CN105567235A - Nitric oxide red long-lasting phosphor material and preparation method thereof - Google Patents
Nitric oxide red long-lasting phosphor material and preparation method thereof Download PDFInfo
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- CN105567235A CN105567235A CN201610093535.7A CN201610093535A CN105567235A CN 105567235 A CN105567235 A CN 105567235A CN 201610093535 A CN201610093535 A CN 201610093535A CN 105567235 A CN105567235 A CN 105567235A
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- 239000000463 material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title abstract 12
- 230000005923 long-lasting effect Effects 0.000 title abstract 6
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 3
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 229910000765 intermetallic Inorganic materials 0.000 claims description 8
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 2
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 2
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- 230000005284 excitation Effects 0.000 abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 abstract description 2
- 150000002736 metal compounds Chemical class 0.000 abstract 2
- 239000002994 raw material Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 230000002688 persistence Effects 0.000 description 8
- 238000001354 calcination Methods 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000002050 diffraction method Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000007850 fluorescent dye Substances 0.000 description 4
- 238000001215 fluorescent labelling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- -1 rare earth ion Chemical class 0.000 description 2
- 229910006360 Si—O—N Inorganic materials 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000000904 thermoluminescence Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides a nitric oxide red long-lasting phosphor material and a preparation method thereof, and relates to a rare earth luminescent material. The chemical general formula of the nitric oxide red long-lasting phosphor material is M(1-x-y)Si2O2N2:Ybx,Lny, wherein M is selected from at least one of Mg, Ca, Sr and Ba, and Ln is selected from at least one of Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm and the like. The preparation method comprises the steps that a sintering aid is added into a mixture of a metal compound containing M, Si, Yb and Ln, sintering is performed in reduction gas, and then the nitric oxide red long-lasting phosphor material is obtained; or silicate containing M is synthesized and then mixed with the metal compound containing M, Si, Yb and Ln, the sintering aid is added, sintering is performed in the reduction gas, and then the nitric oxide red long-lasting phosphor material is obtained. The nitric oxide red long-lasting phosphor material is simple in preparation method, stable in chemical performance and suitable for application scenes which take a white light LED or natural light as an excitation light source.
Description
Technical field
The present invention relates to rare earth luminescent material, specifically relate to a kind of oxynitride red long afterglow luminous material and preparation method thereof.
Background technology
Long after glow luminous material is a class energy storage material, can be stored in the defect level of material by part luminous energy when irradiating by high-energy light, realizes the continuous illumination of several seconds to number h after removing rayed by the energy stored by the form slow releasing of thermoluminescence.Owing to possessing this special characteristics of luminescence, long after glow luminous material has been widely used in the fields such as guidance lighting at night, anti-fake mark.Going deep into further in recent years along with research, the range of application of long after glow luminous material extends to gradually and exchanges the emerging field such as white light LEDs and biological fluorescent labelling.In the potential application of above-mentioned emerging field, the user demand different from night light is proposed for long after glow luminous material, such as in biological fluorescent labelling, the luminescence of long after glow luminous material must be in biological through window (within the scope of 600 ~ 1300nm), and light-emitting particles must possess less size, better chemical stability etc.
Through the lasting research of nearly 20 years, investigators were comparatively ripe for launching blue light and the silicate of green glow and the development and application of aluminate class long after glow luminous material, several silicate and aluminate class material (such as, Sr
2mgSi
2o
7: Eu
2+, Dy
3+, SrAl
2o
4: Eu
2+, Dy
3+deng) time of persistence of commercial fluorescent material reach 10h (document 1:K.Eechhout etc., material (Materials), 2010,3 volumes, 2536-2566 page; Document 2:K.Eechhout etc., material (Materials), 2013,6 volumes, 2789-2818 page).Compare with green long-time afterglow luminescent powder with blueness, red long-afterglow phosphor kind much less known at present, only different materials (such as, Y
2o
2s:Eu
2+, Mg
2+, Ti
4+) on time of persistence and chemical stability compared to blue or green long-time afterglow luminescent powder gap is larger.Therefore, exploitation has the novel red long after glow luminous material of enough chemical stabilities and excellent optical properties for the application advancing long after glow luminous material, particularly (exchanges white light LED part to need to use in high temperature environments in the application of emerging field; Biological fluorescent labelling technology uses under needing high humidity environment) significant.
The most of long after glow luminous material found need ability storage power after the electromagnetic wave irradiation that X-ray, ultraviolet or short wavelength's purple light homenergic are higher and realize long-persistence luminous.But, at the use artificial light such as cold light source such as luminescent lamp and white LED lamp as under the application scenarios of irradiating source, require that long after glow luminous material can be stored luminous energy effectively by under the radiation of visible light of blue light or longer wavelength.So far, long after glow luminous material that is lasting, bright burn can be launched after the radiation of visible light of blue light or longer wavelength very rare.On the other hand, according to up-to-date literature survey, in rare earth ion doped long after glow luminous material, luminescence center is Eu mainly
2+, also comprise Ce
3+, Eu
3+, Tb
3+, Dy
3+deng.So far there are no with Yb
2+as the report of the long after glow luminous material of luminescence center.
Summary of the invention
The object of this invention is to provide stable chemical performance, be applicable to white light LEDs or natural light as excitation light source with Yb
2+for a kind of oxynitride red long afterglow luminous material of luminescence center.
Another object of the present invention is to provide simply, efficiency is high and be conducive to the preparation method of a kind of oxynitride red long afterglow luminous material of suitability for industrialized production.
The chemical general formula of described oxynitride red long afterglow luminous material is: M
1-x-ysi
2o
2n
2: Yb
x, Ln
y; M in formula is at least one in Mg, Ca, Sr, Ba etc.; Ln is at least one in Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm etc.; 0.001≤x≤0.1 in formula, 0≤y≤0.1; Preferably 0.005≤x≤0.05,0≤y≤0.05; M at least comprises Sr element.
The preparation method of described oxynitride red long afterglow luminous material, its concrete steps are as follows:
In the mixture of the metallic compound containing M, Si, Yb, Ln, add sintering aid, sinter in reducing gas, obtain oxynitride red long afterglow luminous material; Or
The first silicate of synthesis containing M, then mix with the metallic compound containing M, Si, Yb, Ln, and add sintering aid, sinter in reducing gas, obtain oxynitride red long afterglow luminous material.
Described metallic compound can be oxide compound, nitride or carbonate; Metallic compound containing Si can be SiO
2and Si
3n
4mixture; Described sintering aid can be selected from SrF
2, SrCl
2, CaF
2, BaF
2, AlF
3, NH
4f, Al
2o
3, H
3bO
3, Li
2cO
3, Na
2cO
3, K
2cO
3deng at least one; Described reducing gas can adopt gas mixture, the pure hydrogen or CO (carbon monoxide converter) gas etc. of nitrogen and hydrogen; The temperature of described sintering can be 1200 ~ 1800 DEG C, and the time of sintering can be 2 ~ 12h, the temperature of sintering preferably 1400 ~ 1600 DEG C.
Oxynitride red long afterglow luminous material prepared by the present invention can by the optical excitation in 250 ~ 480nm wavelength region, stop the exciting light of this wave band according to after, the red long-afterglow that peak wavelength that is bright, that continue is positioned near 600nm can be produced luminous.Oxynitride red long afterglow luminous material preparation method provided by the invention is simple, stable chemical performance, be applicable to white light LEDs or the natural light application scenarios as excitation light source.
The invention has the advantages that:
(1) Late Cambrian is with Yb
2+as the oxynitride long after glow luminous material of luminescence center;
(2) long after glow luminous material emission wavelength provided by the invention is positioned near 600nm, night guidance lighting and biological fluorescent labelling field have potential application;
(3) the matrix MSi of long after glow luminous material provided by the invention
2o
2n
2for oxynitride, luminescence center Yb
2+be coated in the networks of atoms of Si-O-N composition, under comparatively high temps and higher levels of humidity condition, show excellent chemical stability and anti-aging characteristic;
(4) long after glow luminous material provided by the invention can be launched lasting, bright red long afterglow luminous material by after the radiation of visible light of blue light or longer wavelength;
(5) a large amount of defect can be introduced by mixing altogether of trivalent rare earth ions Ln, significantly improve luminous intensity and the time of persistence of steady persistence.
Accompanying drawing explanation
Fig. 1 is XRD figure spectrum and the standard card of the long after glow luminous material obtained by embodiment 1.
Fig. 2 is the long after glow luminous material obtained by embodiment 4, after the LED light source of 455nm irradiates 5min, and the long-persistence luminous spectrum that interval 1 ~ 10min records.
Fig. 3 is the long after glow luminous material obtained by embodiment 1 and embodiment 4, after 455nm Blue-LED lamp 5min, at the steady persistence extinction curve that room temperature records.
Embodiment
Below with reference to accompanying drawing, embodiments of the invention are described in detail.
Embodiment 1
According to SrCO
3: 9.8mmol, Si
3n
4: 5.8mmol, SiO
2: 2.5mmol, Yb
2o
3: 0.1mmol takes raw material respectively, and to add be the sintering aid SrF of above-mentioned raw materials total mass 1% by mass percentage
2, use agate grinding rod and mortar fully to grind 30min in an atmosphere.Said mixture is packed into Al
2o
3in crucible, be then placed in the tube furnace of gas mixture circulation (nitrogen and hydrogen ratio are 95: 5, flow be about 100mLPM) of nitrogen and hydrogen.After 1550 DEG C of calcination 6h, naturally cool to room temperature and take out, after pulverizing and sieving, obtain long after glow luminous material.Sample appearance is orange-yellow powder.
Use X-ray diffractometer (D8, Bruker) crystalline structure diffraction analysis is carried out to the sample that above-mentioned preparation method obtains, gained XRD figure spectrum as shown in Figure 1, diffraction pattern conforms to ICSD standard card (#17-2877), do not have visible mix peak appearance.
The LED light source adopting peak wavelength to be positioned at 395nm irradiates sample 5min, and sample presents bright emitting red light; After closing the LED light source of above-mentioned 395nm, visible faint red long-afterglow is luminous; Close LED light source after the LED light source using peak wavelength to be positioned at 455nm irradiates sample 5min, same visible faint red long-afterglow is luminous.
Use xenon lamp (MAX302, AsahiSpectra) excited sample 5min, test the steady persistence extinction curve of sample after closing light source, as shown in Figure 3.Writing time is 0.1 ~ 120min.
Embodiment 2 ~ 10
Use SrCO
3, CaCO
3, BaCO
3, Si
3n
4, SiO
2, Yb
2o
3, and containing the rare earth oxide of Ln as raw material, take respectively according to molar weight shown in table 1, and add the sintering aid SrF of raw material total mass 1%
2or Al
2o
3, use agate grinding rod and mortar fully to grind 30min in an atmosphere.Said mixture is packed into Al
2o
3in crucible, be then placed in the tube furnace of gas mixture circulation (nitrogen and hydrogen ratio are 95: 5, flow be about 100mLPM) of nitrogen and hydrogen.After 1550 DEG C of calcination 6h, naturally cool to room temperature and take out, after pulverizing and sieving, obtain long after glow luminous material.Sample appearance is orange red powder.
Use X-ray diffractometer to carry out crystalline structure diffraction analysis to embodiment 2 ~ 10 gained sample, gained XRD diffraction pattern conforms to ICSD standard card (#17-2877), and assorted peak does not occur as seen.
The LED light source adopting peak wavelength to be positioned at 395nm irradiates sample 5min, and sample presents bright emitting red light; After closing the LED light source of above-mentioned 395nm, red color visible is long-persistence luminous; Close LED light source after the LED light source using peak wavelength to be positioned at 455nm irradiates sample 5min, same red color visible is long-persistence luminous.Fiber spectrometer (USB2000+, OceanOptics) is used to record the long-persistence luminous spectrum of embodiment 4 as shown in Figure 2, after every bar spectral line is respectively and closes light source 1 ~ 10min, at interval of the long-persistence luminous spectrum that 1min records.
Embodiment 1 uses different Si from embodiment 2
3n
4/ SiO
2as raw material, all can obtain the material launching emitting red light and red long-afterglow luminescence, but the material emission that embodiment 2 obtains is more weak.
In embodiment 3 ~ 5, adopt and mix different trivalent rare earth element Ln altogether, luminescence and the embodiment 1 of the sample of acquisition are similar, but long-persistence luminous intensity is different with time of persistence.Wherein embodiment 4 mixes Ho altogether
2o
3the material obtained afterwards about improves 2 orders of magnitude relative to the long-persistence luminous intensity of embodiment 1, as shown in Figure 3.
Embodiment 6 and embodiment 7, add 20mol%Ca and 20mol%Ba respectively and replace Sr, can obtain the red long afterglow luminous material of same crystal structure (ICSD standard card #17-2877).Compared with embodiment 1, the sample luminescence that embodiment 6 and embodiment 7 obtain is moved toward long wavelength all slightly.
Embodiment 8 and embodiment 9, adopt lower luminescent center ion concentration to mix agent ionic concn together respectively, all can the red long afterglow luminous material of same crystal structure, but long-persistence luminous intensity declines to some extent relative to embodiment 4.
Al is used in embodiment 10
2o
3substitute SrF
2as sintering aid, the red long afterglow luminous material of same crystal structure can be obtained.The sample that embodiment 10 obtains is more fine and close, but long-persistence luminous intensity is more weak compared with embodiment 4, and time of persistence is shorter.
The raw material composition of embodiment 1 ~ 10 correspondence is see table 1.
Table 1
Embodiment 11
According to SrCO
3: 9.6mmol, Si
3n
4: 5.8mmol, SiO
2: 2.5mmol, Yb
2o
3: 0.1mmol, Ho
2o
3: 0.1mmol takes raw material respectively, and adds the sintering aid SrF of above-mentioned raw materials total mass 1%
2, use agate grinding rod and mortar fully to grind 30min in an atmosphere.Said mixture is packed into Al
2o
3in crucible, be then placed in the tube furnace of gas mixture circulation (nitrogen and hydrogen ratio are 90:10, flow be about 100mLPM) of nitrogen and hydrogen.After 1550 DEG C of calcination 6h, naturally cool to room temperature and take out, after pulverizing and sieving, obtain long after glow luminous material.Sample appearance is orange-yellow powder.
Use X-ray diffractometer (D8, Bruker) crystalline structure diffraction analysis is carried out to the sample that above-mentioned preparation method obtains, diffraction pattern conforms to ICSD standard card (#17-2877), do not have visible mix peak appearance.
The LED light source adopting peak wavelength to be positioned at 395nm irradiates sample 5min, and sample presents bright emitting red light; After closing the LED light source of above-mentioned 395nm, visible faint red long-afterglow is luminous; Close LED light source after the LED light source using peak wavelength to be positioned at 455nm irradiates sample 5min, same visible faint red long-afterglow is luminous.
Comparative example 11 and embodiment 4, the crystalline structure of the sample obtained under different reducing atmosphere and the characteristics of luminescence are without significant difference.
Embodiment 12
According to SrCO
3: 9.6mmol, Si
3n
4: 5.8mmol, SiO
2: 2.5mmol, Yb
2o
3: 0.1mmol, Ho
2o
3: 0.1mmol takes raw material respectively, and adds the sintering aid SrF of above-mentioned raw materials total mass 1%
2, use agate grinding rod and mortar fully to grind 30min in an atmosphere.Said mixture is packed into Al
2o
3in crucible, be then placed in the tube furnace of gas mixture circulation (nitrogen and hydrogen ratio are 95:5, flow be about 100mLPM) of nitrogen and hydrogen.After 1400 DEG C of calcination 6h, naturally cool to room temperature and take out, after pulverizing and sieving, obtain long after glow luminous material.Sample appearance is orange-yellow powder.
Use X-ray diffractometer (D8, Bruker) crystalline structure diffraction analysis is carried out to the sample that above-mentioned preparation method obtains, diffraction pattern conforms to ICSD standard card (#17-2877), do not have visible mix peak appearance.
The LED light source adopting peak wavelength to be positioned at 395nm irradiates sample 5min, and sample presents bright emitting red light; After closing the LED light source of above-mentioned 395nm, red color visible is long-persistence luminous; Close LED light source after the LED light source using peak wavelength to be positioned at 455nm irradiates sample 5min, same red color visible is long-persistence luminous.
Comparative example 12 and embodiment 4, sample luminous intensity and the long-persistence luminous intensity of the acquisition of employing lower sintering temperature are more weak.
Embodiment 13
According to SrCO
3: 9.6mmol, SiO
2: 4.0mmol, Yb
2o
3: 0.1mmol, Ho
2o
3: 0.1mmol takes raw material respectively, uses agate grinding rod and mortar fully to grind 30min in an atmosphere.Said mixture is packed into Al
2o
3in crucible, be then placed in the tube furnace of gas mixture circulation (nitrogen and hydrogen ratio are 95:5, flow be about 100mLPM) of nitrogen and hydrogen, after 1300 DEG C of calcination 3h, naturally cool to room temperature and take out, after pulverizing, obtain faint yellow outward appearance powder.Use X-ray diffractometer (D8, Bruker) to characterize, above-mentioned powder is mainly-Sr
2siO
4with-Sr
2siO
4phase.The powder obtained and 5.3mmolSi
3n
4mixing, and add the sintering aid SrF of above-mentioned raw materials gross weight 1wt%
2, be packed into Al
2o
3in crucible, be then placed in the tube furnace of same air-flow, after 1550 DEG C of calcination 6h, naturally cool to room temperature and take out, after pulverizing and sieving, obtain long after glow luminous material.Sample appearance is orange-yellow powder.
Use X-ray diffractometer (D8, Bruker) crystalline structure diffraction analysis is carried out to the sample that above-mentioned preparation method obtains, diffraction pattern conforms to ICSD standard card (#17-2877), do not have visible mix peak appearance.
The LED light source adopting peak wavelength to be positioned at 395nm irradiates sample 5min, and sample presents bright emitting red light; After closing the LED light source of above-mentioned 395nm, red color visible is long-persistence luminous; Close LED light source after the LED light source using peak wavelength to be positioned at 455nm irradiates sample 5min, same red color visible is long-persistence luminous.
Compared to the one-step synthesis method of embodiment 4, adopt the two step synthetic method of embodiment 13, the red long afterglow luminous material that luminous intensity is larger can be obtained.
Claims (10)
1. an oxynitride red long afterglow luminous material, is characterized in that its chemical general formula is: M
1-x-ysi
2o
2n
2: Yb
x, Ln
y; M in formula is at least one in Mg, Ca, Sr, Ba; Ln is at least one in Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm; 0.001≤x≤0.1 in formula, 0≤y≤0.1.
2. a kind of oxynitride red long afterglow luminous material as claimed in claim 1, is characterized in that 0.005≤x≤0.05,0≤y≤0.05.
3. a kind of oxynitride red long afterglow luminous material as claimed in claim 1, is characterized in that M at least comprises Sr element.
4. the preparation method of oxynitride red long afterglow luminous material as claimed in claim 1, is characterized in that its concrete steps are as follows:
In the mixture of the metallic compound containing M, Si, Yb, Ln, add sintering aid, sinter in reducing gas, obtain oxynitride red long afterglow luminous material; Or
The first silicate of synthesis containing M, then mix with the metallic compound containing M, Si, Yb, Ln, and add sintering aid, sinter in reducing gas, obtain oxynitride red long afterglow luminous material.
5. the preparation method of oxynitride red long afterglow luminous material as claimed in claim 4, is characterized in that described metallic compound is oxide compound, nitride or carbonate.
6. the preparation method of oxynitride red long afterglow luminous material as claimed in claim 4, is characterized in that the metallic compound containing Si is SiO
2and Si
3n
4mixture.
7. the preparation method of oxynitride red long afterglow luminous material as claimed in claim 4, is characterized in that described sintering aid is selected from SrF
2, SrCl
2, CaF
2, BaF
2, AlF
3, NH
4f, Al
2o
3, H
3bO
3, Li
2cO
3, Na
2cO
3, K
2cO
3in at least one.
8. the preparation method of oxynitride red long afterglow luminous material as claimed in claim 4, is characterized in that described reducing gas adopts the gas mixture of nitrogen and hydrogen, pure hydrogen or CO (carbon monoxide converter) gas.
9. the preparation method of oxynitride red long afterglow luminous material as claimed in claim 4, it is characterized in that the temperature of described sintering is 1200 ~ 1800 DEG C, the time of sintering is 2 ~ 12h.
10. the preparation method of oxynitride red long afterglow luminous material as claimed in claim 9, is characterized in that the temperature of described sintering is 1400 ~ 1600 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610093535.7A CN105567235B (en) | 2016-02-19 | 2016-02-19 | A kind of nitrogen oxides red long afterglow luminous material and preparation method thereof |
Applications Claiming Priority (1)
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| CN106147757A (en) * | 2016-06-13 | 2016-11-23 | 郑甘裕 | A kind of alkaline earth nitrogen silicate luminescent material, preparation method and applications |
| CN106634976A (en) * | 2016-11-18 | 2017-05-10 | 厦门大学 | Orange red long-afterglow fluorescent powder and preparation method thereof |
| US20180259908A1 (en) * | 2015-11-27 | 2018-09-13 | Nemoto Lumi-Materials Company Limited | Reddish light emitting phosphorescent phosphor |
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| CN102325856A (en) * | 2008-12-22 | 2012-01-18 | 锦湖电气株式会社 | Oxynitride phosphor, method for preparing the same, and light-emitting device |
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| CN102325856A (en) * | 2008-12-22 | 2012-01-18 | 锦湖电气株式会社 | Oxynitride phosphor, method for preparing the same, and light-emitting device |
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| XUEWEN XU ET AL.: "Synthesis and photoluminescence properties of two-bands excited SrSi2O2N2: Yb2+ phosphors", 《ADVANCED MATERIALS RESEARCH》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180259908A1 (en) * | 2015-11-27 | 2018-09-13 | Nemoto Lumi-Materials Company Limited | Reddish light emitting phosphorescent phosphor |
| US10845762B2 (en) * | 2015-11-27 | 2020-11-24 | Nemoto & Co., Ltd. | Reddish light emitting phosphorescent phosphor |
| CN106147757A (en) * | 2016-06-13 | 2016-11-23 | 郑甘裕 | A kind of alkaline earth nitrogen silicate luminescent material, preparation method and applications |
| CN106634976A (en) * | 2016-11-18 | 2017-05-10 | 厦门大学 | Orange red long-afterglow fluorescent powder and preparation method thereof |
| CN106634976B (en) * | 2016-11-18 | 2019-04-09 | 厦门大学 | A kind of orange light long lad phosphor and preparation method thereof |
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