CN114716142B - ZnS-doped quantum dot luminescent glass and preparation method and application thereof - Google Patents
ZnS-doped quantum dot luminescent glass and preparation method and application thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 78
- 239000002096 quantum dot Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 239000002019 doping agent Substances 0.000 claims abstract description 4
- -1 silicon germanium borate Chemical compound 0.000 claims abstract description 4
- 239000005385 borate glass Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 11
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000156 glass melt Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical class [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000005496 eutectics Effects 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- CHYRFIXHTWWYOX-UHFFFAOYSA-N [B].[Si].[Ge] Chemical compound [B].[Si].[Ge] CHYRFIXHTWWYOX-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
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- 239000000956 alloy Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/235—Heating the glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- 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
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
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- Power Engineering (AREA)
- Luminescent Compositions (AREA)
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Abstract
The invention relates to ZnS-doped quantum dot luminescent glass and a preparation method thereof. The luminescent glass material takes transparent silicon germanium borate glass as a matrix and ZnS and Ni 2+ The ions are dopants. The luminescent glass material is obtained by a simple eutectic method, and has the advantages of small self-absorption effect, excellent optical performance and high reliability.
Description
Technical Field
The invention relates to the field of luminescent materials, in particular to a Ni alloy 2+ An ion doped ZnS quantum dot luminescent glass and a preparation method thereof.
Background
The semiconductor quantum dot has excellent photoelectric performance due to the unique size effect, has wide application in the fields of display, illumination, lasers, photovoltaics and the like, and becomes one of the most active and attractive cross research fields in recent decades. Various high quality semiconductor quantum dots, such as II-VI (ZnS, znSe, znTe, cdS, cdSe, cdTe, etc.), IVB-VIA (PbS, pbSe, pbTe, etc.), and halide perovskite (CsPbBr) 3 Etc.) colloidal quantum dots have been successfully synthesized. However, most of the colloidal quantum dots synthesized by the wet chemical method are unstable and sensitive to the atmospheric environment, and dispersing the colloidal quantum dots in high molecular matrix materials such as polymers, sol-gel films and the like can be influenced by the chemical and mechanical property instability of the matrix materials, so that the application of the colloidal quantum dots in photoelectric devices is limited. Amorphous glass is easy to useThe processing has excellent chemical and physical stability, and the high density and uniform composition can also protect the quantum dots from the surrounding environment. In addition, aggregation or dissolution of quantum dot particles in a glass host can be prevented, and the size and distribution of nested quantum dots can be conveniently and effectively controlled. The quantum dot microcrystalline glass formed by combining the quantum dots and the inorganic glass can fully utilize the advantages of the quantum dots and the inorganic amorphous glass, and is a very promising optical material. Glasses incorporating group II-VI, IV-VI elemental semiconductor quantum dots and perovskite quantum dots have been reported. However, the main components of the high-performance quantum dot glass developed at present almost all contain heavy metal elements such as Cd, pb and the like which are harmful to human bodies and are not friendly to the environment. While cadmium chalcogenides, lead chalcogenides, and lead perovskite quantum dot glasses are considered a promising material, they have not been suitable for large scale applications due to the toxicity of lead and cadmium elements. Therefore, developing a quantum dot luminescent glass that is simple to prepare, stable in performance, non-toxic or low-toxic, and environmentally friendly is an urgent task. Excellent optical properties can be obtained by conditioning a low-toxicity ZnS semiconductor having a wider band gap with transition metal ions, but ZnS is extremely easily oxidized at high temperature, S 2- It is difficult to survive in high temperature melting glass systems and to obtain ZnS-containing quantum dot glass by high temperature melting. The quantum dots with specific properties are dispersed into glass by a sol-gel method or porous glass, and then the quantum dot glass is prepared by low-temperature sintering, so that the preparation process is complex and complicated, the physical and chemical properties of a glass system are generally poor, and the use environment is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a ZnS quantum dot doped luminescent glass which comprises a low-toxicity ZnS semiconductor material with wider band gap and Ni 2+ Ion co-doped silicon germanium boron glass is directly subjected to a simple eutectic method to obtain the Ni-containing glass 2+ The ion doped ZnS quantum dot glass obtains excellent optical performance.
The specific technical scheme of the invention is as follows: znS-doped quantum dot luminescent glass, which emits lightThe optical glass material takes transparent silicon germanium borate glass as a matrix, znS and NiO as doping agents, and comprises the following raw materials in percentage by mole: siO (SiO) 2 20～40%，B 2 O 3 10～30%，GeO 2 10～30%，Al 2 O 3 5～30%，ZnF 2 5～15%，NaF 5～20%，ZnS 0.5～10%，Ni 2+ 0.01～4%。SiO 2 ，B 2 O 3 And GeO 2 The three oxide glass network forming bodies can effectively ensure the physical and chemical properties of the glass system, and are beneficial to obtaining a stable glass system; znS is an inorganic compound semiconductor material of II-VI groups, has the widest band gap in the semiconductor material of II-VI groups, has a forbidden band width of 3.6 and eV, is an excellent fluorescent material matrix, and has great luminous regulation and control potential; al (Al) 2 O 3 , ZnF 2 And NaF can effectively adjust the network structure of the glass system, so that ZnS quantum dots are easier to separate out in the system; f (F) - The ions can also effectively reduce the phonon energy of the system, reduce the unnecessary energy transfer process, and are beneficial to obtaining excellent optical performance; in addition ZnF 2 Additional Zn can also be provided in the system 2+ Ions help the system lock S in the high temperature melting process 2- Ions inhibit oxidation thereof. When B in the system 2 O 3 When the proportion is higher, the thermodynamic property of the obtained luminescent glass is relatively poor, and the corresponding SiO 2 And GeO 2 At higher ratios, the thermodynamic properties will be relatively good.
Preferably, the Ni-containing alloy is obtained by eutectic method 2+ Ion doped ZnS quantum dot glass. ZnS and Ni ions in a ratio of 1:20, ni 2+ The doping proportion of the ions is 0.1-1%. The proportion of ZnS in the system is not too high, and when the proportion is too high, a large amount of bubbles in the melt cannot be effectively discharged due to the oxidation of ZnS in the system, so that the quality of glass is low, and the use of the glass is affected. When ZnS is higher, the protective atmosphere can be properly conducted.
Preferably, the luminous glass is prepared from the following raw materials in mole percent: siO (SiO) 2 30%，B 2 O 3 15%，GeO 2 15.8%，Al 2 O 3 15%，ZnF 2 10%，NaF 10%，ZnS 4%，Ni 2+ 0.2%。
The preparation method of the ZnS-doped quantum dot luminescent glass sequentially comprises the following steps:
(1) Preparing raw materials: calculating the mass of each corresponding component according to the mole percentage of the glass composition, and weighing the corresponding raw materials;
(2) The preparation technology comprises the following steps: after all the raw material components are uniformly mixed by a mixer to form a mixture, the mixture is placed into a corundum crucible and placed into a resistance furnace with the temperature of 1100-1600 ℃ to be covered and melted for 20-60 minutes, and uniform glass melt is obtained after homogenization and clarification;
(3) Pouring: pouring the glass melt obtained in the step (2) onto a mould preheated to 200-500 ℃ for cooling and molding to obtain preformed glass;
(4) And (3) heat treatment: and (3) placing the formed glass obtained in the step (3) into a resistance furnace which is heated to 400-650 ℃, preserving heat for 5-30 hours, and naturally cooling along with the furnace to obtain the corresponding quantum dot luminescent glass.
The oxides of all components added in the preparation method of the ZnS-doped quantum dot luminescent glass can be added in the form of corresponding hydroxides, salts or compounds. Such as B 2 O 3 Can be added in the form of boric acid or sodium borate; al (Al) 2 O 3 May be added as aluminum oxide, aluminum hydroxide or other compounds; ni (Ni) 2+ The ions may be added as nickel oxide, nickel sulfide or other compounds of nickel.
The application of the ZnS quantum dot doped luminescent glass is that the luminescent glass has orange-yellow, orange-red or reddish brown transparent glass, the material can be excited by ultraviolet-near ultraviolet light, and broadband red light emission can be obtained when the material is excited by an LED with the wavelength of 225-500 nm.
The invention has the beneficial effects that:
(1) The invention uses ZnS and Ni 2+ The action of two kinds of ion dopants in glass system to generate Ni 2+ The doped ZnS quantum dot ensures that the doped ZnS quantum dot glass has a wide absorption range in the ultraviolet region and can effectively absorb ultraviolet or near ultravioletAnd emits broadband red light.
(2) The invention is transparent luminescent glass, compared with red light material in the prior art, ni is used as luminescent main body 2+ The ion doped ZnS quantum dots are directly separated out in a glass matrix, and can be directly used for processing transparent luminescent glass into a required form to be applied to products when in application, thereby being more suitable for decorative or high-color-rendering lighting devices with long service life.
(3) The transparent luminescent glass has the advantages of small self-absorption effect and large Stokes displacement, can effectively convert short-wave light into broadband visible long-wave luminescence, and can be applied to the field of efficient spectrum conversion.
(4) Heavy metal components are not used in the raw materials, and the mixing and sintering processes are carried out in the air, so that compared with sulfide or perovskite quantum dot materials containing Pb or Cd, the material is environment-friendly, and the cost is far lower than that of commercial nitride red powder.
(5) Through proper component design, the oxidation problem of ZnS in the high-temperature melting process is solved, so that the system can directly separate out the quantum dots through proper heat treatment, the raw materials are low in cost, and the preparation method is simple and suitable for industrial production.
Drawings
FIG. 1 is an absorption spectrum of luminescent glasses prepared in example 1, example 2 and example 3 of the present invention.
FIG. 2 is a graph showing the excitation spectra of luminescent glasses prepared in example 1, example 2 and example 3 according to the present invention.
FIG. 3 is an emission spectrum of luminescent glasses prepared in example 1, example 2 and example 3 according to the present invention.
Detailed Description
The following specific examples are given to illustrate the present invention and to assist in further understanding thereof, but the specific details of the embodiments are merely for the purpose of illustrating the invention and are not to be construed as limiting the general technical scope of the invention, and some insubstantial additions and modifications, such as simple changes or substitutions of technical features with the same or similar technical effects, which do not depart from the spirit of the invention are within the scope of the invention.
Example 1
The preparation process of the ZnS-doped quantum dot luminescent glass comprises the following steps: weighing SiO 2 ，B 2 O 3 ，GeO 2 ，Al 2 O 3 ，ZnF 2 The molar ratio of NaF, znS and NiO raw materials is 20:10:27.9:15:10:15:2:0.1, after the raw materials are fully ground and uniformly mixed, placing the mixture into a corundum crucible, then placing the corundum crucible into a high-temperature furnace at 1400 ℃ for capping and melting for 40 minutes, pouring the obtained glass melt into a mold preheated to 300 ℃ for cooling and molding, and then placing the molded glass into a resistance furnace at 400 ℃ for heat preservation for 12 hours to obtain the ZnS quantum dot doped luminescent glass.
Example 2
The preparation process of the ZnS-doped quantum dot luminescent glass comprises the following steps: weighing SiO 2 ，B 2 O 3 ，GeO 2 ，Al 2 O 3 ，ZnF 2 The mole ratio of NaF, znS and NiO raw materials is 25:10:20.8:15:15:10:4:0.2, after the raw materials are fully ground and uniformly mixed, placing the mixture into a corundum crucible, placing the corundum crucible into a high-temperature furnace at 1400 ℃ for capping and melting for 40 minutes, pouring the obtained glass melt into a mould preheated to 300 ℃ for cooling and forming, and placing the formed glass into a resistance furnace at 550 ℃ for heat preservation for 12 hours to obtain Ni 2+ Ion doped ZnS quantum dot luminescent glass.
Example 3
The preparation process of the ZnS-doped quantum dot luminescent glass comprises the following steps: weighing SiO 2 ，B 2 O 3 ，GeO 2 ，Al 2 O 3 ，ZnF 2 The molar ratio of NaF, znS and NiO raw materials is 30:15:15.8:15:10:10:4:0.2, after the raw materials are fully ground and uniformly mixed, placing the mixture into a corundum crucible, placing the corundum crucible into a high-temperature furnace at 1500 ℃ for capping and melting for 60 minutes, pouring the obtained glass melt into a mold preheated to 400 ℃ for cooling and molding, and placing the molded glass into a resistance furnace at 450 ℃ for heat preservation for 36 minutesAnd (3) obtaining the ZnS-doped quantum dot luminescent glass after the time is hours. Under the condition, the ratio of ZnS to Ni ions is 1:20, and the optical properties such as excitation emission spectrum of the sample are ideal after heat treatment.
Claims (7)
1. A ZnS quantum dot doped luminescent glass is characterized in that the luminescent glass takes transparent silicon germanium borate glass as a matrix and ZnS and Ni 2+ Ions are dopants, znS and Ni 2+ The ion ratio is 1:10-30;
the luminous glass comprises the following raw materials in mole percent: siO (SiO) 2 20～40%，B 2 O 3 10～30%，GeO 2 10～30%，Al 2 O 3 5～30%，ZnF 2 5～15%，NaF 5～20%，ZnS 0.5～10%，Ni 2+ 0.01～4%；
The preparation method of the ZnS-doped quantum dot luminescent glass sequentially comprises the following steps:
(1) Preparing raw materials: calculating the mass of each corresponding component according to the mole percentage of the glass composition, and weighing the corresponding raw materials;
(2) The preparation technology comprises the following steps: all the raw material components are uniformly mixed by a mixer to form a mixture, and then the mixture is melted, and uniform glass melt is obtained after homogenization and clarification;
(3) Pouring: casting the glass melt obtained in the step (2) onto a mould preheated to 200-500 ℃ for cooling and forming to obtain preformed glass;
(4) And (3) heat treatment: and (3) placing the preformed glass obtained in the step (3) into a resistance furnace which is heated to 400-650 ℃, preserving heat, and naturally cooling along with the furnace to obtain the corresponding quantum dot luminescent glass.
2. The doped ZnS quantum dot luminescent glass of claim 1, wherein ZnS and Ni 2+ Ion ratio of 1:20, ni 2+ The doping proportion of the ions is 0.1-1%.
3. The doped ZnS quantum dot luminescent glass according to claim 1, wherein the luminescent glass comprises the chemical composition in mole percent of, for exampleThe preparation method comprises the following steps: siO (SiO) 2 30%，B 2 O 3 15%，GeO 2 15.8%，Al 2 O 3 15%，ZnF 2 10%，NaF 10%，ZnS 4%，Ni 2+ 0.2%。
4. The doped ZnS quantum dot luminescent glass according to claim 1, wherein B 2 O 3 In the form of boric acid or sodium borate compounds.
5. The doped ZnS quantum dot luminescent glass according to claim 1, wherein the Al 2 O 3 Added as aluminum oxide, aluminum hydroxide.
6. The doped ZnS quantum dot luminescent glass according to claim 1, wherein Ni 2+ Ions, added in the form of nickel oxide or nickel sulfide.
7. The use of a ZnS-doped quantum dot luminescent glass according to claim 1, wherein the quantum dot luminescent glass has an appearance of orange, red-orange or reddish brown; the quantum dot luminescent glass can be excited by ultraviolet-near ultraviolet light, and when excited by an LED with the wavelength of 225-500 nm, the quantum dot luminescent glass obtains broadband red light emission.
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|---|---|---|---|---|
| US2503140A (en) * | 1945-08-25 | 1950-04-04 | Corning Glass Works | Glass tube and composition |
| CN1526673A (en) * | 2003-03-03 | 2004-09-08 | 华东理工大学 | Quick flashing glass and its prepn process |
| CN109437562A (en) * | 2018-11-16 | 2019-03-08 | 华南理工大学 | A kind of 2 μm of super wideband and tunables shine be precipitated quantum dot mix rare earth laser glass and preparation method thereof |
| CN110963711A (en) * | 2019-12-13 | 2020-04-07 | 深圳第三代半导体研究院 | Composite quantum dot glass and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1590304A1 (en) * | 2002-12-31 | 2005-11-02 | Corning Incorporated | GLASS CERAMICS BASED ON ZnO |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2503140A (en) * | 1945-08-25 | 1950-04-04 | Corning Glass Works | Glass tube and composition |
| CN1526673A (en) * | 2003-03-03 | 2004-09-08 | 华东理工大学 | Quick flashing glass and its prepn process |
| CN109437562A (en) * | 2018-11-16 | 2019-03-08 | 华南理工大学 | A kind of 2 μm of super wideband and tunables shine be precipitated quantum dot mix rare earth laser glass and preparation method thereof |
| CN110963711A (en) * | 2019-12-13 | 2020-04-07 | 深圳第三代半导体研究院 | Composite quantum dot glass and preparation method thereof |
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