CN113555459B - Selenium sulfide doped copper oxide with strong luminescence characteristic - Google Patents
Selenium sulfide doped copper oxide with strong luminescence characteristic Download PDFInfo
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- CN113555459B CN113555459B CN202110820587.0A CN202110820587A CN113555459B CN 113555459 B CN113555459 B CN 113555459B CN 202110820587 A CN202110820587 A CN 202110820587A CN 113555459 B CN113555459 B CN 113555459B
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- cuo
- copper oxide
- doped copper
- ses
- selenium sulfide
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 26
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 26
- 229960005265 selenium sulfide Drugs 0.000 title claims abstract description 22
- 238000004020 luminiscence type Methods 0.000 title claims abstract description 10
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical compound [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000000137 annealing Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims 1
- 238000005424 photoluminescence Methods 0.000 abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052581 Si3N4 Inorganic materials 0.000 abstract 1
- 238000004151 rapid thermal annealing Methods 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 abstract 1
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 1
- JNMWHTHYDQTDQZ-UHFFFAOYSA-N selenium sulfide Chemical compound S=[Se]=S JNMWHTHYDQTDQZ-UHFFFAOYSA-N 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910000338 selenium disulfide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0321—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 characterised by the doping material
-
- 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
- C01B19/04—Binary compounds including binary selenium-tellurium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses selenium sulfide doped copper oxide with strong luminescence property, which is prepared by firstly utilizing a powder tabletting method to mix CuO powder and SeS 2 The powder is mixed and tabletted according to the molar ratio of 4: 1-12: 1 to form a wafer, and then the obtained wafer is subjected to rapid thermal annealing treatment at 450-650 ℃ for 2-10 min to prepare the silicon nitride/silicon oxide/silicon. SeS is doped in CuO 2 Modifying to improve the photoelectric property of CuO and to dope SeS 2 The photoluminescence intensity of the CuO material can reach about 14 times of the photoelectric property of the pure CuO material, and the material is expected to become a novel material in the field of photoelectric property materials.
Description
Technical Field
The invention belongs to the technical field of semiconductor photoelectric materials, and particularly relates to selenium sulfide doped copper oxide with strong luminescence property.
Background
Semiconductor materials play an increasingly important role in the field of optoelectronics. However, high performance single crystal semiconductor materials are expensive to fabricate, limiting their wide-scale application. The amorphous or nanocrystalline material has low production cost and is suitable for large-scale application.
Copper oxide (CuO) is a p-type semiconductor material, is black, belongs to a monoclinic system, is a typical transition metal oxide, and has rich earth resources and low toxicity. And CuO has a very ideal band gap (1.4eV) and a very high light absorption coefficient. However, CuO has a high melting point (1446 ℃ C.), and decomposes around the melting point. At present, the main preparation methods of CuO semiconductor materials include a magnetron sputtering method, a gel method, a hydrothermal method and the like. CuO prepared by the methods is mostly in an amorphous and nanocrystalline structure, has more defects and serious carrier recombination, and seriously limits the application of the CuO in the photoelectric field. Therefore, there is a need to develop a doping method that can maintain the CuO in the amorphous or nano-crystalline state with good photoelectric properties.
Disclosure of Invention
The invention aims to overcome the problems of a CuO semiconductor material and provide selenium sulfide doped copper oxide with strong luminescence property.
Aiming at the purposes, the selenium sulfide doped copper oxide with strong luminescence property is prepared by the following method: mixing CuO powder with SeS 2 The powder is fully mixed according to the molar ratio of 4: 1-12: 1, then tabletting is carried out, and annealing is carried out at 450-650 ℃ for 2-10 min.
In the above production method, CuO powder and SeS are preferably used 2 And fully mixing the powder according to the molar ratio of 6: 1-10: 1, and tabletting.
In the preparation method, the pressed sheet is kept for 8-10 s under the pressure of 12-15 MPa to form a wafer with the thickness of 0.6-1.0 mm.
In the above preparation method, annealing at 500 to 600 ℃ is further preferably performed for 3 to 5 min.
The invention has the following beneficial effects:
1. the invention is characterized in that a small amount of SeS is doped 2 The method is simple, convenient, low in cost and applicable to large-scale application. Firstly, CuO and SeS with different molar ratios are mixed 2 Mixing and tabletting through a simple machine, and then annealing CuO and SeS by adopting an annealing furnace 2 Fully mixed and reacted to form CuO and SeS 2 To obtain a new semiconductor composite material. The photoelectric performance of the composite material can reach the highest independently annealed CuO and SeS 2 About 14 times.
2. The CuO semiconductor material adopted by the invention comprises: high light absorption coefficient, stable chemical property, rich earth reserves, low manufacturing cost, non-harsh synthesis conditions, wide temperature window and the like, and is very suitable for large-scale application. And SeS 2 As a common chemical, the compound also has the advantages of low cost, abundant reserves, non-harsh preparation conditions and the like.
Drawings
Figure 1 is a PL profile of selenium sulfide doped copper oxide prepared in example 1.
Figure 2 is an XRD pattern of selenium sulphide doped copper oxide prepared in example 1.
Figure 3 is a PL profile of the selenium sulfide doped copper oxide prepared in example 2.
Figure 4 is an XRD pattern of selenium sulphide doped copper oxide prepared in example 2.
Figure 5 is a PL profile of selenium sulfide doped copper oxide prepared in example 3.
Figure 6 is an XRD pattern of selenium sulphide doped copper oxide prepared in example 3.
Figure 7 is a PL profile of selenium sulfide doped copper oxide prepared in example 4.
Figure 8 is an XRD pattern of the selenium disulfide doped copper oxide prepared in example 4.
Figure 9 is a PL profile of selenium sulfide doped copper oxide prepared in example 5.
Figure 10 is an XRD pattern of selenium sulfide doped copper oxide prepared in example 5.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited to these examples.
Example 1
Mixing CuO powder with SeS 2 Fully grinding and mixing the powder according to a molar ratio of 4:1, and then tabletting by using a tabletting machine under the pressure of 15MPa for 8-10 s to form a wafer with the thickness of 0.6-0.8 mm. And (3) annealing the wafer on quartz glass in an annealing furnace at the annealing temperature of 500 ℃ for 3min to obtain the selenium sulfide doped copper oxide.
Photoluminescence (PL) and X-ray diffraction (XRD) characterization was performed on this material, and the results are shown in fig. 1 and fig. 2. The PL test results in fig. 1 show that the PL peak intensity of the resulting material is 5.38 times that of CuO alone at the same annealing temperature and time (the peak intensity is 701 times that of the original CuO alone)Up to 3772). XRD testing of FIG. 2 shows that a large amount of CuO and newly formed CuSe exist in the obtained material 2 。
Example 2
Mixing CuO powder with SeS 2 Fully grinding and mixing the powder according to the molar ratio of 6:1, and then tabletting by using a tabletting machine under the pressure of 15MPa for 8-10 s to form a wafer with the thickness of 0.6-0.8 mm. And (3) annealing the wafer on quartz glass in an annealing furnace at the annealing temperature of 500 ℃ for 3min to obtain the selenium sulfide doped copper oxide.
Photoluminescence (PL) and X-ray diffraction (XRD) characterization was performed on this material, and the results are shown in fig. 3 and 4. The PL test results of fig. 3 show that the PL peak intensity of the resulting material is 7.82 times higher than CuO alone at the same annealing temperature and time (the peak intensity increases from 701 to 5483). XRD testing of FIG. 4 shows that a significant amount of CuO and newly formed CuSe are present in the resulting material 2 。
Example 3
Mixing CuO powder with SeS 2 Fully grinding and mixing the powder according to a molar ratio of 10:1, and then tabletting by using a tabletting machine under the pressure of 15MPa for 8-10 s to form a wafer with the thickness of 0.6-0.8 mm. And (3) annealing the wafer on quartz glass in an annealing furnace at the annealing temperature of 500 ℃ for 3min to obtain the selenium sulfide doped copper oxide.
Photoluminescence (PL) and X-ray diffraction (XRD) characterization was performed on this material, and the results are shown in fig. 5 and 6. The PL test results of fig. 5 show that the PL peak intensity of the resulting material is 8.81 times higher than CuO alone at the same annealing temperature and time (the peak intensity increases from 701 to 6174). XRD testing of FIG. 6 shows that the resulting material contains a significant amount of CuO and newly formed Cu 5 Se 4 And Cu 7 Se 4 。
Example 4
Mixing CuO powder with SeS 2 Fully grinding and mixing the powder according to the molar ratio of 6:1, and then tabletting by using a tabletting machine under the pressure of 15MPa for 8-10 s to form a wafer with the thickness of 0.6-0.8 mm. The obtained wafer is placed on quartz glass and annealed in an annealing furnace at the annealing temperature of 600 ℃ for 3min to obtain the disulfideSelenium doped copper oxide.
Photoluminescence (PL) and X-ray diffraction (XRD) characterization was performed on this material, and the results are shown in fig. 7 and 8. The PL test results of fig. 7 show that the PL peak intensity of the resulting material is 13.91 times higher than CuO alone at the same annealing temperature and time (the peak intensity increases from 1483 to 20633). XRD testing of FIG. 4 shows that a significant amount of CuO and newly formed CuSe are present in the resulting material 2 And Cu 7 Se 4 。
Example 5
Mixing CuO powder with SeS 2 Fully grinding and mixing the powder according to the molar ratio of 12:1, and then tabletting by using a tabletting machine under the pressure of 15MPa for 8-10 s to form a wafer with the thickness of 0.6-0.8 mm. And (3) annealing the wafer on quartz glass in an annealing furnace at the annealing temperature of 500 ℃ for 3min to obtain the selenium sulfide doped copper oxide.
Photoluminescence (PL) and X-ray diffraction (XRD) characterization was performed on this material, and the results are shown in fig. 9 and 10. The PL test results in fig. 9 show that the PL peak intensity of the resulting material is 3.59 times higher than CuO alone at the same annealing temperature and time (the peak intensity increases from 701 to 2517). XRD testing of FIG. 10 shows that the resulting material contains a significant amount of CuO and newly formed Cu 2 S。
Example 6
Mixing CuO powder with SeS 2 Fully grinding and mixing the powder according to the molar ratio of 8:1, and then tabletting by using a tabletting machine under the pressure of 15MPa for 8-10 s to form a wafer with the thickness of 0.6-0.8 mm. And placing the obtained wafer on quartz glass, and annealing in an annealing furnace at the annealing temperature of 650 ℃ for 3min to obtain the selenium sulfide doped copper oxide.
Photoluminescence (PL) characterization is carried out on the material, and PL test results show that the PL peak intensity of the obtained material is 2.09 times that of CuO alone at the same annealing temperature and time (the peak intensity is increased to 3241 from 1554 originally).
Claims (4)
1. The selenium sulfide doped copper oxide with strong luminescence property is characterized in that the material is prepared by the following method: mixing CuO powder with SeS 2 Powder according to moleFully mixing the raw materials according to the ratio of 4: 1-12: 1, tabletting, and annealing at 500-650 ℃ for 2-10 min.
2. The selenium sulfide doped copper oxide with strong luminescence property of claim 1, wherein: mixing CuO powder with SeS 2 And fully mixing the powder according to the molar ratio of 6: 1-10: 1, and tabletting.
3. The selenium sulfide doped copper oxide with strong luminescence property of claim 1 or 2, wherein: the tabletting is kept for 8-10 s under the pressure of 12-15 MPa to form a wafer with the thickness of 0.6-1.0 mm.
4. The selenium sulfide doped copper oxide with strong luminescence property of claim 1 or 2, wherein: annealing at 500-600 ℃ for 3-5 min.
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| US5731031A (en) * | 1995-12-20 | 1998-03-24 | Midwest Research Institute | Production of films and powders for semiconductor device applications |
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| US5731031A (en) * | 1995-12-20 | 1998-03-24 | Midwest Research Institute | Production of films and powders for semiconductor device applications |
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