CN107699238A - A kind of terbium ion Tb3+The niobates green emitting phosphor of activation, preparation method and application - Google Patents
A kind of terbium ion Tb3+The niobates green emitting phosphor of activation, preparation method and application Download PDFInfo
- Publication number
- CN107699238A CN107699238A CN201710937146.2A CN201710937146A CN107699238A CN 107699238 A CN107699238 A CN 107699238A CN 201710937146 A CN201710937146 A CN 201710937146A CN 107699238 A CN107699238 A CN 107699238A
- Authority
- CN
- China
- Prior art keywords
- ion
- terbium
- solution
- niobates
- activation
- 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.)
- Pending
Links
- 229910052771 Terbium Inorganic materials 0.000 title claims abstract description 45
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 230000004913 activation Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 13
- 230000005284 excitation Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 3
- 239000010955 niobium Substances 0.000 claims description 47
- -1 terbium ion Chemical class 0.000 claims description 42
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 15
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 229910052758 niobium Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 8
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 7
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910019804 NbCl5 Inorganic materials 0.000 claims description 6
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- LMEHHJBYKPTNLM-UHFFFAOYSA-H terbium(3+);tricarbonate Chemical compound [Tb+3].[Tb+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O LMEHHJBYKPTNLM-UHFFFAOYSA-H 0.000 claims description 4
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 4
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 3
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 3
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000002453 shampoo Substances 0.000 claims description 2
- 238000009877 rendering Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 abstract 1
- 235000015165 citric acid Nutrition 0.000 description 11
- 239000008236 heating water Substances 0.000 description 11
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 235000005979 Citrus limon Nutrition 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910001417 caesium ion Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- CMBJJRLWNDIJTC-UHFFFAOYSA-N nitric acid;terbium Chemical compound [Tb].O[N+]([O-])=O CMBJJRLWNDIJTC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052844 willemite Inorganic materials 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
- C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
- C09K11/7744—Chalcogenides
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of terbium ion Tb3+The niobates green emitting phosphor of activation, preparation method and application.The chemical formula of fluorescent material is Cs5‑5x Tb5x Nb13O35, wherein,xFor terbium ion Tb3+The molar percentage coefficient of doping, 0.0001≤x≤ 0.15, belong to phosphor technical field., 230~400nm is ultraviolet, under the exciting of black light, sends bright green fluorescence, luminous intensity height, excitation wave length and width, stability and colour rendering are good for it, are coincide very much with the launch wavelength of near ultraviolet semiconductor chip.Preparation method of the present invention is sol-gal process, and obtained product quality is stable, favorable reproducibility, easily operated and industrialized production.
Description
Technical field
The present invention relates to a kind of luminescent material, more particularly to a kind of terbium ion Tb3+The green luminescent material of niobates of activation, system
Preparation Method and its application.
Background technology
At present, with the continuous development of the arts such as plasma display, flat board, electroluminescent, fluorescence detection, urgently
Need to provide that stability is more preferable, brightness is higher, colour rendering is more preferable, the more convenient luminescent material of industrial processes.Rare earth ion is mixed
Miscellaneous material is always content widely studied in recent years because of its excellent luminescent properties.Rare earth ion is characterised by part
The 4f layers of filling can be well by 5s2And 5p6Track shields, therefore sharp emission peak occurs in emission spectrum.It is based on
The rare earth doped fluorescent material of linear f-f transition can narrow emission peak high to visible-range, light conversion efficiency.It is dilute
Earth elements occupy the status do not replaced in actual applications, generally as the dopant, activator or sensitizer of luminescent material.
When rare earth element is as dopant, europium, cerium, samarium, the application of terbium are quite varied.
Traditional commercial green emitting phosphor BaAl12O19：Mn2+And Zn2SiO4：Mn2+It is with Mn2+As the centre of luminescence, due to
Mn2+Spin forbidden4T1→6A1Transmitting, makes its twilight sunset overlong time, is unfavorable for the display of dynamic menu.Therefore, permitted both at home and abroad
More researchers are exploring the new green emitting phosphor of exploitation.At present in green luminescent material, Tb3+The luminescent material of doping can be sent out
Bright green fluorescence is projected, monochromaticjty is good, so as to be widely applied to the technologies such as display imaging, new light sources, X ray intensifying screen
In field.With Mn2+Compare, Tb3+'s5D4→7F5Characteristic transition mainly launches the green glow in 542~550 nanometer ranges, lights
Intensity is high, and quantum efficiency is high.In addition, Tb3+Spin coupling can shield spin forbidden, so as to improve its quenching concentration, drop
The low sunset glow time, overcome Mn2+The shortcomings that, so green emitting phosphor often made activator with Tb in recent years.
Tb3+Luminescent properties also depend on host material, researcher both domestic and external is constantly searching for being adapted to Tb3+Mix
Miscellaneous host material.Niobates has unique property, such as chemistry and electrochemical stability, photocatalytic activity, excellent hair
Optical property etc..In recent years, niobates was used in photocatalysis, solar cell, fiber waveguide, optical information storage etc. by wide coverage
Cross.Tb3+Lighted in some niobates as effective activator as high quantum.But at present on niobate luminescent material
Research it is still immature, there is an urgent need to explore the new terbium doped niobate luminescent material with high-quantum efficiency.
The content of the invention
The present invention is in view of the deficienciess of the prior art, provide a kind of new terbium doped niobates with high-quantum efficiency
Luminescent material and preparation method thereof, the technical fields such as plasma display, cathode-ray tube, light emitting diode can be widely applied to
In.
To achieve the above objectives, the technical solution adopted by the present invention is to provide a kind of terbium ion Tb3+The niobates of activation is green
Color fluorescent material, its chemical formula are：Cs5-5x Tb5x Nb13O35, wherein,xFor terbium ion Tb3+The molar percentage coefficient of doping,
0.0001≤x≤0.15。
Fluorescent material provided by the invention launches main ripple under the ultraviolet of 230~400 nanometers of wavelength, near ultraviolet excitation
A length of 543 nanometers of green fluorescence.
Technical solution of the present invention also includes preparing terbium ion Tb as described above3+The side of the niobates green emitting phosphor of activation
Method, using sol-gal process, comprise the following steps：
（1）With Cs containing cesium ion+Compound, Nb containing niobium ion5+Compound, Tb containing terbium ion3+Compound be raw material,
By chemical formula Cs5-5x Tb5x Nb13O35In corresponding stoichiometric proportion weigh each raw material, wherein,xFor terbium ion Tb3+Doping rubs
That percent coefficient, 0.0001≤x≤0.15；
（2）Contain cesium ion Cs by what is weighed+Compound be dissolved in dilute nitric acid solution, stirring is to being completely dissolved, then by caesium
Ion Cs+0.6~3.0% addition complexing agent of molal weight, obtains solution A；Contain niobium ion Nb by what is weighed5+Compound
It is dissolved in hydrofluoric acid solution or methanol solution, in the case where temperature is 60~80 DEG C of water bath condition, stirring is to being completely dissolved, then presses
Niobium ion Nb5+0.6~3.0% addition complexing agent of molal weight, obtains B solution；Contain terbium ion Tb by what is weighed3+Chemical combination
Thing is dissolved in dilute nitric acid solution, and stirring is to being completely dissolved, then by terbium ion Tb3+0.6~3.0% addition complexing of molal weight
Agent, obtain C solution；
（3）Solution A, B solution and C solution are slowly mixed together, in the water-bath that temperature is 60~80 DEG C, under stirring condition, slowly steamed
Shampoo point, then drying processing, obtain fluffy foam-like presoma；
（4）Presoma is placed in Muffle furnace, the precalcining in air atmosphere, precalcining temperature is 300~500 DEG C, precalcining
Time is 2~8 hours；
（5）Product after calcining is cooled to room temperature, sample is taken out, is fully ground and is well mixed, calcined in reducing atmosphere,
Calcining heat is 700~1100 DEG C, and calcination time is 8~16 hours, you can obtains a kind of terbium ion Tb3+The niobates of activation is green
Color fluorescent material.
Cs containing cesium ion described in technical solution of the present invention+Compound be cesium nitrate CsNO3, cesium carbonate Cs2CO3, chlorine
Change one kind in caesium CsCl；Described Nb containing niobium ion5+Compound be niobium pentaoxide Nb2O5, niobium chloride NbCl5In one
Kind；Described Tb containing terbium ion3+Compound be terbium oxide Tb4O7, terbium nitrate Tb (NO3)3, terbium carbonate Tb2(CO3)3, terbium chloride
TbCl3In one kind；Described complexing agent is one kind in citric acid, oxalic acid.
Terbium ion Tb3+In the preparation method of the niobates green emitting phosphor of activation, step（4）Described in precalcining temperature
Preferably 350~450 DEG C, precalcination time is preferably 3~8 hours.Step（5）Described in calcining heat be preferably 750~
1050 DEG C, calcination time is preferably 8~16 hours.
The terbium ion Tb that the present invention is prepared3+The niobates green emitting phosphor of activation, available for plasma display, the moon
Extreme ray pipe, LED device.
Compared with prior art, the remarkable advantage of technical solution of the present invention is：
1. the host material that technical solution of the present invention provides, not only easily realizes the reduction of the trivalent of terbium ion, and trivalent terbium
Ion can also be stabilized among the matrix, its excitation area and use at present 350~410nm of near ultraviolet radiation
The light that InGaN tube cores excite matches, and therefore, can be applied to the LED that the InGaN tube cores of 350~410nm of near ultraviolet radiation excite
In fluorescent material.
2. fluorescent material provided by the invention can launch bright green glow, stability and colour rendering are good.
3. the CIE coordinates of fluorescent material provided by the invention are x=0.3093, y=0.3696, in ultraviolet, near ultraviolet excitation
Under send green light, coordinate blueness and red fluorescence powder to prepare white light LEDs.
Brief description of the drawings
Fig. 1 is the Cs prepared by the technical scheme of the embodiment of the present invention 14.9995Tb0.0005Nb13O35The x-ray powder of sample spreads out
Penetrate collection of illustrative plates；
Fig. 2 is the Cs prepared by the technical scheme of the embodiment of the present invention 14.9995Tb0.0005Nb13O35The SEM spectrum of sample；
Fig. 3 is the Cs prepared by the technical scheme of the embodiment of the present invention 14.9995Tb0.0005Nb13O35Sample obtains under 543 nanometers of monitorings
The exciting light spectrogram arrived；
Fig. 4 is the Cs prepared by the technical scheme of the embodiment of the present invention 14.9995Tb0.0005Nb13O35Sample is in the case where 263 nanometers excite
Luminescent spectrum figure；
Fig. 5 is the Cs prepared by the technical scheme of the embodiment of the present invention 44.95Tb0.05Nb13O35The X-ray powder diffraction pattern of sample；
Fig. 6 is the Cs prepared by the technical scheme of the embodiment of the present invention 44.95Tb0.05Nb13O35The SEM spectrum of sample；
Fig. 7 is the Cs prepared by the technical scheme of the embodiment of the present invention 44.95Tb0.05Nb13O35Sample obtains under 543 nanometers of monitorings
Exciting light spectrogram；
Fig. 8 is the Cs prepared by the technical scheme of the embodiment of the present invention 44.95Tb0.05Nb13O35Sample excited at 380 nanometers under hair
Light spectrogram.
Embodiment
Technical solution of the present invention is further described with reference to the accompanying drawings and examples.
Embodiment 1
Prepare Cs4.9995Tb0.0005Nb13O35
According to chemical formula Cs4.9995Tb0.0005Nb13O35The stoichiometric proportion of middle each element, weigh cesium nitrate CsNO3：3.248 gram,
It is dissolved in dilute nitric acid solution, is stirred continuously, until being completely dissolved, adds 6.404 grams of citric acids, obtain solution A；Weigh
Niobium pentaoxide Nb2O5：5.759 grams, it is dissolved in appropriate hydrofluoric acid solution, 80 DEG C of heating water baths, and is stirred continuously straight
It is completely dissolved to niobium pentaoxide, the pH value of ammoniacal liquor regulation solution is added dropwise to 9, generates white precipitate, filtering, repeatedly uses nothing
Water-ethanol and deionized water washing, then white depositions are dissolved in appropriate citric acid solution, obtain B solution；Weigh oxidation
Terbium Tb4O7：0.0003 gram, it is dissolved in dilute nitric acid solution, is stirred continuously, until being completely dissolved, adds 0.0006 gram of lemon
Acid, obtain C solution；A, B, C solution are mixed, 80 DEG C of heating water baths, are stirred continuously 4 hours, stands, drying, obtains fluffy
Foam-like presoma.
First presoma is placed in Muffle furnace, the precalcining 3 hours at air atmosphere, 350 DEG C, then by after precalcining
Product is cooled to room temperature, takes out sample, is fully ground and is well mixed, then in reducing atmosphere, calcine 8 hours at 750 DEG C, i.e.,
It can obtain a kind of terbium ion Tb3+The niobates green emitting phosphor of activation.
Referring to accompanying drawing 1, it is the X-ray powder diffraction pattern that sample is prepared by the present embodiment technical scheme, and XRD tests are tied
Fruit shows no dephasign.
Referring to accompanying drawing 2, it is the scanning electron microscope (SEM) photograph that sample is prepared by the present embodiment technical scheme, and SEM test results are shown
Sample crystallization is good, and mean particle size is 0.48 micron.
Referring to accompanying drawing 3, it is exciting light of the sample prepared by the present embodiment technical scheme in the case where monitoring 543 nanometers of wavelength
Spectrum, as seen from the figure, the green emitting of the material excites ultraviolet, black light area of the source mainly between 230~400 nanometers
Domain.
Referring to accompanying drawing 4, it is luminous light of the sample prepared by the present embodiment technical scheme in the case where 263 nano wave lengths excite
Spectrogram.As seen from the figure, the main center emission wavelength of the material is 543 nanometers of green emitting wave band, calculates, learns through CIE
Its coordinate is x=0.3093, y=0.3696, is fallen in green area.
The host material that the present embodiment provides, not only easily realizes the reduction of the trivalent of terbium ion, and trivalent terbium ion
It can also be stabilized among the matrix.As shown in Figure 4, prepared Cs4.9995Tb0.0005Nb13O35Its excitation area of material
The light excited with the InGaN tube cores of 350~410nm of the near ultraviolet radiation used at present matches, and therefore, can be applied near ultraviolet
In the LED fluorescent powder that the InGaN tube cores of 350~410nm radiation excite.
Embodiment 2
Prepare Cs4.995Tb0.005Nb13O35
According to chemical formula Cs4.995Tb0.005Nb13O35The stoichiometric proportion of middle each element, weigh cesium carbonate Cs2CO3：2.712 gram,
It is dissolved in dilute nitric acid solution, is stirred continuously, until being completely dissolved, adds 7.998 grams of citric acids, obtain solution A；Weigh
Niobium pentaoxide Nb2O5：5.759 grams, it is dissolved in appropriate hydrofluoric acid solution, 80 DEG C of heating water baths, and is stirred continuously straight
It is completely dissolved to niobium pentaoxide, the pH value of ammoniacal liquor regulation solution is added dropwise to 9, generates white precipitate, filtering, repeatedly uses nothing
Water-ethanol and deionized water washing, then white depositions are dissolved in appropriate citric acid solution, obtain B solution；Weigh nitric acid
Terbium Tb (NO3)3：0.006 gram, it is dissolved in dilute nitric acid solution, is stirred continuously, until being completely dissolved, adds 0.008 gram of lemon
Lemon acid, obtains C solution；Finally A, B, C solution are mixed, 80 DEG C of heating water baths, are stirred continuously 4 hours, stands, drying, obtains
Fluffy foam-like presoma.
First presoma is placed in Muffle furnace, the precalcining 4 hours under conditions of air atmosphere, 400 DEG C of temperature, then will
Product after precalcining is cooled to room temperature, takes out sample, is fully ground and is well mixed, then in reducing atmosphere, temperature 800
Calcined 9 hours under conditions of DEG C, you can obtain a kind of terbium ion Tb3+The niobates green emitting phosphor of activation.
The present embodiment technical scheme prepares the X-ray powder diffraction pattern of sample, scanning electron microscope (SEM) photograph, exciting light spectrogram, hair
Light spectrogram is consistent with the sample prepared in embodiment 1.The material provided can be used for preparing plasma display, cathode-ray
Pipe, LED device.
Embodiment 3
Prepare Cs4.975Tb0.025Nb13O35
According to chemical formula Cs4.975Tb0.025Nb13O35The stoichiometric proportion of middle each element, weigh cesium chloride CsCl：2.792 gram, will
It is dissolved in dilute nitric acid solution, is stirred continuously, until being completely dissolved, is added 4.479 grams of oxalic acid, is obtained solution A；Weigh five oxygen
Change two niobium Nb2O5：5.759 grams, it is dissolved in appropriate hydrofluoric acid solution, 80 DEG C of heating water baths, and is stirred continuously until five
Aoxidize two niobiums to be completely dissolved, the pH value of ammoniacal liquor regulation solution is added dropwise to 9, generates white precipitate, filters, repeatedly with anhydrous second
Alcohol and deionized water washing, then white depositions are dissolved in appropriate oxalic acid solution, obtain B solution；Weigh terbium carbonate Tb2
(CO3)3：0.021 gram, it is dissolved in dilute nitric acid solution, is stirred continuously, until being completely dissolved, adds 0.023 gram of oxalic acid, obtain
To C solution；Finally A, B, C solution are mixed, 80 DEG C of heating water baths, are stirred continuously 4 hours, stands, drying, obtains fluffy bubble
Foam shape presoma.
First presoma is placed in Muffle furnace, in air atmosphere, temperature be precalcining 5 hours under conditions of 450 DEG C, so
The product after precalcining is cooled to room temperature afterwards, sample is taken out, is fully ground and is well mixed, then in reducing atmosphere, temperature
To calcine 9 hours under conditions of 850 DEG C, you can obtain a kind of terbium ion Tb3+The niobates green emitting phosphor of activation.
The present embodiment technical scheme prepares the X-ray powder diffraction pattern of sample, scanning electron microscope (SEM) photograph, exciting light spectrogram, hair
Light spectrogram is consistent with the sample prepared in embodiment 1.
Embodiment 4
Prepare Cs4.95Tb0.05Nb13O35
According to chemical formula Cs4.95Tb0.05Nb13O35The stoichiometric proportion of middle each element, weigh cesium nitrate CsNO3：1.930 gram, will
It is dissolved in dilute nitric acid solution, is stirred continuously, until being completely dissolved, is added 1.902 grams of citric acids, is obtained solution A；Weigh chlorine
Change niobium NbCl5：7.024 grams, it is dissolved in appropriate methanol, 60 DEG C of heating water baths, and is stirred continuously up to being completely dissolved,
4.996 grams of citric acids are added, obtain B solution；Weigh terbium oxide Tb4O7：0.019 gram, it is dissolved in dilute nitric acid solution, no
Disconnected stirring, until being completely dissolved, adds 0.019 gram of citric acid, obtains C solution；Finally A, B, C solution are mixed, 80 DEG C of water
Bath heating, is stirred continuously 4 hours, stands, drying, obtains fluffy foam-like presoma.
First presoma is placed in Muffle furnace, in air atmosphere, temperature be precalcining 5 hours under conditions of 400 DEG C, so
The product after precalcining is cooled to room temperature afterwards, sample is taken out, is fully ground and is well mixed, then in reducing atmosphere, 900 DEG C
Lower calcining 10 hours, you can obtain a kind of terbium ion Tb3+The niobates green emitting phosphor of activation.
Referring to accompanying drawing 5, it is the X-ray powder diffraction pattern that sample is prepared by the present embodiment technical scheme, and XRD tests are tied
Fruit shows no dephasign.
Referring to accompanying drawing 6, it is the scanning electron microscope (SEM) photograph that sample is prepared by the present embodiment technical scheme, and SEM test results are shown
Sample crystallization is good, and mean particle size is 0.11 micron.
Referring to accompanying drawing 7, it is exciting light of the sample prepared by the present embodiment technical scheme in the case where monitoring 543 nanometers of wavelength
Spectrum, as seen from the figure, the green emitting of the material excites ultraviolet, black light area of the source mainly between 230~400 nanometers
Domain.
Referring to accompanying drawing 8, it is luminous light of the sample prepared by the present embodiment technical scheme in the case where 380 nano wave lengths excite
Spectrogram.As seen from the figure, the main center emission wavelength of the material is 543 nanometers of green emitting wave band, calculates, learns through CIE
Its coordinate is x=0.3098, y=0.4456, is fallen in green area.
Embodiment 5
Prepare Cs4.6Tb0.4Nb13O35
According to chemical formula Cs4.6Tb0.4Nb13O35The stoichiometric proportion of middle each element, weigh cesium carbonate Cs2CO3：1.499 grams, by it
It is dissolved in dilute nitric acid solution, is stirred continuously, until being completely dissolved, adds 2.485 grams of oxalic acid, obtain solution A；Weigh niobium chloride
NbCl5：7.024 grams, it is dissolved in appropriate methanol, 60 DEG C of heating water baths, and is stirred continuously until being completely dissolved, then add
Enter 7.023 grams of oxalic acid, obtain B solution；Weigh terbium carbonate Tb2(CO3)3：0.199 gram, it is dissolved in dilute nitric acid solution, constantly
Stirring, until being completely dissolved, 0.216 gram of oxalic acid is added, obtains C solution；Finally A, B, C solution are mixed, 80 DEG C of water-baths add
Heat, and be stirred continuously 4 hours, stand, drying, obtain fluffy foam-like presoma.
First presoma is placed in Muffle furnace, in air atmosphere, precalcining 5 hours under 430 DEG C of temperature conditionss, then will
Product after precalcining is cooled to room temperature, takes out sample, is fully ground and is well mixed, then in reducing atmosphere, 950 DEG C of temperature
Under the conditions of calcine 12 hours, you can obtain a kind of terbium ion Tb3+The niobates green emitting phosphor of activation.
The present embodiment technical scheme prepares the X-ray powder diffraction pattern of sample, scanning electron microscope (SEM) photograph, exciting light spectrogram, hair
Light spectrogram is consistent with the sample prepared in embodiment 4.
Embodiment 6
Prepare Cs4.4Tb0.6Nb13O35
According to chemical formula Cs4.4Tb0.6Nb13O35The stoichiometric proportion of middle each element, weigh cesium chloride CsCl：1.482 grams, by it
It is dissolved in dilute nitric acid solution, is stirred continuously, until being completely dissolved, adds 2.536 grams of citric acids, obtain solution A；Weigh chlorination
Niobium NbCl5：7.024 grams, it is dissolved in appropriate methanol, 60 DEG C of heating water baths, and is stirred continuously until be completely dissolved, then
7.493 grams of citric acids are added, obtain B solution；Weigh terbium nitrate Tb (NO3)3：0.414 gram, it is dissolved in dilute nitric acid solution, no
Disconnected stirring, until being completely dissolved, adds 0.346 gram of citric acid, obtains C solution；Finally A, B, C solution are mixed, 80 DEG C of water
Bath heating, and be stirred continuously 4 hours, stand, drying, obtain fluffy foam-like presoma.
First presoma is placed in Muffle furnace, in air atmosphere, precalcining 4 hours under 350 DEG C of temperature conditionss, then will
Product after precalcining is cooled to room temperature, takes out sample, is fully ground and is well mixed, then in reducing atmosphere, 1000 DEG C of temperature
Calcined 12 hours under the conditions of degree, you can obtain a kind of terbium ion Tb3+The niobates green emitting phosphor of activation.
The present embodiment technical scheme prepares the X-ray powder diffraction pattern of sample, scanning electron microscope (SEM) photograph, exciting light spectrogram, hair
Light spectrogram is consistent with the sample prepared in embodiment 4.
Embodiment 7
Prepare Cs4.25Tb0.75Nb13O35
According to chemical formula Cs4.25Tb0.75Nb13O35The stoichiometric proportion of middle each element, weigh cesium nitrate CsNO3：1.657 gram, will
It is dissolved in dilute nitric acid solution, is stirred continuously, until being completely dissolved, is added 1.913 grams of oxalic acid, is obtained solution A；Weigh chlorination
Niobium NbCl5：7.024 grams, it is dissolved in appropriate methanol, 60 DEG C of heating water baths, and is stirred continuously until be completely dissolved, then
5.853 grams of oxalic acid are added, obtain B solution；Weigh terbium chloride TbCl3：0.396 gram, it is dissolved in dilute nitric acid solution, constantly stirs
Mix, until being completely dissolved, add 0.338 gram of oxalic acid, obtain C solution；Finally A, B, C solution are mixed, 80 DEG C of heating water baths,
And it is stirred continuously 4 hours, stands, drying, obtain fluffy foam-like presoma.
First presoma is placed in Muffle furnace, then will be pre-calcined in air atmosphere, precalcining 8 hours at a temperature of 400 DEG C
Product after burning is cooled to room temperature, takes out sample, is fully ground and is well mixed, then in reducing atmosphere, at a temperature of 1050 DEG C
Calcining 16 hours, you can obtain a kind of terbium ion Tb3+The niobates green emitting phosphor of activation.
The present embodiment technical scheme prepares the X-ray powder diffraction pattern of sample, scanning electron microscope (SEM) photograph, exciting light spectrogram, hair
Light spectrogram is consistent with the sample prepared in embodiment 4.
Claims (7)
- A kind of 1. terbium ion Tb3+The niobates green emitting phosphor of activation, it is characterised in that：Its chemical formula is：Cs5- 5x Tb5x Nb13O35, wherein,xFor terbium ion Tb3+The molar percentage coefficient of doping, 0.0001≤x≤0.15。
- A kind of 2. terbium ion Tb according to claim 13+The niobates green emitting phosphor of activation, it is characterised in that：It is described For fluorescent material under the ultraviolet of 230~400 nanometers of wavelength, near ultraviolet excitation, it is 543 nanometers green glimmering to launch dominant wavelength Light.
- A kind of 3. terbium ion Tb as claimed in claim 13+The preparation method of the niobates green emitting phosphor of activation, its feature exist In using sol-gal process, comprise the following steps：（1）With Cs containing cesium ion+Compound, Nb containing niobium ion5+Compound, Tb containing terbium ion3+Compound be raw material, press Chemical formula Cs5-5x Tb5x Nb13O35In corresponding stoichiometric proportion weigh each raw material, wherein,xFor terbium ion Tb3+Mole of doping Percent coefficient, 0.0001≤x≤0.15；（2）Contain cesium ion Cs by what is weighed+Compound be dissolved in dilute nitric acid solution, stirring to being completely dissolved, then by caesium from Sub- Cs+0.6~3.0% addition complexing agent of molal weight, obtains solution A；Contain niobium ion Nb by what is weighed5+Compound it is molten Solution is in hydrofluoric acid solution or methanol solution, and in the case where temperature is 60~80 DEG C of water bath condition, stirring is to being completely dissolved, then by niobium Ion Nb5+0.6~3.0% addition complexing agent of molal weight, obtains B solution；Contain terbium ion Tb by what is weighed3+Compound It is dissolved in dilute nitric acid solution, stirring is to being completely dissolved, then by terbium ion Tb3+0.6~3.0% addition complexing agent of molal weight, Obtain C solution；（3）Solution A, B solution and C solution are slowly mixed together, in the water-bath that temperature is 60~80 DEG C, under stirring condition, slowly steamed Shampoo point, then drying processing, obtain fluffy foam-like presoma；（4）Presoma is placed in Muffle furnace, the precalcining in air atmosphere, precalcining temperature is 300~500 DEG C, precalcining Time is 2~8 hours；（5）Product after calcining is cooled to room temperature, sample is taken out, is fully ground and is well mixed, calcined in reducing atmosphere, Calcining heat is 700~1100 DEG C, and calcination time is 8~16 hours, you can obtains a kind of terbium ion Tb3+The niobates of activation is green Color fluorescent material.
- A kind of 4. terbium ion Tb according to claim 33+The preparation method of the niobates green emitting phosphor of activation, its feature It is：Described Cs containing cesium ion+Compound be cesium nitrate CsNO3, cesium carbonate Cs2CO3, one kind in cesium chloride CsCl；Institute The Nb containing niobium ion stated5+Compound be niobium pentaoxide Nb2O5, niobium chloride NbCl5In one kind；Described Tb containing terbium ion3 +Compound be terbium oxide Tb4O7, terbium nitrate Tb (NO3)3, terbium carbonate Tb2(CO3)3, terbium chloride TbCl3In one kind；Described Complexing agent is one kind in citric acid, oxalic acid.
- A kind of 5. terbium ion Tb according to claim 33+The preparation method of the niobates green emitting phosphor of activation, its feature It is：Step（4）Described precalcining temperature is 350~450 DEG C, and precalcination time is 3~8 hours.
- A kind of 6. terbium ion Tb according to claim 33+The preparation method of the niobates green emitting phosphor of activation, its feature It is：Step（5）Described calcining heat is 750~1050 DEG C, and calcination time is 8~16 hours.
- A kind of 7. terbium ion Tb as claimed in claim 13+The application of the niobates green emitting phosphor of activation, it is characterised in that： For plasma display, cathode-ray tube, LED device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710937146.2A CN107699238A (en) | 2017-10-10 | 2017-10-10 | A kind of terbium ion Tb3+The niobates green emitting phosphor of activation, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710937146.2A CN107699238A (en) | 2017-10-10 | 2017-10-10 | A kind of terbium ion Tb3+The niobates green emitting phosphor of activation, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107699238A true CN107699238A (en) | 2018-02-16 |
Family
ID=61184133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710937146.2A Pending CN107699238A (en) | 2017-10-10 | 2017-10-10 | A kind of terbium ion Tb3+The niobates green emitting phosphor of activation, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107699238A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108865129A (en) * | 2018-08-03 | 2018-11-23 | 广东工业大学 | A kind of preparation method of low temperature preparation ytterbium Er ions lithium niobate up-conversion luminescence powder |
| CN109957397A (en) * | 2019-04-28 | 2019-07-02 | 江苏师范大学 | A kind of Tb3+ activation fluoboric acid strontium barium green emitting phosphor and its preparation and application |
| CN110129046A (en) * | 2019-05-30 | 2019-08-16 | 江苏师范大学 | A kind of Tb3+The fluorine niobium tantalates fluorescent powder of doping and its synthesis and application |
-
2017
- 2017-10-10 CN CN201710937146.2A patent/CN107699238A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 周媛媛: "铌酸盐纳米发光材料的制备与表征", 《中国博士学位论文全文数据库》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108865129A (en) * | 2018-08-03 | 2018-11-23 | 广东工业大学 | A kind of preparation method of low temperature preparation ytterbium Er ions lithium niobate up-conversion luminescence powder |
| CN109957397A (en) * | 2019-04-28 | 2019-07-02 | 江苏师范大学 | A kind of Tb3+ activation fluoboric acid strontium barium green emitting phosphor and its preparation and application |
| CN109957397B (en) * | 2019-04-28 | 2021-04-27 | 江苏师范大学 | Tb3+ activated barium strontium fluoborate green fluorescent powder and preparation and application thereof |
| CN110129046A (en) * | 2019-05-30 | 2019-08-16 | 江苏师范大学 | A kind of Tb3+The fluorine niobium tantalates fluorescent powder of doping and its synthesis and application |
| CN110129046B (en) * | 2019-05-30 | 2021-09-17 | 江苏师范大学 | Tb3+Doped fluoroniobium tantalate fluorescent powder and synthesis and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102851026B (en) | Red light material for bi-primary-color white light LEDs (light-emitting diodes) and preparation method thereof | |
| CN109370587B (en) | Nitride near-infrared fluorescent material, the light emitting device containing nitride near-infrared fluorescent material | |
| Kang et al. | A novel far-red emitting phosphor activated Ba2LuTaO6: Mn4+: Crystal structure, optical properties and application in plant growth lighting | |
| CN105694886B (en) | Eu (Eu)2+Preparation method and application of doped fluosilicate-based luminescent material | |
| CN103627392A (en) | Antimonate-based red phosphor powder and preparation method and application thereof | |
| CN107699238A (en) | A kind of terbium ion Tb3+The niobates green emitting phosphor of activation, preparation method and application | |
| CN106833636A (en) | Can be by near ultraviolet and blue light activated red fluorescence powder, preparation method and application | |
| CN109988575B (en) | Eu (Eu)3+Ion-activated vanadium-phosphorus niobate red fluorescent powder, preparation method and application thereof | |
| CN106701074B (en) | A kind of metatitanic acid alkali red up-conversion luminescent material and preparation method thereof | |
| CN110591711B (en) | Gallate red fluorescent powder for white light LED and preparation method thereof | |
| CN115746850B (en) | Manganese ion activated oxyhalide red luminescent material and preparation method thereof | |
| CN105419798B (en) | A kind of preparation method and application of orange red antimonate luminescent materials | |
| CN108504357A (en) | A kind of titanium aluminate-base up-conversion luminescent material, preparation method and application | |
| CN103627393B (en) | Tungsten molybdate red phosphor powder and preparation method and application thereof | |
| CN103275711B (en) | Fluorine titanium salt red-light material for white LED with two primary colors and preparation method of material | |
| CN106010528A (en) | Bismuth-manganese-doped blue fluorescent powder and preparation method and application thereof | |
| CN102341478A (en) | Oxide luminescent materials activated by trivalent thulium and their preparations | |
| JP2013531710A (en) | Yttrium oxide phosphor and method for producing the same | |
| CN104927856A (en) | Method for preparing red phosphors of tungstate based on sol-gel combustion method | |
| CN105419797B (en) | A kind of orange red fluorescent powder of suitable near ultraviolet excitation and its preparation and application | |
| CN109762564B (en) | Europium ion Eu3+Activated titanate red fluorescent powder, preparation method and application thereof | |
| CN102660267A (en) | Preparation method of aluminate fluorescent powde | |
| CN109179481B (en) | Quadrivalent manganese ion doped barium fluoscandate red light-emitting material and preparation method thereof | |
| CN116875307B (en) | Tetravalent manganese ion activated titanate-based red luminescent material and preparation method thereof | |
| CN112607775B (en) | Ho3+Activated green down-conversion phosphor and method of making |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180216 |