CN115029129B - Luminescent ion doped silicon dioxide fluorescent powder and preparation method thereof - Google Patents
Luminescent ion doped silicon dioxide fluorescent powder and preparation method thereof Download PDFInfo
- Publication number
- CN115029129B CN115029129B CN202210719399.3A CN202210719399A CN115029129B CN 115029129 B CN115029129 B CN 115029129B CN 202210719399 A CN202210719399 A CN 202210719399A CN 115029129 B CN115029129 B CN 115029129B
- Authority
- CN
- China
- Prior art keywords
- silicon dioxide
- reaction chamber
- rare earth
- powder
- reaction
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 106
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 64
- 239000000843 powder Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 50
- 150000003624 transition metals Chemical class 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 29
- 239000010439 graphite Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052786 argon Inorganic materials 0.000 claims abstract description 5
- 238000010891 electric arc Methods 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 238000009833 condensation Methods 0.000 claims description 24
- 230000005494 condensation Effects 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000002070 nanowire Substances 0.000 abstract description 69
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 59
- 150000002910 rare earth metals Chemical class 0.000 abstract description 45
- 208000028659 discharge Diseases 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 29
- 239000000047 product Substances 0.000 abstract description 15
- 239000011159 matrix material Substances 0.000 abstract description 7
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 description 23
- 230000005284 excitation Effects 0.000 description 17
- 239000000498 cooling water Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 15
- 229910052721 tungsten Inorganic materials 0.000 description 15
- 239000010937 tungsten Substances 0.000 description 15
- 238000000103 photoluminescence spectrum Methods 0.000 description 14
- -1 rare earth ions Chemical class 0.000 description 11
- 230000007704 transition Effects 0.000 description 9
- 238000000295 emission spectrum Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000004005 microsphere Substances 0.000 description 6
- 238000000695 excitation spectrum Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910001428 transition metal ion Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000593 microemulsion method Methods 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77342—Silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
- C09K11/7442—Aluminates; Silicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/77062—Silicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
- C09K11/77212—Silicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
- C09K11/77492—Silicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7759—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing samarium
- C09K11/7764—Aluminates; Silicates
-
- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides luminescent ion doped silicon dioxide fluorescent powder and a preparation method thereof, relates to the technical field of luminescent materials, and mainly aims to realize a novel method for adjusting luminescent properties of doping of different rare earth or transition metals by the same matrix material and preparing amorphous silicon dioxide nanowires. The preparation method comprises the following steps: (1) Placing a reaction raw material containing silicon dioxide powder and rare earth oxide or transition metal powder into a tabletting mold, pressing into an ingot, and placing the prepared ingot into a graphite crucible anode positioned in a reaction chamber of a direct current arc discharge device; (2) Introducing air or argon into the reaction chamber, and then performing discharge treatment; (3) And collecting reaction products in the reaction chamber, wherein the collected products are the luminescent ion doped silicon dioxide fluorescent powder.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a plurality of rare earth or transition metal doped silicon dioxide fluorescent powders and a preparation method thereof.
Background
Silica has received much attention as a typical inorganic oxide material having advantages of high biocompatibility, stable physicochemical properties, high mechanical strength, good flexibility, and the like. When the silicon dioxide is used as a matrix to prepare the rare earth or transition metal doped luminescent material, the silicon dioxide has high transparency, so that the influence of the matrix material on the luminescence of rare earth ions or transition metal ions can be effectively avoided, and meanwhile, the unique three-dimensional network structure of the silicon dioxide and a large number of hydroxyl groups stored in the silicon dioxide can effectively stabilize and protect the rare earth ions or transition metal ions doped in the silicon dioxide, so that the luminescence performance of the material is improved. Therefore, the rare earth or transition metal doped silica materials prepared by different methods have important value in expanding the application of the rare earth or transition metal doped silica materials in the fields of biological imaging, illumination, optoelectronic equipment and the like.
Along with the continuous research and development of material chemistry, rare earth or transition metal doped materials are paid attention to because of having unique physical properties such as light, electricity, magnetism and the like, and have great application prospects in the fields of illumination, display, catalysis, sensing, photoelectric equipment, biology and the like. At present, many reports about preparing luminescent materials by rare earth or transition metal doped silicon dioxide exist, and widely adopted preparation methods mainly include a hydrothermal method, a high-temperature solid-phase method and the like, but most of the methods need severe reaction conditions, such as heating under high pressure, a high-temperature calcination process, inert gas protection and the like. When the silicon dioxide is used as a matrix to prepare the rare earth or transition metal doped luminescent material, the mild preparation condition of the silicon dioxide material can be effectively utilized, the required product can be obtained at normal temperature and normal pressure, the energy consumption is greatly reduced, and the luminescent material is one of the very promising rare earth doped matrix materials. The research of the current rare earth or transition metal doped silicon dioxide luminescent materials is relatively few, the morphology is single, most of the rare earth or transition metal doped silicon dioxide luminescent materials are spherical or small particles, and the rare earth or transition metal doped silicon dioxide luminescent materials are probably difficult to consider due to the special amorphous structure of silicon dioxide. This series of problems greatly constrains the use of rare earth or transition metal doped silica luminescent materials. In addition, research shows that the luminous performance of the rare earth or transition metal doped material is closely related to factors such as a preparation method, product morphology and size.
At present, the method for forming the composite fluorescent nano material by the rare earth or transition metal complex and the silicon dioxide mainly comprises an inverse microemulsion method, a sol-gel method, a surface modification method, an organic ligand sensitized fluorescence enhancement technology and the like. Qin Pinzhu Eu (TTA) is prepared by reverse microemulsion method 3 phen is a core, and silica obtained by hydrolysis under the catalysis of TEOS alkali is a long-life luminescent nanoparticle with a shell. However, the reverse microemulsion method is more suitable for preparing ultrafine nano particles, and the prepared fluorescent microspheres are easy to agglomerate, have high cost, are difficult to remove organic components, and are easily influenced by a plurality of factors such as experimental conditions. Yu et al used polyvinylpyrrolidone as rare earth complex Eu (DBM) 3 phen surfactant, using positive siliconThe spherical nano composite material of the silicon dioxide coated rare earth complex is prepared by hydrolysis under the catalysis of the acid ethyl ester base. Although the traditional sol-gel method can obtain a product with good sphericity, the obtained fluorescent microsphere has poor monodispersity due to the aggregation of the rare earth complex, the irregularity of the morphology of the rare earth complex and the high activity of silicon hydroxyl on the surface of the silicon dioxide of the coating layer, the uniformity distribution of the particle size is difficult to realize to a certain extent, and the addition amount of the rare earth complex needed by the composite material obtained through coating is more. Zhang et al grafts rare earth complex on the surface of the silicon dioxide microsphere by a surface modification method, and prepares green and red fluorescent microsphere with stronger luminous intensity. However, the surface modification method consumes the silicon hydroxyl groups on the surface of the fluorescent microsphere, thereby reducing the surface activity and biocompatibility of the fluorescent microsphere. The preparation method has long preparation period, needs high temperature, high pressure and other conditions, and has low yield, so that the search of a synthesis route which has mild reaction conditions, simple and convenient operation, low cost and environmental friendliness to realize the controllability of the size and the morphology of the rare earth or transition metal doped silicon dioxide material is a problem to be solved by researchers at present.
In order to solve the problems, the technology aims at preparing luminescent materials doped with different rare earth ions and transition metal ions by using a plasma arc method, so that convenience in the preparation process of the silica nanowires is ensured, and technical possibility is provided for realizing the adjustment of luminescent properties doped with different rare earth ions and transition metal by using the same matrix material.
Disclosure of Invention
The invention aims to provide luminescent ion doped amorphous silicon dioxide fluorescent powder and a preparation method thereof, which solve the technical problem that rare earth or transition metal doped silicon dioxide nanowires are difficult to prepare in the prior art. The preferred technical solutions of the technical solutions provided by the present invention can produce a plurality of technical effects described below.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the invention provides a preparation method of a rare earth or transition metal doped silicon dioxide nanowire, which comprises the following steps:
(1) Placing a reaction raw material containing silicon dioxide powder and rare earth powder or transition metal powder into a tabletting mold, compacting into an ingot, and placing the prepared ingot into a graphite crucible anode positioned in a reaction chamber of a direct current arc discharge device;
(2) Introducing air or oxygen into the reaction chamber, and then performing discharge treatment;
(3) And collecting reaction products in the reaction chamber, wherein the collected products are the silicon dioxide fluorescent powder.
When the discharge treatment is carried out, the reaction chamber is in a high-temperature and high-energy environment, and plasma generated by a direct current arc in the high-temperature environment is a key point for preparing the rare earth or transition metal doped silicon dioxide nanowire. The processing mode is simple and convenient to operate, the reaction condition is relatively mild, the subsequent recycling is relatively convenient, and the high-purity rare earth or transition metal doped amorphous silicon dioxide nanowire can be prepared relatively simply.
On the basis of the technical scheme, the invention can be improved as follows.
As a further improvement of the present invention, in the step (1), the rare earth oxide powder is Eu 2 O 3 、 Tb 4 O 7 、Sm 2 O 3 、Dy 2 O 3 、CeO 2 Or one or more of transition metals (Bi powder), or a mixture of rare earth oxide powder and transition metal powder.
The rare earth element or the transition metal has better luminescence property, so that products prepared by using the rare earth oxide or the transition metal as raw materials have better application prospects in the optical field, and can provide a new research direction for the research and development of nanoscale materials in the field of light-emitting devices.
As a further improvement of the present invention, the molar ratio of the silica powder to the rare earth oxide powder or transition metal powder is 100:1-5.
As a further improvement of the present invention, in the step (2), the discharge condition in the reaction chamber is: the voltage range is 10-30V, the current is 80-120A, and the reaction time is 2-10 min. Under these conditions, a suitable high temperature, high energy environment can be created in the reaction chamber, which aids in the reaction.
As a further improvement of the invention, in the step (2), the gas in the reaction chamber can be air or argon, and the final pressure is in the range of 10-40 kPa.
As a further development of the invention, a condensation wall is provided in the reaction chamber, on which condensation wall at least part of the reaction products condense.
As a further improvement of the present invention, before proceeding to step (2), it is necessary to feed cooling water to the graphite crucible anode and the condensation wall.
As a further development of the invention, a cathode is also provided in the reaction chamber, which cathode is formed by a tungsten rod. The cathode formed by the tungsten rod has better high-temperature resistance effect.
As a further improvement of the invention, in the step (2), the reaction chamber is vacuumized first, and then the protective gas is introduced.
The invention also provides a rare earth or transition metal doped silica nanowire, which has the diameter of about 30-50 nm and the length of 10-20 mu m as a further improvement of the invention. The luminescence of the silicon dioxide fluorescent powder can be regulated by regulating doped functional ions.
Compared with the prior art, the preparation method of the rare earth or transition metal doped silicon dioxide nanowire provided by the preferred embodiment of the invention has the advantages of simple conditions, easiness in operation, high efficiency, energy conservation, environmental friendliness and no generation of any harmful gas in the process. The rare earth or transition metal doped silicon dioxide nanowire prepared by the method has higher purity, can realize the successful doping of rare earth ions or transition metals by the silicon dioxide nanowire, and provides infinite possibility for devices in the light-emitting field of nanoscale materials.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural view of a reaction chamber used in the method of the present invention;
FIG. 2 is a scanning electron microscope, transmission electron microscope map of the silica nanowires prepared by the invention;
FIG. 3 is an XRD pattern for a first embodiment of a rare earth doped silica nanowire of the invention;
FIG. 4 is a PL spectrum of a first embodiment of the rare earth doped silica nanowire of the present invention;
FIG. 5 is an XRD pattern for two embodiments of rare earth doped silica sodium Mi Xiandi of the invention;
FIG. 6 is a PL spectrum of two examples of rare earth doped silica sodium Mi Xiandi of the invention;
FIG. 7 is an XRD pattern for a third embodiment of a transition metal doped silica nanowire of the invention;
FIG. 8 is a PL spectrum of a third embodiment of a transition metal doped silica nanowire of the present invention;
FIG. 9 is a PL spectrum of a fourth embodiment of the rare earth doped silica nanowire of the present invention;
FIG. 10 is a PL spectrum of a fifth embodiment of the rare earth doped silica nanowire of the present invention;
FIG. 11 is a PL spectrum of a sixth embodiment of the rare earth doped silica nanowire of the present invention;
FIG. 12 is a PL spectrum of a sixth embodiment of the rare earth doped silica nanowire of the present invention;
FIG. 13 is an XRD pattern for a silica nanowire prepared using a direct current arc process in accordance with the present invention;
FIG. 14 is a PL profile of a silica nanowire prepared by the direct current arc method of the present invention;
in the figure: 1. a reaction chamber; 2. a condensation wall; 3. a tungsten cathode; 4. a reaction raw material; 5. a graphite crucible anode; 6. A cooling water port; 7. an air inlet; 8. a vent port; 9. a condensing wall water inlet; 10. and a water outlet of the condensation wall.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in fig. 1 are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
The technical scheme of the invention is specifically described below with reference to the accompanying drawings.
FIG. 1 is a schematic structural view of a reaction chamber used in the method of the present invention.
As shown in fig. 1, a condensation wall 2, a tungsten cathode 3 and a graphite crucible anode 5 are arranged in the reaction chamber 1, wherein a reaction raw material 4 (which is formed by mixing the reaction raw materials and pressing the mixture by a tablet press) is filled on one side of the graphite crucible anode 5 facing the tungsten cathode 3, and the graphite crucible anode 5 and the tungsten cathode 3 are connected with a direct current power supply. In order to ensure the smooth condensation of the reaction products, circulating cooling water is introduced into the graphite crucible anode 5 and the condensation wall 2, wherein a cooling water inlet and a cooling water outlet are arranged below the graphite crucible anode 5, namely a cooling water outlet 6 (the cooling water outlet 6 comprises a water inlet and a water outlet) in fig. 1, and two ends of the condensation wall 2 are respectively provided with a condensation wall water inlet 9 and a condensation wall water outlet 10. After the reaction is completed, the obtained product is the silicon dioxide nanowire material.
The reaction chamber 1 is internally provided with a condensation wall 2, before the step (2) is carried out, cooling water (which can be recycled) is introduced into the positions of the graphite crucible anode 5 and the condensation wall 2 so as to reduce the temperature of the positions of the graphite crucible anode 5 and the condensation wall 2, and after the discharge reaction is finished, at least part of reaction products can be condensed on the condensation wall 2.
The invention provides a preparation method of a novel rare earth or transition metal doped silicon dioxide nanowire, which comprises the following steps:
(1) Placing a reaction raw material containing silicon dioxide powder and rare earth oxide powder or transition metal powder into a tabletting mold to be pressed into an ingot 4, and placing the prepared ingot 4 into a graphite crucible anode 5 positioned in a reaction chamber 1 of a direct current arc discharge device (at the moment, a cathode material in the reaction chamber 1 is a tungsten rod with better high-temperature resistance effect, namely a tungsten cathode 3);
(2) Introducing air or argon into the reaction chamber 1, and then performing discharge treatment;
(3) And collecting reaction products in the reaction chamber 1, wherein the collected products are the silicon dioxide nanowires.
In the process of discharge treatment, the structure of the reaction chamber 1 is shown in fig. 1, the inside of the reaction chamber is a high-temperature and high-energy environment, and plasma generated by a direct current arc in the high-temperature environment is a key point for preparing the rare earth or transition metal doped silicon dioxide nanowire. The specific working principle is as follows: under the dynamic extreme environment of high temperature, high ionization and high quenching, the direct current arc is easy to form reactant clusters with high reactivity in nanometer scale through high temperature evaporation, sublimation and electron and ion beam detonation. These clusters facilitate the doping of large radius rare earth ions or transition metal ions into the silica matrix under appropriate nucleation conditions. The anode formed by the graphite crucible can effectively resist high temperature, and in the reaction process, the graphite crucible can effectively reduce substances except rare earth ions in rare earth-containing powder, so that the sample is uniformly doped and has high purity. The rare earth element or the transition metal element has better luminescence property, so that the prepared product has better application prospect in the optical field, and provides infinite possibility for devices in the luminescence field of nanoscale materials. Compared with other processing methods, the processing method is simple and convenient to operate, the reaction condition is relatively mild, the subsequent recycling is relatively convenient, and the rare earth or transition metal doped silicon dioxide nanowire can be relatively simply prepared.
Note that, when introducing the shielding gas into the reaction chamber 1, it is necessary to achieve this through the gas inlet 7 and the gas outlet 8.
In order to ensure the reaction effect, the specific reaction conditions need to be limited:
in step (2), the discharge conditions in the reaction chamber 1 are: the voltage range is 10-40V, the current is 80-120A, and the reaction time is 2-10 min. Under these conditions, a suitable high-temperature, high-energy environment can be created in the reaction chamber 1, contributing to the progress of the reaction. In addition, in step (2), in order to avoid the influence of oxygen and water on the reaction, the reaction chamber 1 needs to be evacuated first, and then a reaction protecting gas, such as air or argon, is introduced. The final gas pressure in the reaction chamber 1 before the discharge treatment is 10 to 40KPa.
The diameter of the silicon dioxide nanowire prepared by the method is about 30-50 nm, and the length is 10-20 mu m.
It should be noted that the final physical properties of the product are affected by the raw materials, and the luminescence characteristics thereof may also vary to some extent depending on whether the raw materials contain rare earth elements or transition metal elements and the types of the rare earth elements or transition metal elements contained therein.
In the step (1), the reaction raw material is rare earth oxide powder Eu 2 O 3 、 Tb 4 O 7 、Sm 2 O 3 、Dy 2 O 3 、CeO 2 Or a transition metal such as Bi powder.
It should be noted that the above-mentioned reaction raw materials containing rare earth elements or transition metals may also be rare earth or transition metal simple substances, rare earth oxides or transition metal oxides, or the like.
As an alternative embodiment, the molar ratio of silica powder to rare earth oxide powder or transition metal powder is 100:1. when the undoped silicon dioxide nanowire and the silicon dioxide nanowire contain a certain amount of rare earth elements or transition metal elements, the undoped silicon dioxide nanowire and the silicon dioxide nanowire can emit visible light under the corresponding light excitation. For example:
Eu 2+ the doped silicon dioxide nanowire emits light with yellow light emitted by 480nm under the excitation of 335 nm; eu (Eu) 3+ The doped silicon dioxide nanowire emits light, and under excitation of 278nm, the doped silicon dioxide nanowire emits red light with the wavelength of 610 nm; tb (Tb) 3+ The doped silicon dioxide nanowire emits light, and under the excitation of 257nm, the light has green light emitted by 540 nm; sm (Sm) 2+ The doped silicon dioxide nanowire emits light, and under the excitation of 468nm, the doped silicon dioxide nanowire emits red light with 682 nm; dy (Dy) 3+ The doped silicon dioxide nanowire emits light with orange light emitted by 574nm under excitation of 350 nm; ce (Ce) 3+ The doped silicon dioxide nanowire emits light with green light emitted at 438nm under the excitation of 335 nm; bi (Bi) 3+ The doped silicon dioxide nanowire emits light, and blue light emitted by 430nm is emitted under the excitation of 323 nm; the undoped silicon dioxide nanowire emits light and has near ultraviolet light emitted by 390nm under the excitation of 250 nm.
The specific reaction conditions and the products obtained will also vary somewhat depending on the starting materials.
Example 1:
as shown in FIGS. 3 to 4, the present embodiment provides Eu production by the DC arc method 2+ The preparation process of the ion doped silicon dioxide nanowire is as follows:
mixing silicon dioxide powder with Eu 2 O 3 The powder is prepared from the following components in percentage by weight: 1, putting the mixture into a tabletting mould, and using a tabletting machine to press the mixture into ingots to obtain cylinders with the diameter of 1.8cm and the height of 2 cm. Placing the obtained ingot in a graphite crucible anode 5 (the specific position of the ingot is shown in figure 1), and introducing circulating cooling water into the anode 5 and a condensation wall 2; firstly, the reaction chamber 1 is vacuumized, air enters the direct current arc plasma reaction chamber 1 through a pipeline, and when the air pressure is 20KPa, the gas charging pipeline is closed, and discharge is started. Put onThe voltage is kept at 30V and the current is 120A in the electric process, and the reaction is carried out for 5min. Collecting and grinding the reaction product obtained after discharge in the graphite crucible and at the inner side of the contact edge of the tungsten rod, namely Eu 2+ Ion doped silicon dioxide nanowires.
As can be seen from the XRD diffraction peak pattern of fig. 3, the prepared sample has a broad diffraction peak at 2θ=20 to 30 °, which is attributed to the characteristic peak of amorphous silica, while no diffraction peak of other impurities is found, indicating that the purity of the sample is very high; the PL excitation spectrum of FIG. 4 has a broad hump at 335nm at 200nm-450nm, derived from Eu 2+ 4f of ions 7 →4f 6 5d transition, emission spectrum extending from 380nm to 750nm, peak at 480nm, due to Eu 2+ 4f of ions 6 5d→4f 7 Is able to see Eu 2+ Successful doping of the ions causes the silica nanowires to emit green light at 480nm under excitation at 335 nm.
Example 2:
as shown in fig. 5-6, the present embodiment provides a method of doping Tb using direct current arc method 3+ An ionic silica nanowire prepared as follows:
mixing silicon dioxide powder with Tb 4 O 7 The powder is prepared from the following components in percentage by weight: 1, putting the mixture into a tabletting mould, and using a tabletting machine to press the mixture into ingots to obtain cylinders with the diameter of 1.8cm and the height of 2 cm. Placing the obtained ingot in a graphite crucible anode 5 (the specific position of the ingot is shown in figure 1), and introducing circulating cooling water into the anode 5 and a condensation wall 2; firstly, the reaction chamber 1 is vacuumized, air enters the direct current arc plasma reaction chamber 1 through a pipeline, and when the air pressure is 30KPa, the gas charging pipeline is closed, and discharge is started. The voltage was kept at 20V and the current at 90A during the discharge for 5min. Collecting and grinding the reaction product obtained after discharge in the graphite crucible and at the inner side of the contact edge of the tungsten rod, namely the doped Tb 3+ An ionic silica nanowire.
As can be seen from the XRD diffraction peak pattern of FIG. 5, the prepared sample has a broad diffraction peak in the range of 2θ=20 to 30℃and is attributed to amorphous dioxygenCharacteristic peaks of silicon are formed, and diffraction peaks of other impurities are not found at the same time, so that the purity of the sample is high; the PL excitation spectrum of FIG. 6 extends from 200nm to 550nm, with a strong band centered at about 257nm belonging to Tb 3+ 4f of ions 8 →4f 7 5d 1 Is Tb at 317nm, 364nm, 378nm, 483nm 3+ Of ions 7 F 6 → 5 H 7 、 7 F 6 → 5 D 2 、 7 F 6 → 5 G 6 、 7 F 6 → 5 D 4 Is not limited by the absorption transition of (a); the emission spectrum extends from 450nm to 700nm, and has obvious peaks at 488nm, 540nm, 589nm and 625nm due to Tb 3+ Of ions 5 D 4 → 7 F 6 、 5 D 4 → 7 F 5 、 5 D 4 → 7 F 4 、 5 D 4 → 7 F 3 Can be seen from the transition of Tb 3+ Successful doping of the ions causes the silica nanowires to emit 540nm green light under 257nm excitation.
Example 3:
as shown in FIGS. 7-8, the present example provides the preparation of Bi doped by DC arc method 3+ The preparation process of the ion silicon dioxide nanowire is as follows:
mixing silicon dioxide powder and Bi powder according to the weight ratio of 100:1, putting the mixture into a tabletting mould, and using a tabletting machine to press the mixture into ingots to obtain cylinders with the diameter of 1.8cm and the height of 2 cm. Placing the obtained ingot in a graphite crucible anode 5, and introducing circulating cooling water into the anode 5 and a condensation wall 2; firstly, the reaction chamber 1 is vacuumized, air enters the direct current arc plasma reaction chamber 1 through a pipeline, and when the air pressure is 35KPa, the gas charging pipeline is closed, and discharge is started. The voltage was kept at 20V and the current was 100A during the discharge for 2min. Collecting and grinding the reaction product obtained after discharge in the graphite crucible and at the inner side part of the contact edge of the tungsten rod, thus obtaining the Bi doped material 3+ An ionic silica nanowire.
As can be seen from the XRD diffraction peak pattern of FIG. 7, the preparationThe prepared sample has a wide diffraction peak in the range of 2 theta = 20-30 degrees, belongs to the characteristic peak of amorphous silicon dioxide, and has no diffraction peak of other impurities, so that the purity of the sample is high; in FIG. 8, the PL spectrum has a broad hump at 251nm at 200nm-350nm, derived from Bi 3+ Of ions 1 S 0 → 1 P 1 The emission spectrum extends from 330nm to 600nm, peaking at 391nm due to Bi 3+ Of ions 3 P 1 → 1 S 0 Is to see Bi 3+ The doped silicon dioxide nanowire emits light and has 391nm emitted near ultraviolet light under the excitation of 251 nm.
Example 4:
the embodiment provides a method for preparing Dy doped material by DC arc method 3+ An ionic silica nanowire prepared as follows:
mixing silicon dioxide powder with Dy 2 O 3 The powder is prepared from the following components in percentage by weight: 1, putting the mixture into a tabletting mould, and using a tabletting machine to press the mixture into ingots to obtain cylinders with the diameter of 1.8cm and the height of 2 cm. Placing the obtained ingot in a graphite crucible anode 5, and introducing circulating cooling water into the anode 5 and a condensation wall 2; firstly, the reaction chamber 1 is vacuumized, air enters the direct current arc plasma reaction chamber 1 through a pipeline, and when the air pressure is 20KPa, the gas charging pipeline is closed, and discharge is started. The voltage was kept at 20V and the current was 100A during the discharge for 4min. Collecting and grinding the reaction product obtained after discharge in the graphite crucible and at the inner side of the contact edge of the tungsten rod to obtain Dy doped reaction product 3+ An ionic silica nanowire.
Dy 3+ PL spectra of doped silica nanowires are shown in figure 9. In FIG. 9, the PL excitation spectrum extends from 200nm to 500nm centered at 350nm, and strong bands at about 300nm, 323nm, 350nm, 386nm, 423nm, 451nm, 472nm correspond to Dy, respectively 3+ Of ions 6 H 15/2 → 6 K 15/2 、 6 H 15/2 → 4 I 9/2 、 6 H 15/2 → 6 P 7/2 、 6 H 15/2 → 4 I 11/2 、 6 H 15/2 → 4 G 11/2 、 6 H 15/2 → 4 I 15/2 、 6 H 15/2 → 4 F 9/2 Is a transition of electrons of (a); the emission spectra at 481nm, 573nm and 664nm correspond to Dy respectively 3+ Of ions 4 F 9/2 → 6 H 15/2 、 4 F 9/2 → 6 H 13/2 、 4 F 9/2 → 6 H 11/2 Dy can be seen from the electron transition of (C) 3+ The doped silica nanowires have orange light emitted at 574nm under excitation at 350 nm.
Example 5:
the present example provides a method for preparing Eu doped using DC arc method 3+ The preparation process of the ion silicon dioxide nanowire is as follows:
mixing silicon dioxide powder with Eu 2 O 3 The powder is prepared from the following components in percentage by weight: 1, putting the mixture into a tabletting mould, and using a tabletting machine to press the mixture into ingots to obtain cylinders with the diameter of 1.8cm and the height of 2 cm. Placing the obtained ingot in a graphite crucible anode 5, and introducing circulating cooling water into the anode 5 and a condensation wall 2; firstly, the reaction chamber 1 is vacuumized, air enters the direct current arc plasma reaction chamber 1 through a pipeline, and when the air pressure is 20KPa, the gas charging pipeline is closed, and discharge is started. The voltage was kept at 15V and the current was 80A during the discharge for 2min. Collecting and grinding the reaction product obtained after discharge in the graphite crucible and at the inner side of the contact edge of the tungsten rod to obtain Eu doped 3+ An ionic silica nanowire.
Eu 3+ PL spectra of doped silica nanowires are shown in figure 10. In FIG. 10, the PL excitation spectrum extends from 200nm to 550nm, and a broad band centered at about 278nm is the result of charge transfer absorption (CTB). Has obvious peak values at 322nm, 362nm, 382nm, 395nm, 416nm and 465nm, is Eu 3+ Ion(s) 7 F 0 → 5 H 4 、 7 F 0 → 5 D 4 、 7 F 0 → 5 G 2 、 7 F 0 → 5 L 6 、 7 F 0 → 5 D 3 、 7 F 0 → 5 D 2 Is a transition of (2); the emission spectrum extends from 570nm to 720nm, corresponding to 586nm, 610nm, 623nm, 707 and nm, respectively 5 D 0 → 7 F 0 、 5 D 0 → 7 F 1 、 5 D 0 → 7 F 2 、 5 D 0 → 7 F 3 、 5 D 0 → 7 F 4 Is able to see Eu 3+ The ion doped silica nanowire has a red light emission of 610nm under excitation of 278 nm.
Example 6:
the embodiment provides the preparation of the Ce doped material by the direct current arc method 3+ The preparation process of the ion silicon dioxide nanowire is as follows:
mixing silicon dioxide powder with CeO 2 The powder is prepared from the following components in percentage by weight: 1, putting the mixture into a tabletting mould, and using a tabletting machine to press the mixture into ingots to obtain cylinders with the diameter of 1.8cm and the height of 2 cm. Placing the obtained ingot in a graphite crucible anode 5, and introducing circulating cooling water into the anode 5 and a condensation wall 2; firstly, the reaction chamber 1 is vacuumized, air enters the direct current arc plasma reaction chamber 1 through a pipeline, and when the air pressure is 35KPa, the gas charging pipeline is closed, and discharge is started. The voltage was kept at 20V and the current was 100A during the discharge for 3min. Collecting and grinding the reaction product obtained after discharge in the graphite crucible and at the inner side part of the contact edge of the tungsten rod, thus obtaining the Ce doped material 3+ An ionic silica nanowire.
Ce 3+ PL spectra of doped silica nanowires are shown in figure 11. In FIG. 11, the PL spectrum has a broad hump at 335nm at 200nm-400nm, derived from Ce 3+ The transition of ion 4 f-5 d, the emission spectrum extends from 360nm to 650nm, and peaks at 438nm, due to Ce 3+ The transition of ion 5d to 4f can be seen as Ce 3+ The doped silicon dioxide nanowire emits light with 438nm emission under the excitation of 335nmGreen light of (a) is provided.
Example 7:
this example provides the preparation of Sm doped with Sm by direct current arc method 2+ The preparation process of the ion silicon dioxide nanowire is as follows:
mixing silicon dioxide powder with Sm 2 O 3 The powder is prepared from the following components in percentage by weight: 1, putting the mixture into a tabletting mould, and using a tabletting machine to press the mixture into ingots to obtain cylinders with the diameter of 1.8cm and the height of 2 cm. Placing the obtained ingot in a graphite crucible anode 5, and introducing circulating cooling water into the anode 5 and a condensation wall 2; firstly, the reaction chamber 1 is vacuumized, air enters the direct current arc plasma reaction chamber 1 through a pipeline, and when the air pressure is 40KPa, the gas charging pipeline is closed, and discharge is started. The voltage was kept at 25V and the current was 100A during the discharge for 4min. Collecting and grinding the reaction product obtained after discharge in the graphite crucible and at the inner side of the contact edge of the tungsten rod to obtain Sm doped with Sm 2+ An ionic silica nanowire.
Sm 2+ PL spectra of doped silica nanowires are shown in figure 12. In FIG. 12, the strong band centered around 468nm of the PL excitation spectrum belongs to Sm 2+ 4f of ions 6 →4f 5 5d 1 The absorption transition of (2) is that the emission spectrum extends from 600nm to 850nm, and obvious peaks at 682nm, 703nm, 725nm, 761nm and 809nm are caused by Sm 2+ Of ions 5 D 0 → 7 F 0 、 5 D 0 → 7 F 1 、 5 D 0 → 7 F 2 、 5 D 0 → 7 F 3 、 5 D 0 → 7 F 4 Is able to see Sm 2+ The ion doped silica nanowire emits light with red light emitted by 682nm under excitation of 468 nm.
In addition, the application also discloses a product of the silica nanowire pure product prepared by the preparation method, and the corresponding physical characteristics and luminous characteristics of the product are shown in fig. 13 and 14.
As can be seen from the XRD diffraction peak pattern of fig. 13, the prepared sample has a broad diffraction peak in the range of 2θ=20 to 30 °, which is attributed to the characteristic peak of amorphous silica, while no diffraction peak of other impurities is found, indicating that the purity of the sample is very high; as can be seen from the PL spectrum of FIG. 14, the prepared sample exhibited a near ultraviolet spectrum at 390nm under excitation at 250 nm.
By taking figures 13 and 14 as blank control, the rare earth or transition metal doped silicon dioxide nanowire prepared by the method provided by the invention can be further proved to have an amorphous silicon dioxide structure, and basically no redundant impurities except rare earth elements or transition metal elements are introduced, so that the prepared rare earth or transition metal doped silicon dioxide nanowire product has higher purity.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (3)
1. The preparation method of the luminescent ion doped silicon dioxide fluorescent powder is characterized by comprising the following steps of:
(1) The molar ratio was set to 100:1-5, mixing the reaction raw materials of silicon dioxide powder and rare earth oxide powder or transition metal powder, putting the mixture into a tabletting mold, pressing the mixture into ingots, and placing the prepared ingots into a graphite crucible anode positioned in a reaction chamber of a direct current arc discharge device;
(2) After the reaction chamber is vacuumized, introducing air or argon into the reaction chamber, wherein the air pressure range is 10-40 kPa; then, carrying out direct current plasma discharge; the discharge conditions in the reaction chamber were: the voltage range is 10-30V, the current is 80-120A, and the reaction time is 2-10 min;
(3) Collecting the reaction product in the reaction chamber to obtain luminescent ion doped silicon dioxide fluorescent powder, wherein the silicon dioxide fluorescent powder is in an amorphous state, the shape of the silicon dioxide fluorescent powder is linear, the diameter is 30-50 nm, and the length is 10-20 mu m.
2. The method of producing a silica phosphor according to claim 1, wherein in step (1), the rare earth oxide powder is Eu 2 O 3 、Tb 4 O 7 、Sm 2 O 3 、Dy 2 O 3 、CeO 2 One or more of the following; the transition metal is Bi.
3. The method of claim 1, wherein a condensation wall is disposed within the reaction chamber, at least a portion of the reaction product condensing on the condensation wall.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210719399.3A CN115029129B (en) | 2022-06-23 | 2022-06-23 | Luminescent ion doped silicon dioxide fluorescent powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210719399.3A CN115029129B (en) | 2022-06-23 | 2022-06-23 | Luminescent ion doped silicon dioxide fluorescent powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115029129A CN115029129A (en) | 2022-09-09 |
| CN115029129B true CN115029129B (en) | 2024-01-19 |
Family
ID=83126613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210719399.3A Active CN115029129B (en) | 2022-06-23 | 2022-06-23 | Luminescent ion doped silicon dioxide fluorescent powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115029129B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519203A (en) * | 2009-02-27 | 2009-09-02 | 吉林大学 | Silicon-carbon-oxygen compound amorphous nanometer wire and preparation method thereof |
| CN103159407A (en) * | 2013-03-19 | 2013-06-19 | 东华大学 | Fluorescent powder/silicon-based mesoporous material composite fluorescent glass and preparation method thereof |
| JP2015089866A (en) * | 2013-11-07 | 2015-05-11 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Surface-modified silica nano wire complex and method of producing the same |
| CN111748343A (en) * | 2020-06-29 | 2020-10-09 | 新余学院 | Rare earth ion doped silicon oxynitride-based fluorescent powder, preparation method thereof and combustion synthesis device |
| CN114517091A (en) * | 2022-03-09 | 2022-05-20 | 渤海大学 | Rare earth ion doped silicon nitride nanowire and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9409141B2 (en) * | 2011-07-14 | 2016-08-09 | University Of Louisville Research Foundation | Methods for synthesizing metal oxide nanowires |
-
2022
- 2022-06-23 CN CN202210719399.3A patent/CN115029129B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519203A (en) * | 2009-02-27 | 2009-09-02 | 吉林大学 | Silicon-carbon-oxygen compound amorphous nanometer wire and preparation method thereof |
| CN103159407A (en) * | 2013-03-19 | 2013-06-19 | 东华大学 | Fluorescent powder/silicon-based mesoporous material composite fluorescent glass and preparation method thereof |
| JP2015089866A (en) * | 2013-11-07 | 2015-05-11 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Surface-modified silica nano wire complex and method of producing the same |
| CN111748343A (en) * | 2020-06-29 | 2020-10-09 | 新余学院 | Rare earth ion doped silicon oxynitride-based fluorescent powder, preparation method thereof and combustion synthesis device |
| CN114517091A (en) * | 2022-03-09 | 2022-05-20 | 渤海大学 | Rare earth ion doped silicon nitride nanowire and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 以单分散纳米二氧化硅颗粒为基质稀土掺杂Tb~(3+)的发光材料的制备与性质研究;齐霞;王喜贵;薄素玲;娜米拉;;内蒙古师范大学学报(自然科学汉文版)(第06期);第689-693页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115029129A (en) | 2022-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ramasamy et al. | Upconversion nanophosphors for solar cell applications | |
| Hou et al. | Luminescent properties of nano-sized Y2O3: Eu fabricated by co-precipitation method | |
| CN113620262B (en) | Preparation method of rare earth doped boron nitride nanosheet and nanosheet | |
| CN109233821B (en) | Multicolor luminous carbon quantum dot and preparation method and application thereof | |
| Rajkumar et al. | A highly intense double perovskite BaSrYZrO5. 5: Eu3+ phosphor for latent fingerprint and security ink applications | |
| CN104031647A (en) | Preparation method for circular disk-like europium-doped lanthanum vanadate red phosphors | |
| Yu et al. | Energy transfer processes in electrospun LaOCl: Ce/Tb nanofibres | |
| Naixu et al. | Luminescent properties and energy transfer of color-tunable Sr3Y2 (SiO3) 6: Ce3+, Tb3+ phosphors | |
| CN115029129B (en) | Luminescent ion doped silicon dioxide fluorescent powder and preparation method thereof | |
| CN102584202B (en) | Preparation method for YAG (Yttrium Aluminum Garnet) powder and reaction device thereof | |
| CN103614142B (en) | Glucose assisted hydrothermal method for preparing spherical LaVO4:Eu<3+> red phosphor | |
| CN114517091B (en) | Rare earth ion doped silicon nitride nanowire and preparation method thereof | |
| Li et al. | A neoteric approach to achieve BaF2: Yb3+, Er3+ one-dimensional nanostructures with color-tuned up-conversion luminescence | |
| CN105038791A (en) | Preparation method of spherical red phosphor powder capable of being excited by ultraviolet-blue light | |
| CN103666447B (en) | For the two conversion of solar cell core-shell structured nanomaterials and preparation method thereof | |
| Lu et al. | High-efficient, bicolor-emitting GdVO4: Dy3+ phosphor under near ultraviolet excitation | |
| Wang et al. | Oxalate-assisted morphological effect of NaYF4: Yb3+, Er3+ on photoelectrochemical performance for dye-sensitized solar cells | |
| CN107033907B (en) | Rare earth doped nanocrystals and methods of making the same | |
| Li et al. | Design and electrospinning synthesis of SrF2: Er3+/Yb3+ unidimensional nanostructural materials with tunable upconverting fluorescence | |
| CN106753347A (en) | A kind of near ultraviolet excitated red fluorescence powder and preparation method thereof | |
| CN102433117A (en) | Chemical solution preparation method for tungsten molybdate solid solution luminescent microcrystal | |
| Gao et al. | Hydrothermal synthesis of Y2O3 coated Y2O3: Eu3+ nanotubes for enhanced photoluminescence properties | |
| CN110041931B (en) | Near-infrared fluorescent film, preparation method thereof and near-infrared LED | |
| CN105199731B (en) | A kind of LED NaLaMgWO6:xSm3+Red fluorescence powder and preparation method thereof | |
| CN105110376B (en) | A kind of quick method preparing olive-shaped wolframic acid lanthanum sodium |
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 |