CN108358177A - A kind of high temperature and high pressure preparation process of zinc selenide polycrystalline bulk material - Google Patents
A kind of high temperature and high pressure preparation process of zinc selenide polycrystalline bulk material Download PDFInfo
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- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000013590 bulk material Substances 0.000 title claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 43
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 43
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000012774 insulation material Substances 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003287 optical effect Effects 0.000 abstract description 8
- 238000005245 sintering Methods 0.000 abstract description 8
- 239000011787 zinc oxide Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000011669 selenium Substances 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000002834 transmittance Methods 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005083 Zinc sulfide Substances 0.000 abstract description 2
- 238000007731 hot pressing Methods 0.000 abstract description 2
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 238000004321 preservation Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 2
- 229910052903 pyrophyllite Inorganic materials 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
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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
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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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
本发明提供的一种硒化锌多晶块体材料的高温高压制备方法，其以硒粉(Se)和锌粉(Zn)两种单质为原料，经原料混合、压块、组装、高温高压合成、冷却卸压的工艺过程制得二碳化钼钨块状材料；本发明采用高温高压合成方法制备高纯度、高透过率硒化锌光学材料；通过优化质量配比和调节合成温度、压力来调整硒化锌的材料组分及纯度，制备出高纯度块体硒化锌光学材料；本发明工艺流程简单,不需要锌的氧化物和硫化物做为原料；通过调节单质原料的配比、温度和压力来提高硒化锌的纯度，并制备出了较高纯度的块体硒化锌材料；此外，本发明大大缩短了传统热压烧结法的制备周期和烧结的时间，合成的块体材料有利于优化其光学性能。
The invention provides a high-temperature and high-pressure preparation method for a zinc selenide polycrystalline block material, which uses two simple substances of selenium powder (Se) and zinc powder (Zn) as raw materials, and undergoes raw material mixing, briquetting, assembly, high temperature and high pressure Molybdenum tungsten carbide block materials are obtained through the process of synthesis, cooling and pressure relief; the present invention adopts a high-temperature and high-pressure synthesis method to prepare high-purity, high-transmittance zinc selenide optical materials; by optimizing the mass ratio and adjusting the synthesis temperature and pressure to adjust the material components and purity of zinc selenide, and prepare high-purity bulk zinc selenide optical materials; the process of the invention is simple, and does not require zinc oxide and sulfide as raw materials; by adjusting the ratio of simple raw materials , temperature and pressure to improve the purity of zinc selenide, and prepared a higher purity bulk zinc selenide material; in addition, the present invention greatly shortens the preparation cycle and sintering time of the traditional hot pressing sintering method, and the synthesized block Bulk materials are beneficial to optimize their optical properties.
Description
技术领域technical field
本发明涉及锂离子电池正极材料的改性方法，特别涉及一种硒化锌多晶块体材料的高温高压制备方法。The invention relates to a modification method of a positive electrode material of a lithium ion battery, in particular to a high-temperature and high-pressure preparation method of a zinc selenide polycrystalline bulk material.
背景技术Background technique
硒化锌材料是Ⅱ-Ⅵ族半导体发光基质材料，其性能优异，具有能带间隙宽、高折射率、高透光率等特点，广泛应用于物理学、光学、传感器、光电材料等领域。ZnSe的本征发射处于蓝光区或者绿光区，特别是在可见光范围内具有优异的光电催化及光电转化活性，以及良好的透射性能和稳定的折射性能，使得ZnSe成为制造光电器件的理想材料之一。硒化锌材料在传统的光电应用方面具有不可替代的优势，例如:蓝色发光器件、红外热成像仪、全天候光学装置、短波长激光器以及透射窗口材料等，无论是在基础研究还是实际应用方面都有着极为广阔的应用前景。Zinc selenide material is a II-VI semiconductor light-emitting matrix material with excellent performance, wide energy band gap, high refractive index, high light transmittance, etc. It is widely used in physics, optics, sensors, optoelectronic materials and other fields. The intrinsic emission of ZnSe is in the blue or green light region, especially in the visible light range, it has excellent photocatalytic and photoelectric conversion activity, as well as good transmission performance and stable refraction performance, making ZnSe one of the ideal materials for manufacturing optoelectronic devices. one. Zinc selenide materials have irreplaceable advantages in traditional optoelectronic applications, such as: blue light-emitting devices, infrared thermal imagers, all-weather optical devices, short-wavelength lasers, and transmission window materials, whether in basic research or practical applications All have very broad application prospects.
硒化锌块体材料合成方法主要有化学气相沉积法和真空烧结法。利用气相沉积法制备的硒化锌晶体散射损失低而且杂质吸收非常少、甚至几乎没有。真空烧结法制备硒化锌是由两种或者两种以上不同的锌化物和硒粉烧结制备而成。即制备这类材料，首先需要制备出不同的锌化物原材料，其次还需要混料、热压高温烧结等复杂的技术环节。因此，制备过程中不同锌化物原材料的粒径、混合均匀性等因素对最终制备的硒化锌材料性能有很大的影响。直接利用单质元素，利用高温高压法制备高纯度硒化锌块体材料，还未见报道。发展一种新的制备方法，对于提高该类光学材料的性能，推广其应用均有十分重要的意义。The synthesis methods of zinc selenide bulk materials mainly include chemical vapor deposition and vacuum sintering. The zinc selenide crystal prepared by the vapor deposition method has low scattering loss and very little or even almost no impurity absorption. Zinc selenide prepared by vacuum sintering method is prepared by sintering two or more different zinc compounds and selenium powder. That is to say, to prepare such materials, firstly, different zinc oxide raw materials need to be prepared, and secondly, complex technical links such as material mixing, hot-pressing and high-temperature sintering are required. Therefore, factors such as particle size and mixing uniformity of different zinc oxide raw materials in the preparation process have a great influence on the performance of the final prepared zinc selenide material. It has not been reported that high-purity zinc selenide bulk materials are prepared directly by simple elements and by high-temperature and high-pressure methods. The development of a new preparation method is of great significance for improving the performance of this type of optical material and promoting its application.
发明内容Contents of the invention
本发明提供一种硒化锌多晶块体材料的高温高压制备方法包括如下步骤：The invention provides a high-temperature and high-pressure preparation method of a zinc selenide polycrystalline bulk material comprising the following steps:
步骤一:将分析纯粒度1～5微米的硒粉与粒度1～5微米的锌粉按摩尔比1∶1充分混合，之后利用液压机按合成腔体大小将混合物压成圆柱状的样品；Step 1: fully mix the selenium powder with a particle size of 1 to 5 microns and the zinc powder with a particle size of 1 to 5 microns in a molar ratio of 1:1, then use a hydraulic press to press the mixture into a cylindrical sample according to the size of the synthesis cavity;
步骤二:将步骤一中挤压成型的样品装入加热容器当中；之后将加热容器放入合成腔体中对样品进行高温高压合成；所述的高温高压合成，所述的高温高压合成，条件是:压力为2.0～6.0GPa、温度为1300～1700K,保温保压15～60分钟；Step 2: put the sample extruded in step 1 into the heating container; then put the heating container into the synthesis cavity to perform high-temperature and high-pressure synthesis on the sample; the high-temperature and high-pressure synthesis, the high-temperature and high-pressure synthesis, the conditions Yes: the pressure is 2.0-6.0GPa, the temperature is 1300-1700K, and the heat preservation and pressure are maintained for 15-60 minutes;
步骤三:待步骤二中的样品完成高温高压合成后,停止对加热容器的通电加热,待样品在加热容器内自然冷却至常温后，卸压即得到硒化锌块状材料。Step 3: After the high temperature and high pressure synthesis of the sample in step 2 is completed, the heating of the heating container is stopped, and after the sample is naturally cooled to normal temperature in the heating container, the zinc selenide bulk material is obtained by releasing the pressure.
优选的，所述步骤二中的加热容器内部采用石墨热管,其外部采用叶腊石做保温材料，利用六角氮化硼保护腔体。Preferably, graphite heat pipe is used inside the heating container in the step 2, and pyrophyllite is used as insulation material outside, and hexagonal boron nitride is used to protect the cavity.
优选的，所述步骤二中合成压力值为3.0GPa，合成温度为1300K，保温保压时间为15分钟。Preferably, in the second step, the synthesis pressure value is 3.0 GPa, the synthesis temperature is 1300K, and the heat preservation and pressure holding time is 15 minutes.
优选的，所述步骤二中合成压力值为3.0GPa，合成温度为1300K，保温保压时间为30分钟。Preferably, in the second step, the synthesis pressure value is 3.0 GPa, the synthesis temperature is 1300K, and the heat preservation and pressure holding time is 30 minutes.
优选的，所述步骤二中合成压力值为3.0GPa，合成温度为1500K，保温保压时间为30分钟。Preferably, in the second step, the synthesis pressure value is 3.0 GPa, the synthesis temperature is 1500K, and the heat preservation and pressure holding time is 30 minutes.
优选的，所述步骤二中合成压力值为3.0GPa，合成温度为1700K，保温保压时间为30分钟。Preferably, in the second step, the synthesis pressure value is 3.0 GPa, the synthesis temperature is 1700K, and the heat preservation and pressure holding time is 30 minutes.
优选的，所述步骤二中合成压力值为3.0GPa，合成温度为1700K，保温保压时间为60分钟。Preferably, in the second step, the synthesis pressure value is 3.0 GPa, the synthesis temperature is 1700K, and the heat preservation and pressure holding time is 60 minutes.
本发明采用高温高压合成方法制备高纯度、高透过率硒化锌光学材料；该方法不需要硒粉——氧化锌和硫化锌——做为原料、直接以硒粉和锌粉单质为原料，通过优化质量配比和调节合成温度、压力来调整硒化锌的材料组分及纯度，制备出高纯度块体硒化锌光学材料；本发明工艺流程简单,不需要锌的氧化物和硫化物做为原料；通过调节单质原料的配比、温度和压力来提高硒化锌的纯度，并制备出了较高纯度的块体硒化锌材料；此外，本发明大大缩短了传统热压烧结法的制备周期和烧结的时间，合成的块体材料有利于优化其光学性能。The invention adopts a high-temperature and high-pressure synthesis method to prepare high-purity, high-transmittance zinc selenide optical materials; the method does not need selenium powder——zinc oxide and zinc sulfide—as raw materials, and directly uses selenium powder and zinc powder as raw materials , adjust the material composition and purity of zinc selenide by optimizing the mass ratio and adjusting the synthesis temperature and pressure to prepare a high-purity bulk zinc selenide optical material; the process of the invention is simple and does not require zinc oxide and sulfide material as a raw material; the purity of zinc selenide is improved by adjusting the ratio, temperature and pressure of the elemental raw material, and a higher-purity bulk zinc selenide material is prepared; in addition, the present invention greatly shortens the time required for traditional hot-press sintering The preparation cycle of the method and the time of sintering, the synthesized bulk material is conducive to optimizing its optical properties.
附图说明Description of drawings
图1是实施例1制备的硒化锌X光衍射图；Fig. 1 is the zinc selenide X-ray diffraction pattern that embodiment 1 prepares;
图2是实施例2制备的硒化锌X光衍射图；Fig. 2 is the zinc selenide X-ray diffraction figure that embodiment 2 prepares;
图3是实施例3制备的硒化锌X光衍射图；Fig. 3 is the zinc selenide X-ray diffraction figure that embodiment 3 prepares;
图4是实施例4制备的硒化锌X光衍射图；Fig. 4 is the zinc selenide X-ray diffraction figure that embodiment 4 prepares;
图5是实施例5制备的硒化锌X光衍射图；Fig. 5 is the zinc selenide X-ray diffraction figure that embodiment 5 prepares;
图6是实施例1制备的硒化锌透射电镜能谱图；Fig. 6 is the zinc selenide transmission electron microscope energy spectrum figure prepared by embodiment 1;
图7是实施例2制备的硒化锌透射电镜能谱图；Fig. 7 is the zinc selenide transmission electron microscope energy spectrogram that embodiment 2 prepares;
图8是实施例3制备的硒化锌透射电镜能谱图；Fig. 8 is the zinc selenide transmission electron microscope energy spectrogram prepared by embodiment 3;
图9是实施例4制备的硒化锌透射电镜能谱图；Fig. 9 is the zinc selenide transmission electron microscope energy spectrum figure prepared by embodiment 4;
图10是实施例5制备的硒化锌透射电镜能谱图。Fig. 10 is a transmission electron microscope energy spectrum diagram of zinc selenide prepared in Example 5.
具体实施方式Detailed ways
下面对本发明的一个具体实施方式进行详细描述，但应当理解本发明的保护范围并不受具体实施方式的限制。A specific embodiment of the present invention will be described in detail below, but it should be understood that the protection scope of the present invention is not limited by the specific embodiment.
本发明实施例提供的一种硒化锌多晶块体材料的高温高压制备方法；A high temperature and high pressure preparation method of zinc selenide polycrystalline bulk material provided by the embodiment of the present invention;
实施例1Example 1
将分析纯粒度1～5微米的硒粉(Se)与粒度1～5微米的锌粉(Zn)按摩尔比1∶1充分混合，利用液压机粉压成型后，将样品装入合成腔体当中；组装腔体中采用石墨热管，用叶腊石做保温材料，利用六角氮化硼保护腔体，合成压力为3.0GPa，合成温度为1300K，保温保压时间为15分钟，停止加热后样品自然冷却至室温后卸压，此条件制备出的硒化锌具体的X光衍射结果见图1，透射能谱结果见图6。Fully mix the analytically pure selenium powder (Se) with a particle size of 1 to 5 microns and the zinc powder (Zn) with a particle size of 1 to 5 microns at a molar ratio of 1:1, use a hydraulic press to form the powder, and then put the sample into the synthesis chamber ;The graphite heat pipe is used in the assembly chamber, pyrophyllite is used as the insulation material, and hexagonal boron nitride is used to protect the chamber. The synthesis pressure is 3.0GPa, the synthesis temperature is 1300K, and the heat preservation and pressure holding time is 15 minutes. After the heating is stopped, the sample is naturally cooled to After the pressure is released at room temperature, the specific X-ray diffraction results of the zinc selenide prepared under this condition are shown in Figure 1, and the transmission energy spectrum results are shown in Figure 6.
实施例2Example 2
采用与实施例1相同的原材料，按照按摩尔比1∶1混合，粉样品压制成型后采用与实施例1相同的组装，合成压力为3.0GPa，合成温度为1300K，保压保温时间30分钟，停止加热后样品自然冷却至室温后卸压，此条件制备出纯相硒化锌。结合以上两例可以知道，增加时间可以提高硒化锌结晶度。具体的X光衍射结果见图2，透射能谱结果见图7。Using the same raw materials as in Example 1, mixed according to the molar ratio of 1: 1, the powder sample was compressed and formed using the same assembly as in Example 1, the synthesis pressure was 3.0GPa, the synthesis temperature was 1300K, and the pressure holding time was 30 minutes. After the heating was stopped, the sample was naturally cooled to room temperature and then the pressure was released. Under this condition, pure phase zinc selenide was prepared. Combining the above two examples, it can be known that increasing the time can improve the crystallinity of zinc selenide. The specific X-ray diffraction results are shown in Figure 2, and the transmission energy spectrum results are shown in Figure 7.
实施例3Example 3
采用与实施例1相同的原材料，按照按摩尔比1：1混合，粉样品压制成型后采用与实施例1相同的组装，合成压力为3.0GPa，合成温度为1500K，保压保温时间30分钟，停止加热后样品自然冷却至室温后卸压。此条件下合成出了纯度较高的硒化锌。具体的X光衍射结果见图3，透射能谱结果见图8。Using the same raw materials as in Example 1, mixed according to the molar ratio of 1:1, the powder sample was pressed and formed using the same assembly as in Example 1, the synthesis pressure was 3.0GPa, the synthesis temperature was 1500K, and the holding time was 30 minutes. After the heating was stopped, the sample was naturally cooled to room temperature and then the pressure was released. Under this condition, zinc selenide with higher purity was synthesized. The specific X-ray diffraction results are shown in Figure 3, and the transmission energy spectrum results are shown in Figure 8.
实施例4Example 4
采用与实施例1相同的原材料，按照按摩尔比1：1混合，粉样品压制成型后采用与实施例1相同的组装，合成压力为3.0GPa，合成温度为1700K，保压保温时间30分钟，停止加热后样品自然冷却至室温后卸压。此条件下制备出的硒化锌纯度与实例2和实例3相比有所降低。具体的X光衍射结果见图4，透射能谱结果见图9。Using the same raw materials as in Example 1, mixed according to the molar ratio of 1:1, the powder sample was pressed and formed using the same assembly as in Example 1, the synthesis pressure was 3.0GPa, the synthesis temperature was 1700K, and the holding time was 30 minutes. After the heating was stopped, the sample was naturally cooled to room temperature and then the pressure was released. The zinc selenide purity prepared under this condition is compared with example 2 and example 3 and reduces to some extent. The specific X-ray diffraction results are shown in Figure 4, and the transmission energy spectrum results are shown in Figure 9.
实施例5Example 5
采用与实施例1相同的原材料，按照按摩尔比1∶1混合，粉样品压制成型后采用与实施例1相同的组装，合成压力为3.0GPa，合成温度为1700K，保压保温时间60分钟，停止加热后样品自然冷却至室温后卸压。此条件下制备出的硒化锌纯度与实例2和实例3相比有所降低。具体的X光衍射结果见图5。和碳化钼钨的杂质，具体的X光衍射结果见图5，透射能谱结果见图10。Adopt the raw material identical with embodiment 1, mix according to molar ratio 1: 1, adopt the assembly identical with embodiment 1 after powder sample compression molding, synthetic pressure is 3.0GPa, and synthetic temperature is 1700K, and holding pressure heat preservation time is 60 minutes, After the heating was stopped, the sample was naturally cooled to room temperature and then the pressure was released. The zinc selenide purity prepared under this condition is compared with example 2 and example 3 and reduces to some extent. The specific X-ray diffraction results are shown in Figure 5. and molybdenum tungsten carbide impurities, the specific X-ray diffraction results are shown in Figure 5, and the transmission energy spectrum results are shown in Figure 10.
本发明的实验是在国产SPD6×1200型六面顶压机上完成，实验结果表明，合成压力的大小、温度、原材料的配比是影响合成的硒化锌纯度和性质的重要因素。由实施例1～5可以看出，优选的制备条件是：硒粉和锌粉按摩尔比1∶1，合成压力范围为3.0GPa，合成温度范围为1300～1700K，保温保压15～60分钟；为了保证在合成样品的过程当中合成腔体温度的均匀性，本方法采用的加热方式是通电石墨管旁热式加热；为了保证样品不与产生热量的石墨管发生反应，合成样品的腔体采用六角氮化硼保护。The experiment of the present invention is completed on the domestic SPD6 * 1200 type six-sided top press, and the experimental results show that the size of the synthesis pressure, temperature, and the ratio of raw materials are important factors that affect the purity and properties of the synthesized zinc selenide. As can be seen from Examples 1 to 5, the preferred preparation conditions are: the molar ratio of selenium powder and zinc powder is 1: 1, the synthetic pressure range is 3.0GPa, the synthetic temperature range is 1300～1700K, and the heat preservation and pressure holding time is 15～60 minutes ; In order to ensure the uniformity of the temperature of the synthetic cavity in the process of synthesizing the sample, the heating method adopted in this method is the side heating of the energized graphite tube; in order to ensure that the sample does not react with the graphite tube that generates heat, the cavity of the synthetic sample Protected with hexagonal boron nitride.
以上公开的仅为本发明的具体实施例，但是，本发明实施例并非局限于此，任何本领域的技术人员能思之的变化都应落入本发明的保护范围。The above disclosures are only specific embodiments of the present invention, but the embodiments of the present invention are not limited thereto, and any changes conceivable by those skilled in the art shall fall within the protection scope of the present invention.
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| CN115417452A (en) * | 2022-10-19 | 2022-12-02 | 铜仁学院 | A method for improving the fusion synthesis method to produce zinc arsenide |
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