨舟中取出获得的三硒化二铋晶体。 4Ν 铋 powder with a particle size of 150 μΐϋ and 4 Ν selenium powder with a particle size of 200 μm are mixed with 1000g of a ratio of 2: 3. 08 to obtain a mixture; the mixture is loaded into a graphite boat, Put the graphite boat into the quartz tube; place the quartz tube in the horizontal synthesis furnace; pass nitrogen gas into the quartz tube, the flow rate is 0. 3ii] 3 / h and the access time is 15 min; then under the protection of nitrogen gas, make the level The synthesis furnace is heated to 80 CTC at a heating rate of 13 ° C /min, and insulated at 800 Torr for 1.2 h to form a trisethanide compound; after the end of the heat preservation, the horizontal synthesis furnace is naturally cooled to room temperature; the nitrogen gas is stopped; The quartz tube was taken out, and the graphite boat was taken out from the quartz tube, and finally the obtained selenite crystal was taken out from the graphite boat.
实施例 3  Example 3
将粒径 50 μ m的 5N铋粉和粒径为 300 μ m的 4N硒粉按摩尔比 2： 3. 05 的配比配料 1200g 混合， 以获得混料； 将混料装入石墨舟内， 将石墨舟 放入石英管内； 将石英管置于水平合成炉内； 向石英管内通入氮气， 流 量为 0. ImVh且通入时间为 30min; 之后在氮气气体保护下， 使水平合成 炉以 10°C /min的升温速率加热升温至 750°C， 在 750°C保温 2h， 以形成 三硒化二铋化合物； 保温结束后， 使使水平合成炉降自然温至室温； 停 止通氮气； 取出石英管， 再从石英管中取出石墨舟， 最后从石墨舟中取 出获得的三硒化二铋晶体。 5N tantalum powder with a particle size of 50 μm and 4N selenium powder with a particle size of 300 μm are mixed with 1200g of a ratio of 2: 3. 05 to obtain a mixture; the mixture is loaded into a graphite boat, The graphite boat is placed in a quartz tube; the quartz tube is placed in a horizontal synthesis furnace; nitrogen gas is introduced into the quartz tube, the flow rate is 0. ImVh and the introduction time is 30 minutes; then, under the protection of nitrogen gas, the horizontal synthesis furnace is made 10 Heating at a heating rate of °C /min to 750 ° C, and holding at 750 ° C for 2 h to form After the heat preservation, the horizontal synthesis furnace is cooled to room temperature; the nitrogen gas is stopped; the quartz tube is taken out, the graphite boat is taken out from the quartz tube, and finally the selenization is taken out from the graphite boat. Two crystals.
最后给出实施例 1-3 的测试结果。  Finally, the test results of Examples 1-3 are given.
三硒化二铋晶体采用电感耦合等离子体质谱仪 （ICP-MS ) 进行检测 (生产厂家为 PE公司， 型号为： DRC-I I ) ， 该设备的检测条件为： 温度 为 18 °C -28 °C， 相对湿度为 30-70%， 洁净度为 1000 级。 检测原理： 电 感耦合等离子体质谱仪检测方式： 待测元素经过等离子体高温电离后， 以正电荷形式进入质量分析器，根据质量 /电荷比的差异，被检测器接收， 产生信号。 待测元素产生的信号和标准物质该元素信号比值得出待测元 素含量。  The triselenium difluoride crystal was detected by inductively coupled plasma mass spectrometry (ICP-MS) (manufacturer of PE company, model: DRC-I I ). The test conditions of the device are: temperature 18 °C -28 °C, relative humidity is 30-70%, cleanliness is 1000. Detection principle: Inductively coupled plasma mass spectrometer detection method: After the element is subjected to high-temperature ionization by plasma, it enters the mass analyzer in the form of positive charge, and is received by the detector according to the difference of mass/charge ratio to generate a signal. The signal generated by the element to be tested and the reference material of the reference substance are worth the element content to be tested.
表 1 给出了实施例 1-3 的测试结果。  Table 1 shows the test results of Examples 1-3.
表 1 实施例 1-3 的三硒化二铋晶体测试结果 （单位： ppm) Table 1 Test results of triselenized crystals of Examples 1-3 (unit: ppm)
、\\ ^f- - a 里 , \\ ^f- - a
实施例 1 实施例 2 实施例 3 杂质元^  Example 1 Example 2 Example 3 Impurity element ^
A1 0. 4 0. 5 0. 5 A1 0. 4 0. 5 0. 5
Fe 0. 7 32. 6 13. 7Fe 0. 7 32. 6 13. 7
Cu 0. 8 17. 4 3. 4Cu 0. 8 17. 4 3. 4
S i 0. 7 0. 8 0. 7S i 0. 7 0. 8 0. 7
Zn 0. 4 4. 5 3. 1Zn 0. 4 4. 5 3. 1
Ni 0. 6 1. 3 1. 1Ni 0. 6 1. 3 1. 1
Cr 0. 7 3. 4 2. 5Cr 0. 7 3. 4 2. 5
Pb 1. 2 16. 5 6. 1 合计 5. 5 77 31. 1 从表 1可以看出， 实施例 1的三硒化二铋晶体的 度达到 5N， 实施 例 2的三硒化二铋晶体的纯度为 4N, 实施例 3的三硒化二铋晶体的纯度 为 4.5 o Pb 1. 2 16. 5 6. 1 Total 5. 5 77 31. 1 As can be seen from Table 1, the degree of the triselenization crystal of Example 1 reaches 5N, The purity of the di-selenide crystal of Example 2 was 4 N, and the purity of the tri-selenide crystal of Example 3 was 4.5 o.

Claims

1. 一种三硒化二铋的制备方法， 包括步骤： A method for preparing a triselenization diterpene, comprising the steps of:
将硒粉和铋粉按规定摩尔比混合， 以获得混料， 其中硒过量； 将混料装入石墨舟内；  Mixing the selenium powder and the niobium powder in a prescribed molar ratio to obtain a mixture in which the selenium is excessive; the mixture is charged into the graphite boat;
装有混料的石墨舟放入石英管内；  a graphite boat containing the mixture is placed in a quartz tube;
将石英管置于水平合成炉内；  Place the quartz tube in a horizontal synthesis furnace;
向石英管内通入惰性气体；  Introducing an inert gas into the quartz tube;
在惰性气体保护下， 使得水平合成炉加热升温至三硒化二铋的熔点 以上， 以使硒铋和进行合成反应， 以获得三硒化二铋；  Under the protection of an inert gas, the horizontal synthesis furnace is heated to a temperature above the melting point of the triselenization bismuth, so that the selenium bismuth and the synthesis reaction are carried out to obtain the triselenization bismuth;
在合成反应之后， 使水平合成炉降温至室温， 以获得三硒化二铋晶 体。  After the synthesis reaction, the horizontal synthesis furnace was cooled to room temperature to obtain a trisethanized twin crystal.
2. 根据权利要求 1所述的三硒化二铋的制备方法， 其特征在于， 硒 粉的纯度为 4〜5N， 硒粉的粒径为 50〜300 μ ιπ; 铋粉的纯度为 4〜5Ν， 铋 粉的粒径为 50〜150 μ m。 The method for preparing a bismuth diselenide according to claim 1, wherein the purity of the selenium powder is 4 to 5 N, the particle size of the selenium powder is 50 to 300 μm ; and the purity of the niobium powder is 4 to 2. 5Ν, the particle size of the tantalum powder is 50~150 μm.
3. 根据权利要求 1所述的三硒化二铋的制备方法， 其特征在于， 规 定摩尔比为铋：硒 =2 : (3. 05〜3. 12)。  The method of preparing the bismuth tris-selenide according to claim 1, wherein the predetermined molar ratio is 铋: selenium = 2: (3. 05~3. 12).
4. 根据权利要求 1所述的三硒化二铋的制备方法， 其特征在于， 石 墨舟为 5N高纯石墨舟， 石英管为 4N高纯石英管， 惰性气体为氮气或氩 气。  The method for preparing a bismuth selenide according to claim 1, wherein the graphite boat is a 5N high-purity graphite boat, the quartz tube is a 4N high-purity quartz tube, and the inert gas is nitrogen or argon.
5. 根据权利要求 1所述的三硒化二铋的制备方法， 其特征在于， 向 石英管内通入惰性气体时，流量为 0. 1〜0. 5m3/h，通入时间为 10〜30min。  〜5. 5m3/h, access time is 10~30min, when the inert gas is introduced into the quartz tube, the flow rate is 0. 1~0. 5m3/h, the access time is 10~30min .
6. 根据权利要求 1所述的三硒化二铋的制备方法， 其特征在于， 使 水平合成炉加热升温为： 加热升温速率为 10〜15°C /min， 加热至 750〜 850 °C并保温 0. 5〜2h。  The method for preparing a bismuth selenide according to claim 1, wherein the temperature of the horizontal synthesis furnace is heated to: heating at a temperature of 10 to 15 ° C /min, and heating to 750 to 850 ° C. 5〜2小时。 Insulation 0. 5~2h.
7. 根据权利要求 1所述的三硒化二铋的制备方法， 其特征在于， 使 水平合成炉降温至室温为使水平合成炉自然降温至室温。 7. The method for preparing bismuth selenide according to claim 1, wherein the horizontal synthesis furnace is cooled to room temperature to naturally cool the horizontal synthesis furnace to room temperature.
8. 根据权利要求 1所述的三硒化二铋的制备方法， 其特征在于， 还 包括步骤： 在装有混料的石墨舟放入石英管内之后且在将石英管置于水 平合成炉内之前， 在石英管的管口上设置收尘罩。 8. The method according to claim 1, further comprising the steps of: after placing the graphite boat containing the mixture into the quartz tube and placing the quartz tube in the horizontal synthesis furnace Previously, a dust collecting hood was placed on the nozzle of the quartz tube.
9. 根据权利要求 8所述的三硒化二铋的制备方法， 其特征在于， 所 述收尘罩为硅油玻纤布的过滤袋。  The method for preparing a bismuth diselenide according to claim 8, wherein the dust collecting hood is a filter bag of a silicone oil fiberglass cloth.
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