CN116814263A - Single-phase white light fluorescent material and preparation method and application thereof - Google Patents
Single-phase white light fluorescent material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116814263A CN116814263A CN202310674160.3A CN202310674160A CN116814263A CN 116814263 A CN116814263 A CN 116814263A CN 202310674160 A CN202310674160 A CN 202310674160A CN 116814263 A CN116814263 A CN 116814263A
- Authority
- CN
- China
- Prior art keywords
- white light
- formula
- fluorescent material
- phase white
- phase
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 142
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000012071 phase Substances 0.000 claims description 117
- 239000000843 powder Substances 0.000 claims description 21
- 238000000227 grinding Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 230000005284 excitation Effects 0.000 abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 description 34
- 150000002500 ions Chemical class 0.000 description 26
- 239000011159 matrix material Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 11
- 239000013078 crystal Substances 0.000 description 9
- 238000002189 fluorescence spectrum Methods 0.000 description 9
- 238000000695 excitation spectrum Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- -1 rare earth ions Chemical class 0.000 description 5
- 238000009877 rendering Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- UXBZSSBXGPYSIL-UHFFFAOYSA-N phosphoric acid;yttrium(3+) Chemical compound [Y+3].OP(O)(O)=O UXBZSSBXGPYSIL-UHFFFAOYSA-N 0.000 description 4
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 4
- 230000005283 ground state Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005090 crystal field Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002165 resonance energy transfer Methods 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 241001085205 Prenanthella exigua Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention belongs to the technical field of rare earth luminescent materials, and relates to a single-phase white light fluorescent material, a preparation method and application thereof. A single-phase white light fluorescent material, which comprises a chemical composition general formula shown in the following formula (1) or formula (2): lu (Lu) 1‑x‑y NbO 4 :xBi 3+ ,yDy 3+ Formula (1), or, lu 1‑x‑y‑z‑t Bi t NbO 4 :xTm 3+ ,yTb 3+ ,zEu 3+ Formula (2); wherein 0.005 in the formula (1)<x<0.04，0.01<y<0.02; 0.01 in the formula (2)<t<0.10，0.002<x<0.05，0.05<y<0.15，0.002<z<0.12. The single-phase white light fluorescent material can stably and efficiently emit light under the excitation of near ultraviolet light, and the energy consumption of a WLED luminescent device prepared by using the single-phase white light fluorescent material is reduced, so that the purposes of efficiency improvement and energy saving are achieved.
Description
Technical Field
The invention belongs to the technical field of rare earth luminescent materials, and particularly relates to a single-phase white light fluorescent material, a preparation method and application thereof.
Background
According to the report of the world energy report 2022, about 20% of energy consumption is derived from luminescent products worldwide, which means that developing efficient luminescent materials and devices is one of important strategies for coping with energy crisis and realizing energy conservation and emission reduction. In the fields of general illumination, high-quality display and the like, a light conversion type White Light Emitting Diode (WLED) is a light emitting device which is most widely applied and occupies most of market share of light emitting products, a semiconductor LED chip is adopted to excite fluorescent powder, white light emission is realized through light-light conversion, the white light fluorescent powder is a core material for realizing the light conversion function of the WLED device, and the light conversion efficiency of the fluorescent powder is one of key factors for determining the luminous efficiency of the device, so that the light conversion efficiency of the fluorescent powder is greatly improved and is an internal requirement for reducing the energy consumption of the WLED device.
At present, the commercial WLED mainly adopts two light conversion technologies to realize white light emission, and one of the most widely adopted methods is that YAG is excited by blue light of an InGaN chip, and the color of the light emitted by the device is changed along with the driving voltage and the thickness of a fluorescent powder coating, and the color rendering of fluorescence is poor due to the lack of red light components; in the other method, the mixed fluorescent powder of red light, green light and blue light is excited by an ultraviolet-near ultraviolet chip to emit white light, and the ratio of the three primary colors is difficult to regulate and control due to the existence of fluorescence reabsorption among different materials, so that the luminous efficiency is low, and the color reproducibility, the color stability and the like are greatly influenced; meanwhile, the preparation difficulty of the WLED is increased by a coating process of mixing several fluorescent powders, and the production cost is high. It is clear that these conventional WLED techniques emit white light through a combination of multiple fluorescent materials, which is the source of various drawbacks. In order to solve the technical problem, a new method for manufacturing the WLED by exciting the single-phase white light fluorescent powder based on the ultraviolet/near ultraviolet LED chip is provided, and the development of the single-phase white light fluorescent powder capable of stably and efficiently emitting light becomes the key of technical breakthrough.
The preparation of high-efficiency luminous single-phase white light fluorescent material requires the selection of proper matrix materials and matched activators. A process for preparing single-phase white fluorescent material features that the rare-earth Dy is emitted as yellow light 3+ Ion doped to blue-emitting LuNbO 4 Preparation of white light fluorescent Material Lu in matrix 0.99 NbO 4 :xDy 3+ Electron transition of excited substrate using 261nm ultraviolet light produces blue light emission band with center wavelength at 402nm, while substrate sensitizes Dy 3+ The ion emits yellow light with the wavelength of 578nm, and the white light emission of the single-phase fluorescent material can be realized by mixing the light with the two colors (Liang Hong, liu Chunmeng, a single-matrix doped white luminescent material, a preparation method and application thereof, 201610879137.8;Tao Wang Yihua Hu et al.Journal ofLuminescence181 (2017): 189-195). Although the method provides a thought for developing single-phase white light fluorescent materials, because the band gap of the matrix material is wider, the excitation spectrum range of the excitation material for emitting white light is in the deep ultraviolet region and is not matched with the wavelength ranges of the blue light chip and the near ultraviolet chip which can be produced in a mass way at present, so that the practical application of the material is limited. Meanwhile, in order to meet the requirements of device application of the material, the luminous efficiency of the material needs to be further improved. Another idea for preparing single-phase white light fluorescent materials is to dope various rare earth ions with characteristic emission of red light, green light and blue light (three primary colors) into the same matrix material to prepare single-phase fluorescent materials, and then excite the doped ions by using near ultraviolet light and simultaneously emit the three primary colors to realize white light emission. For example: tm capable of characteristic blue light emission 3+ Tb of green light 3+ Eu and Red light 3+ At the same time participate in GdNbO 4 Preparation of single-phase white light fluorescent material GdNbO in matrix 4 :xTm 3+ ,yTb 3+ ,zEu 3+ (Xiaoming Liu, chen Chen et al Inorganic Chemistry 2016, 55:10383-10396.). However, due to energy loss generated by energy transfer between various ions, the quantum efficiency of light emission of such white light fluorescent materials is often low, for example: single-phase white light fluorescent material GdNbO 4 :xTm 3+ ,yTb 3+ ,zEu 3+ The highest quantum yield of white light emission is only 21.5 percent (the external quantum efficiency is lower), and the requirements of practical device application are far from being met.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a single-phase white light fluorescent material and a preparation method and application thereof. The single-phase white light fluorescent material can stably and efficiently emit light under the excitation of near ultraviolet light, and the energy consumption of a WLED luminescent device prepared by using the single-phase white light fluorescent material is reduced, so that the purposes of efficiency improvement and energy saving can be achieved.
To this end, the first aspect of the present invention provides a single-phase white light fluorescent material, which comprises a chemical composition general formula shown in the following formula (1) or formula (2):
Lu 1-x-y NbO 4 :xBi 3+ ,yDy 3+ (1),
or, lu 1-x-y-z-t Bi t NbO 4 :xTm 3+ ,yTb 3+ ,zEu 3+ Formula (2);
wherein 0.005< x <0.04,0.01< y <0.02 in said formula (1); in the formula (2), 0.01< t <0.10,0.002< x <0.05,0.05< y <0.15, and 0.002< z <0.12.
In some embodiments of the present invention, gd is further included in the single-phase white light fluorescent material represented by formula (1) 3+ A chemical composition formula represented by the following formula (3):
(Lu 1-m Gd m ) 1-x-y NbO 4 :xBi 3+ ,yDy 3+ formula (3);
wherein 0< m <0.006,0.005< x <0.04,0.01< y <0.02 in the formula (3).
In some embodiments of the invention, 0.005< x <0.03,0.01< y <0.015 in formula (1). Preferably 0.005< x <0.02,0.01< y <0.014; more preferably 0.005< x <0.01,0.01< y <0.012. In some examples, x in formula (1) may be, but is not limited to, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, or 0.04. In some examples, y in the formula (1) may be, but is not limited to, 0.01, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019 or 0.02.
In some embodiments of the invention, 0.03< t <0.10,0.002< x <0.03,0.05< y <0.10,0.005< z <0.12 in formula (2). Preferably 0.05< t <0.10,0.002< x <0.02,0.05< y <0.09,0.008< z <0.12; more preferably 0.07< t <0.10,0.002< x <0.01,0.05< y <0.08,0.01< z <0.12. In some examples, t in formula (2) may be, but is not limited to, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.10. In some examples, x in the formula (2) may be, but is not limited to, 0.002, 0.003, 0.004,0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, or 0.04. In some examples, y in the formula (2) may be, but is not limited to, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, or 0.15. In some examples, z in the formula (2) may be, but is not limited to, 0.002, 0.003, 0.004,0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, or 0.12.
In some embodiments of the invention, 0.001< m <0.006,0.005< x <0.03,0.01< y <0.015 in the formula (3). Preferably 0.001< m <0.005,0.005< x <0.02,0.01< y <0.014; more preferably 0.001< m <0.004,0.005< x <0.01,0.01< y <0.012. In some examples, m in the formula (3) may be, but is not limited to, 0.001, 0.002, 0.003, 0.004,0.005, or 0.006. In some examples, x in formula (3) may be, but is not limited to, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, or 0.04. In some examples, y in the formula (3) may be, but is not limited to, 0.01, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019 or 0.02.
According to the invention, the single-phase white light fluorescent material comprises a chemical composition general formula shown as follows: lu (Lu) 1-x-y NbO 4 :xBi 3+ ,yDy 3+ Wherein 0.005 of<x<0.04，0.01<y<0.02; preferably, x is 0.01 or 0.03 and y is 0.015.
In the presence of ABO 4 LuNbO with crystal structure 4 In the matrix, nb atoms and O atoms form 4-coordinated BO 4 Tetrahedra, lu and BO forming an 8-coordinate with the O atom 8 The polyhedral, the valence band of the material is mainly composed of p electrons of oxygen atoms, and the conduction band is composed of d electrons of Nb. Bi (Bi) 3+ The ions have 6s 2 Electronic configuration, small amount of Bi 3+ Ion (0.005)<x<0.04 After substitution of Lu at BiO 8 In polyhedron, bi 3+ The ground state energy level of the ion is 1 S0, the excited electron configuration 6S6p has 3 P 0 、 3 P 1 、 3 P 2 And 1 P 1 four states, the action of the crystal field causes Bi to be 3+ Ion ground state energy level 1 S 0 P-electron energy level slightly higher than that of O atom, while Bi 3+ Ion excited state energy level 3 P 1 Distributed near the d electron energy level of Nb, which allows electrons to be extracted from Bi 3+ The energy of the ion ground state energy level excited to the conduction band of the matrix is much smaller than the band gap of the matrix, so that Bi is excited 3+ Ion doped LuNbO 4 The wavelength range of the substrate luminescence goes from the deep ultraviolet region to the near ultraviolet region. Although Bi 3+ Transition of ions from ground to excited states 1 S 0 → 3 P 0 And 1 S 0 → 3 P 2 is spin forbidden, but 1 S 0 → 3 P 1 And 1 S 0 → 1 P 1 the transition is allowed so that a strong broadband light absorption can be obtained, which provides the necessary preconditions for efficient luminescence of the material. Therefore, under the excitation of near ultraviolet light, bi 3+ Doped LuNbO 4 The matrix can emit blue light with wavelength range of 375-575 nm (center wavelength of 460 nm), due to the wavelength range of the emission spectrum and Dy 3+ Characterization of ionsThe excitation peak is completely matched, which is Bi 3+ Ions and LuNbO 4 Matrix Dy 3+ The resonance energy transfer of ions provides conditions, and thus Dy is sensitized by the matrix 3+ The efficiency of yellow light emission is extremely high. The process of matrix sensitized rare earth ion luminescence is completed through exciton mediated energy conduction, when near ultraviolet light excites Lu 1-x-y NbO 4 :xBi 3+ ,yDy 3+ During electron transition, excitons are generated first, and with the aid of exciton movement, excitation energy is transferred from the matrix to RE ion to excite RE to emit blue light and Dy 3+ The emitted yellow light mixes together to form a highly bright white light.
According to the invention, the single-phase white light fluorescent material comprises a chemical composition general formula shown as follows: (Lu) 1- m Gd m ) 1-x-y NbO 4 :xBi 3+ ,yDy 3+ Wherein 0 is<m<0.006，0.005<x<0.04，0.01<y<0.02; preferably, m is 0.001, x is 0.01 or 0.03, and y is 0.015.
Gd is added on the basis 3+ Ion, very small amount of Gd 3+ Ion (0.001)<m<0.006 Substitution of Lu 3+ Incorporated into a matrix with Bi 3+ Synergistic effect of Dy can be further regulated 3+ The crystal field environment and energy transmission channel are located, thereby promoting Dy from matrix to 3+ The energy conduction of the ions further improves the luminous efficiency of the material.
According to the invention, the single-phase white light fluorescent material comprises a chemical composition general formula shown as follows: lu (Lu) 1-x-y-z-t Bi t NbO 4 :xTm 3+ ,yTb 3+ ,zEu 3+ Wherein 0.01<t<0.10，0.002<x<0.05，0.05<y<0.15，0.002<z<0.12; preferably, t is 0.03, x is 0.03, y is 0.1, and z is 0.005 or 0.01.
Bi is mixed with 3+ Ion doping to LuNbO 4 The substrate can adjust the wavelength range of the light emitted by the substrate to near ultraviolet (270 nm-330 nm) region, and the electron transition excited by ultraviolet light 1 S 0 → 3 P 1 And 1 S 0 → 1 P 1 the material is allowed by spin to cause stronger broadband light absorption, so that the material can obtain excitation energy as much as possible, the energy loss in the light excitation process is reduced, and the external quantum efficiency of the material luminescence is improved. Meanwhile, the matrix can emit blue light with the wavelength range of 375nm-575nm (the central wavelength is 460 nm) under the excitation of near ultraviolet light, and the wavelength range of the emission spectrum can be matched with the Tm of rare earth ions 3+ ,Tb 3+ ,Eu 3+ Overlapping wavelength ranges of characteristic excitation peaks of (2) such that Bi 3+ Ions and LuNbO 4 The matrix can simultaneously transfer energy to three ions through resonance energy transfer, thereby sensitizing the three rare earth ions to emit light simultaneously. Since the process of sensitizing rare earth ion luminescence is completed by exciton movement assistance, energy exchange transfer between three ions is suppressed to a certain extent. Due to Tm 3+ ,Tb 3+ ,Eu 3+ The main characteristic emission of the fluorescent dye is blue light, green light and red light respectively, the atomic proportion of three ions is regulated, a single-phase material can emit three primary colors at the same time, and white light with high color rendering property can be obtained by combining the materials. Meanwhile, in order to obtain excitation energy as much as possible, promote energy transfer and avoid the influence of concentration quenching on the luminous efficiency of the material, the invention is characterized in that 4 The matrix is doped with more Bi 3+ Ions such that Bi 3+ Ion doping concentration t reaches 0.01<t<In the range of 0.10, the technical aim of improving the luminous external quantum efficiency of the material can be fulfilled.
According to a second aspect of the present invention, there is provided a method for preparing a single-phase white light fluorescent material according to the first aspect of the present invention, comprising: weighing raw materials comprising elements in the formula (1), the formula (2) or the formula (3) according to chemical dosage, fully grinding and mixing, and heating to perform solid phase reaction.
In some embodiments of the present invention, the preparation method of the single-phase white light fluorescent material represented by formula (1) or formula (3) includes the following specific steps:
s1: weighing Lu as raw material according to chemical dosage 2 O 3 、Nb 2 O 5 、Bi 2 O 3 And Dy 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Or weighing Lu as raw material according to chemical dosage 2 O 3 、Nb 2 O 5 、Bi 2 O 3 、Gd 2 O 3 And Dy 2 O 3 ；
S2: fully grinding and uniformly mixing the raw materials weighed in the step S1, reacting at 1000 ℃ for 6-8h, naturally cooling to room temperature, and then ball milling for 12h;
s3: and (3) placing the material treated in the step (S2) at 1250 ℃ for reaction for 8-12h, cooling to room temperature, and grinding into powder.
In some embodiments of the present invention, the preparation method of the single-phase white light fluorescent material represented by formula (2) includes the following specific steps:
s1: weighing Lu as raw material according to chemical dosage 2 O 3 、Nb 2 O 5 、Bi 2 O 3 、Tm 2 O 3 、Tb 4 O 7 And Eu 2 O 3 ；
S2: fully grinding and uniformly mixing the raw materials weighed in the step S1, reacting at 1000 ℃ for 10-14h, naturally cooling to room temperature, and then ball milling for 12h;
s3: and (2) placing the material treated in the step (S2) at 1250 ℃ for reaction for 10-14h, cooling to room temperature, and grinding into powder.
According to the invention, the starting oxide is pre-burned in advance at 800 ℃ for 2 hours.
A third aspect of the present invention provides an application of the single-phase white light fluorescent material according to the first aspect of the present invention or the single-phase white light fluorescent material prepared by the preparation method according to the second aspect of the present invention in preparing a light conversion type White Light Emitting Diode (WLED).
In some embodiments of the present invention, the single-phase white light fluorescent material is coated on a near ultraviolet chip having a light emission wavelength of 270nm to 330nm to prepare a light conversion type white light emitting diode.
According to the invention, the single-phase white light fluorescent material is uniformly mixed with silica gel and then coated on the surface of a near ultraviolet chip with the luminous wavelength of 270-330 nm.
In some embodiments of the invention, the silica gel is mixed with a single-phase white light fluorescent material according to a mass ratio of 1:1.2-1.6; preferably 1:1.4-1.6. In some examples, the silica gel may be mixed with the single-phase white light fluorescent material in a mass ratio of, but not limited to, 1:1.2, 1:1.3, 1:1.4, 1:1.5, or 1:1.6.
In some embodiments of the present invention, the thickness of the coating layer coated on the surface of the near ultraviolet chip after the single-phase white light fluorescent material is mixed with silica gel is 130-160 μm; preferably 140-150 μm. In some examples, the thickness of the coating applied to the near-UV chip surface after mixing the single-phase white light fluorescent material with silica gel may be, but is not limited to, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, or 160 μm.
The invention has the beneficial effects that:
(1) The invention provides a single-phase white light fluorescent material which is prepared by doping Bi into a LuNbO4 matrix simultaneously 3+ And Dy 3 + The excitation spectrum range can be adjusted from the deep ultraviolet region to the near ultraviolet region, and the light can be stably and efficiently emitted under the excitation of the near ultraviolet light.
(2) The preparation method provided by the invention is used for preparing the single-phase white light fluorescent material, is simple and convenient to operate, and has low production cost.
(3) The single-phase white light fluorescent material provided by the invention is applied to the preparation of WLED, and can solve the problems of low luminous efficiency, high energy consumption and the like caused by the mismatching of the excitation spectrum range of the traditional fluorescent material and the wavelength ranges of the blue light chip and the near ultraviolet chip which can be produced in mass at present or the energy loss generated by the energy transfer between various ions. The single-phase white light fluorescent material provided by the invention has the characteristics of stable and efficient light emission, can be applied to the prepared WLED to stably and efficiently emit light, is suitable for the fields of daily illumination, high-end display and the like, and is suitable for large-scale production.
Drawings
FIG. 1 shows a single-phase white light emitting phosphor (Lu) prepared in example 2 0.999 Gd 0.001 ) 0.975 NbO 4 :0.01Bi 3+ ,0.015Dy 3+ And the single-phase white light fluorescent material (Lu) prepared in example 3 0.999 Gd 0.001 ) 0.955 NbO 4 :0.03Bi 3+ ,0.015Dy 3+ X-ray diffraction pattern of (2)；
FIG. 2 is a single-phase white light emitting phosphor Lu prepared in example 4 0.835 Bi 0.03 NbO 4 :0.03Tm 3+ ,0.1Tb 3+ ,0.005Eu 3+ And the single-phase white light fluorescent material Lu prepared in example 5 0.83 Bi 0.03 NbO 4 :0.03Tm 3+ ,0.1Tb 3+ ,0.01Eu 3+ X-ray diffraction patterns of (2);
FIG. 3 shows a single-phase white light emitting phosphor Lu prepared in example 1 of Experimental example 1 0.975 NbO 4 :0.01Bi 3+ ,0.015Dy 3 + Single-phase white light fluorescent material (Lu) prepared in example 2 0.999 Gd 0.001 ) 0.975 NbO 4 :0.01Bi 3+ ,0.015Dy 3+ Single-phase white light fluorescent material (Lu) prepared in example 3 0.999 Gd 0.001 ) 0.955 NbO 4 :0.03Bi 3+ ,0.015Dy 3+ Single-phase white light fluorescent material Lu prepared in comparative example 1 0.985 NbO 4 :0.015Dy 3+ A photoexcitation spectrum of luminescence at 578 nm;
FIG. 4 is a graph showing fluorescence spectra of single-phase white light fluorescent materials prepared in examples 1 to 3 and comparative example 1 in Experimental example 2 excited by 305nm near ultraviolet light; wherein, the single-phase white light fluorescent material Lu prepared in the A-comparative example 1 0.985 NbO 4 :0.015Dy 3+ B-Single-phase white light fluorescent Material (Lu) prepared in example 3 0.999 Gd 0.001 ) 0.955 NbO 4 :0.03Bi 3+ ,0.015Dy 3+ C-Single-phase white light fluorescent Material Lu prepared in example 1 0.975 NbO 4 :0.01Bi 3+ ,0.015Dy 3+ D-Single-phase white light fluorescent Material (Lu) prepared in example 2 0.999 Gd 0.001 ) 0.975 NbO 4 :0.01Bi 3+ ,0.015Dy 3+ ；
FIG. 5 is a color chart of luminescence of the single-phase white light fluorescent material prepared in examples 2-3 excited by 305nm near ultraviolet light in experiment example 2; wherein, A-Single-phase white light fluorescent material (Lu) prepared in example 2 0.999 Gd 0.001 ) 0.975 NbO 4 :0.01Bi 3+ ,0.015Dy 3+ B-realSingle-phase white light fluorescent material (Lu) prepared in example 3 0.999 Gd 0.001 ) 0.955 NbO 4 :0.03Bi 3+ ,0.015Dy 3 + ；
FIG. 6 shows that the single-phase white light fluorescent material (Lu) prepared in example 2 was excited by 305nm near ultraviolet light in experimental example 3 0.999 Gd 0.001 ) 0.975 NbO 4 :0.01Bi 3+ ,0.015Dy 3+ A quantum efficiency test chart of luminescence;
FIG. 7 is a fluorescence spectrum of the single-phase white light fluorescent material prepared in examples 4 to 5 of Experimental example 4 excited by 305nm near ultraviolet light; wherein, A-example 4 prepared single-phase white light fluorescent material Lu 0.835 Bi 0.03 NbO 4 :0.03Tm 3+ ,0.1Tb 3+ ,0.005Eu 3+ B-Single-phase white light fluorescent Material Lu prepared in example 5 0.83 Bi 0.03 NbO 4 :0.03Tm 3+ ,0.1Tb 3+ ,0.01Eu 3 + ；
FIG. 8 is a color chart of luminescence of the single-phase white light fluorescent materials prepared in examples 4 to 5 excited by 305nm near ultraviolet light in experiment example 4; wherein, A-example 4 prepared single-phase white light fluorescent material Lu 0.835 Bi 0.03 NbO 4 :0.03Tm 3+ ,0.1Tb 3+ ,0.005Eu 3+ B-Single-phase white light fluorescent Material Lu prepared in example 5 0.83 Bi 0.03 NbO 4 :0.03Tm 3+ ,0.1Tb 3+ ,0.01Eu 3+ ；
FIG. 9 is a graph showing the results of the light flux test conducted on the WLED prepared in example 6 in Experimental example 5; wherein, (a) -the luminous spectrum diagram of the WLED and the inset diagram are the physical photos of the WLED, and (b) -the luminous color rendering index of the WLED;
FIG. 10 is a graph of WLED luminescence prepared in Experimental example 6 driven by different voltages for example 6.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
Example 1
The embodiment provides a single-phase white light fluorescent material, which comprises the following chemical composition general formula: lu (Lu) 0.975 NbO 4 :0.01Bi 3+ ,0.015Dy 3+ 。
Pre-burning the oxide raw material at 800 ℃ for 2 hours in advance, and then weighing a proper amount of Lu according to the stoichiometric amount 2 O 3 、Nb 2 O 5 、Bi 2 O 3 And Dy 2 O 3 Fully grinding and uniformly mixing, reacting for 6 hours at 1000 ℃, naturally cooling to room temperature, and ball-milling for 12 hours; then placing the mixture into a muffle furnace to react for 10 hours at 1250 ℃, cooling to room temperature and grinding the mixture into powder.
Example 2
The embodiment provides a single-phase white light fluorescent material, which comprises the following chemical composition general formula: (Lu) 0.999 Gd 0.001 ) 0.975 NbO 4 :0.01Bi 3+ ,0.015Dy 3+ 。
The embodiment also provides a preparation method of the single-phase white light fluorescent material, which comprises the following steps: with Lu 2 O 3 、Nb 2 O 5 、Bi 2 O 3 、Gd 2 O 3 And Dy 2 O 3 Pre-burning oxide raw material at 800 ℃ for 2 hours, and weighing a proper amount of Lu according to stoichiometric amount 2 O 3 、Nb 2 O 5 、Bi 2 O 3 、Gd 2 O 3 And Dy 2 O 3 Fully grinding and uniformly mixing, reacting for 6 hours at 1000 ℃, naturally cooling to room temperature, and ball-milling for 12 hours; then placing the mixture into a muffle furnace to react for 10 hours at 1250 ℃, cooling to room temperature and grinding the mixture into powder.
After grinding into powder, the phase and crystal structure of the material were analyzed by X-ray diffraction, and the results are shown in FIG. 1, which demonstrate that the single-phase white light fluorescent material (Lu) with the xenotime type crystal structure was obtained in this example 0.999 Gd 0.001 ) 0.975 NbO 4 :0.01Bi 3+ ,0.015Dy 3+ 。
Example 3
The embodiment provides a single-phase white lightA fluorescent material comprising the chemical composition formula shown below: (Lu) 0.999 Gd 0.001 ) 0.955 NbO 4 :0.03Bi 3+ ,0.015Dy 3+ 。
This example uses the same preparation method as example 2 to prepare a single-phase white light fluorescent material.
After grinding into powder, the phase and crystal structure of the material were analyzed by X-ray diffraction, and the results are shown in FIG. 1, which demonstrate that the single-phase white light fluorescent material (Lu) with the xenotime type crystal structure was obtained in this example 0.999 Gd 0.001 ) 0.955 NbO 4 :0.03Bi 3+ ,0.015Dy 3+ 。
Example 4
The embodiment provides a single-phase white light fluorescent material, which comprises the following chemical composition general formula: lu (Lu) 0.835 Bi 0.03 NbO 4 :0.03Tm 3+ ,0.1Tb 3+ ,0.005Eu 3+ 。
The embodiment also provides a preparation method of the single-phase white light fluorescent material, which comprises the following steps: with Lu 2 O 3 、Nb 2 O 5 、Bi 2 O 3 、Tm 2 O 3 、Tb 4 O 7 And Eu 2 O 3 Pre-burning oxide raw material at 800 ℃ for 2 hours, and weighing a certain amount of Lu according to stoichiometric amount 2 O 3 、Nb 2 O 5 、Bi 2 O 3 、Tm 2 O 3 、Tb 4 O 7 And Eu 2 O 3 Fully grinding and uniformly mixing, reacting for 12 hours at 1000 ℃, naturally cooling to room temperature, and ball-milling for 12 hours; then placing the mixture into a muffle furnace to react for 12 hours at 1250 ℃, cooling to room temperature and grinding the mixture into powder.
After grinding into powder, the phase and crystal structure of the material are analyzed by X-ray diffraction, and the result is shown in figure 2, which proves that the single-phase white light fluorescent material Lu with xenotime type crystal structure is prepared in the embodiment 0.835 Bi 0.03 NbO 4 :0.03Tm 3 + ,0.1Tb 3+ ,0.005Eu 3+ 。
Example 5
The embodiment provides a single-phase white light fluorescent material, which comprises the following chemical composition general formula: lu (Lu) 0.83 Bi 0.03 NbO 4 :0.03Tm 3+ ,0.1Tb 3+ ,0.01Eu 3+ 。
This example uses the same preparation method as example 4 to prepare a single-phase white light fluorescent material.
After grinding into powder, the phase and crystal structure of the material are analyzed by X-ray diffraction, and the result is shown in figure 2, which proves that the single-phase white light fluorescent material Lu with xenotime type crystal structure is prepared in the embodiment 0.83 Bi 0.03 NbO 4 :0.03Tm 3 + ,0.1Tb 3+ ,0.01Eu 3+ 。
Example 6
The embodiment provides a light conversion type White Light Emitting Diode (WLED), which comprises the following steps:
single-phase white light fluorescent material Lu prepared in example 4 0.835 Bi 0.03 NbO 4 :0.03Tm 3+ ,0.1Tb 3+ ,0.005Eu 3 + The preparation method comprises the steps of uniformly mixing silica gel with single-phase white light fluorescent powder according to the mass ratio of 1:1.4, coating the mixture on the surface of a chip with the luminous wavelength of 310nm, and drying and curing the coating with the thickness of 150 mu m to prepare the WLED.
Comparative example 1
The comparative example provides a single-phase white light fluorescent material, which comprises the following chemical composition general formula: lu (Lu) 0.985 NbO 4 :0.015Dy 3+ 。
Comparative example with Lu 2 O 3 、Nb 2 O 5 、Dy 2 O 3 As a raw material, a single-phase white light fluorescent material was prepared by the same preparation method as in example 1.
Experimental example 1
Single-phase white light fluorescent materials prepared in examples 1 to 3 and comparative example 1 were measured for luminescence (Dy) at 578nm using a fluorescence spectrometer, respectively 3+ Characteristic emission of (c) and the results are shown in fig. 3.
As can be seen from the results of FIG. 3, the single-phase white light fluorescent materials prepared in examples 1-3 were excited to emit light in the near ultraviolet region ranging from 270nm to 330 nm; and the excitation spectrum of the single-phase white light fluorescent material prepared in the comparative example 1 is in the deep ultraviolet region of 225nm-275 nm. The excitation spectrum of the single-phase white light fluorescent material prepared by the invention is in the near ultraviolet region of 270nm-330nm, and the excitation spectrum is matched with the wavelength range of a near ultraviolet chip which can be produced in quantity, so that the single-phase white light fluorescent material can be suitable for a large number of practical applications.
Experimental example 2
The fluorescence spectra of the single-phase white light fluorescent materials prepared in examples 1 to 3, which were excited by near ultraviolet light having a wavelength of 305nm, were measured using a fluorescence spectrometer, respectively, and the fluorescence spectra of the single-phase white light fluorescent material prepared in comparative example 1, which were excited by deep ultraviolet light having a wavelength of 248nm, were measured, and the results are shown in fig. 4. The color coordinates of the single-phase white light fluorescent materials prepared in examples 2 to 3 were shown in fig. 5.
As can be seen from the results of FIG. 4, the single-phase white light fluorescent material Lu prepared in comparative example 1 0.985 NbO 4 :0.015Dy 3+ The fluorescence spectrum of the luminescence is shown as a line A in FIG. 4, and the main luminescence peak comprises a blue luminescence band with a central wavelength of 405nm and a yellow luminescence band with a wavelength of 578 nm; single-phase white light fluorescent material (Lu) prepared in example 3 0.999 Gd 0.001 ) 0.955 NbO 4 :0.03Bi 3+ ,0.015Dy 3+ The fluorescence spectrum of the luminescence is shown as line B in FIG. 4, and the main luminescence peak comprises a blue luminescence band with the center wavelength of 460nm and a yellow luminescence band with the wavelength of 578 nm; single-phase white light fluorescent material Lu prepared in example 1 0.975 NbO 4 :0.01Bi 3+ ,0.015Dy 3+ The fluorescence spectrum of the luminescence is shown as line C in FIG. 4, and the main luminescence peak comprises a blue luminescence band with a center wavelength of 465nm and a yellow luminescence band with a wavelength of 578 nm; the single-phase white light fluorescent material (Lu) prepared in example 2 0.999 Gd 0.001 ) 0.975 NbO 4 :0.01Bi 3 + ,0.015Dy 3+ The fluorescence spectrum of the luminescence is shown in the D line of FIG. 4, and the main luminescence peak includes a blue luminescence band having a center wavelength of 460nm and a yellow luminescence band having a wavelength of 578 nm. Compare line a in fig. 4 withAs can be seen from the C-line spectrum, example 1 of the present invention was doped with Bi as compared with comparative example 1 3+ On one hand, the excitation spectrum range of the material luminescence is adjusted from the deep ultraviolet region to the near ultraviolet region, and meanwhile, the luminescence intensity of the material is also enhanced. As can be seen by comparing the spectra of C line and D line in FIG. 4, the doping of Bi 3+ On the basis of (1) and doped with Gd in a small amount 3+ Although the luminescent color of the material is not significantly changed, the luminous intensity is further enhanced. As can be seen by comparing the spectra of the B line and the D line in FIG. 4, bi is doped 3+ Proper amount of Bi is needed 3+ Too large doping amount is unfavorable for improving the luminous intensity.
As can be seen from the results of FIG. 5, the single-phase white light fluorescent material (Lu 0.999 Gd 0.001 ) 0.975 NbO 4 :0.01Bi 3+ ,0.015Dy 3+ And the single-phase white light fluorescent material (Lu) prepared in example 3 0.999 Gd 0.001 ) 0.955 NbO 4 :0.03Bi 3+ ,0.015Dy 3+ Positive white light is emitted under the excitation of near ultraviolet light of 305 nm. Similarly, the deep ultraviolet light with the wavelength of 248nm is adopted to excite the single-phase white light fluorescent material Lu prepared in the comparative example 1 0.985 NbO 4 :0.015Dy 3+ The color of the luminescence is also in the white light area; single-phase white light fluorescent material Lu prepared in example 1 is excited by near ultraviolet light with wavelength of 305nm 0.975 NbO 4 :0.01Bi 3+ ,0.015Dy 3+ The color of the emitted light is also in the white light region.
Experimental example 3
The quantum efficiency of the single-phase white light fluorescent material prepared in example 2 was measured at 305nm near-ultraviolet excitation, and the absorption rate of the single-phase white light fluorescent material to excitation light and the quantum yield of the material luminescence were calculated, and the results are shown in fig. 6.
As can be seen from the results of fig. 6, the absorption rate (AE) of the single-phase white light fluorescent material prepared in example 2 to excitation light reaches 89.8%, and the quantum yield (plaq) of the light emitted by the measurement material reaches 55.12%. The single-phase white light fluorescent material prepared by the invention has the characteristic of high-efficiency luminescence.
Experimental example 4
The fluorescence spectra of the single-phase white light fluorescent materials prepared in examples 4 to 5, which were excited by near ultraviolet light having a wavelength of 305nm, were measured using a fluorescence spectrometer, respectively, and the results are shown in fig. 7; the color coordinates of the single-phase white light fluorescent material are shown in fig. 8.
As can be seen from the results of FIG. 7, the single-phase white light fluorescent materials prepared in examples 4 to 5 each have a luminescence spectrum including Tm 3+ 、Tb 3+ 、Eu 3+ Is characterized by emission of (a); as can be seen by comparing the A-line and B-line spectra in FIG. 7, eu is increased 3+ Is favorable for improving the luminous intensity.
As can be seen from the results of FIG. 8, the single-phase white light fluorescent material Lu prepared in example 4 0.835 Bi 0.03 NbO 4 :0.03Tm 3+ ,0.1Tb 3+ ,0.005Eu 3+ And the single-phase white light fluorescent material Lu prepared in example 5 0.83 Bi 0.03 NbO 4 :0.03Tm 3+ ,0.1Tb 3+ ,0.01Eu 3+ Positive white light is emitted under the excitation of 305nm near ultraviolet light.
Experimental example 5
The light flux test was performed on the WLED prepared in example 6 using an OHSP-350A/M spectrocolorimeter, hgzhou Hope colorimeter, and the results are shown in FIG. 9.
As can be seen from the results of fig. 9, the correlated color temperature of the WLED luminescence prepared in example 6 of the present invention is 4542K, which indicates that the WLED can emit stronger warm white light; FIG. 9 (b) shows the color rendering index of 15 representative color patches, the average of which reaches 85, demonstrating that WLED prepared in example 6 of the present invention has better color rendering.
Experimental example 6
The luminescence results of the WLED prepared in example 6 under different voltage driving were examined and shown in fig. 10.
As can be seen from the results of fig. 10, WLED prepared in example 6 of the present invention can stably emit strong warm white light under different voltage driving.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (10)
1. A single-phase white light fluorescent material is characterized by comprising a chemical composition general formula shown in the following formula (1) or formula (2):
Lu 1-x-y NbO 4 :xBi 3+ ,yDy 3+ (1),
or, lu 1-x-y-z-t Bi t NbO 4 :xTm 3+ ,yTb 3+ ,zEu 3+ Formula (2);
wherein 0.005< x <0.04,0.01< y <0.02 in said formula (1); in the formula (2), 0.01< t <0.10,0.002< x <0.05,0.05< y <0.15, and 0.002< z <0.12.
2. The single-phase white light emitting phosphor of claim 1, wherein the single-phase white light emitting phosphor of formula (1) further comprises Gd 3+ A chemical composition formula represented by the following formula (3):
(Lu 1-m Gd m ) 1-x-y NbO 4 :xBi 3+ ,yDy 3+ formula (3);
wherein 0< m <0.006,0.005< x <0.04,0.01< y <0.02 in the formula (3).
3. The single-phase white light emitting phosphor of claim 1, wherein 0.005< x <0.03,0.01< y <0.015 in formula (1).
4. The single-phase white light fluorescent material according to claim 1, wherein 0.03< t <0.10,0.002< x <0.03,0.05< y <0.10,0.005< z <0.12 in the formula (2).
5. The single-phase white light emitting phosphor of claim 2, wherein 0.001< m <0.006,0.005< x <0.03,0.01< y <0.015 in formula (3).
6. A method of preparing a single-phase white light emitting phosphor according to any one of claims 1 to 5, comprising: weighing raw materials comprising elements in the formula (1), the formula (2) or the formula (3) according to chemical dosage, fully grinding and mixing, and heating to perform solid phase reaction.
7. The preparation method of the single-phase white light fluorescent material shown in the formula (1) or the formula (3) according to the preparation method of the single-phase white light fluorescent material, which comprises the following specific steps:
s1: weighing Lu as raw material according to chemical dosage 2 O 3 、Nb 2 O 5 、Bi 2 O 3 And Dy 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Or weighing Lu as raw material according to chemical dosage 2 O 3 、Nb 2 O 5 、Bi 2 O 3 、Gd 2 O 3 And Dy 2 O 3 ；
S2: fully grinding and uniformly mixing the raw materials weighed in the step S1, reacting at 1000 ℃ for 6-8h, naturally cooling to room temperature, and then ball milling for 12h;
s3: and (3) placing the material treated in the step (S2) at 1250 ℃ for reaction for 8-12h, cooling to room temperature, and grinding into powder.
8. The preparation method of the single-phase white light fluorescent material shown in the formula (2) according to claim 6 comprises the following specific steps:
s1: weighing Lu as raw material according to chemical dosage 2 O 3 、Nb 2 O 5 、Bi 2 O 3 、Tm 2 O 3 、Tb 4 O 7 And Eu 2 O 3 ；
S2: fully grinding and uniformly mixing the raw materials weighed in the step S1, reacting at 1000 ℃ for 10-14h, naturally cooling to room temperature, and then ball milling for 12h;
s3: and (2) placing the material treated in the step (S2) at 1250 ℃ for reaction for 10-14h, cooling to room temperature, and grinding into powder.
9. Use of a single-phase white light emitting phosphor according to any one of claims 1 to 5 or prepared by a method according to any one of claims 6 to 8 for the preparation of a light-converting white light emitting diode.
10. The use according to claim 9, wherein the single-phase white light fluorescent material is coated on a near ultraviolet chip with a light emission wavelength of 270nm-330nm to prepare a light conversion type white light emitting diode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310674160.3A CN116814263B (en) | 2023-06-07 | 2023-06-07 | Single-phase white light fluorescent material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310674160.3A CN116814263B (en) | 2023-06-07 | 2023-06-07 | Single-phase white light fluorescent material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116814263A true CN116814263A (en) | 2023-09-29 |
| CN116814263B CN116814263B (en) | 2024-05-28 |
Family
ID=88113823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310674160.3A Active CN116814263B (en) | 2023-06-07 | 2023-06-07 | Single-phase white light fluorescent material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116814263B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962542A (en) * | 2010-09-14 | 2011-02-02 | 南昌大学 | Niobate-based red fluorescent powder for white LED as well as preparation method and application thereof |
| CN102002362A (en) * | 2010-09-14 | 2011-04-06 | 南昌大学 | Fluorescent powder for white light LED, preparation method and application thereof |
| CN102492423A (en) * | 2011-12-19 | 2012-06-13 | 重庆市科学技术研究院 | Red fluorescent material used for white LED (light-emitting diode) and preparation method thereof |
| CN104152145A (en) * | 2014-07-23 | 2014-11-19 | 南京航空航天大学 | Three-activator single-matrix white light phosphor and preparation method thereof |
| CN105623660A (en) * | 2016-03-17 | 2016-06-01 | 中南大学 | Warm white fluorescent powder excited by ultraviolet LED |
| CN106554778A (en) * | 2016-10-08 | 2017-04-05 | 中山大学 | A kind of single-substrate single-doping white luminescent material and preparation method and application |
| CN109181697A (en) * | 2018-10-29 | 2019-01-11 | 江苏师范大学 | A kind of niobates fluorescent powder of strong red emission and preparation method thereof |
| CN112852422A (en) * | 2021-02-05 | 2021-05-28 | 成都理工大学 | White LED fluorescent material and preparation method thereof |
-
2023
- 2023-06-07 CN CN202310674160.3A patent/CN116814263B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962542A (en) * | 2010-09-14 | 2011-02-02 | 南昌大学 | Niobate-based red fluorescent powder for white LED as well as preparation method and application thereof |
| CN102002362A (en) * | 2010-09-14 | 2011-04-06 | 南昌大学 | Fluorescent powder for white light LED, preparation method and application thereof |
| CN102492423A (en) * | 2011-12-19 | 2012-06-13 | 重庆市科学技术研究院 | Red fluorescent material used for white LED (light-emitting diode) and preparation method thereof |
| CN104152145A (en) * | 2014-07-23 | 2014-11-19 | 南京航空航天大学 | Three-activator single-matrix white light phosphor and preparation method thereof |
| CN105623660A (en) * | 2016-03-17 | 2016-06-01 | 中南大学 | Warm white fluorescent powder excited by ultraviolet LED |
| CN106554778A (en) * | 2016-10-08 | 2017-04-05 | 中山大学 | A kind of single-substrate single-doping white luminescent material and preparation method and application |
| CN109181697A (en) * | 2018-10-29 | 2019-01-11 | 江苏师范大学 | A kind of niobates fluorescent powder of strong red emission and preparation method thereof |
| CN112852422A (en) * | 2021-02-05 | 2021-05-28 | 成都理工大学 | White LED fluorescent material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| TENGYUE WANG等: "Designing stimuli-responsive and color-tunable indicators via the coexistence of dual emitting centers", MATER. CHEM. FRONT., vol. 7, 30 December 2022 (2022-12-30), pages 535 - 544 * |
| XIAOMING LIU等: "Host-Sensitized and Tunable Luminescence of GdNbO4:Ln3+ (Ln3+=Eu3+/Tb3+/Tm3+) Nanocrystalline Phosphors with Abundant Color", INORG. CHEM., vol. 55, 26 September 2016 (2016-09-26), pages 10383 - 10396 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116814263B (en) | 2024-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112094647B (en) | A kind of narrow-band emitting nitrogen oxide red phosphor and preparation method thereof | |
| CN101029231A (en) | Bivalent-europium-excited base-metal silicate phosphate fluorescent powder and its production | |
| CN113736463A (en) | Purple light excited cyan fluorescent powder and preparation method and application thereof | |
| CN101531902B (en) | Barium-doped cerium-and-lithium-activated silicate orange yellow fluorescent powder and preparation method | |
| CN103555327A (en) | Near-ultraviolet excited double perovskite fluorescent powder for white light LED and preparation method thereof | |
| CN108690612A (en) | It is a kind of to adulterate orange red fluorescent powder and preparation method thereof by the europium of matrix of niobates | |
| Zhu et al. | A novel blue light pumped yellow-emitting phosphor RbZnPO 4: Dy 3+ with satisfactory color tuning and thermal properties for high-power warm white light emitting diodes | |
| CN103122244B (en) | A kind of Eu2+ activated silicate white light phosphor and preparation method thereof | |
| CN111187622A (en) | Single-matrix phosphate phosphor for white light LED and preparation method thereof | |
| Yanna et al. | Synthesis and luminescent properties of polycrystalline Gd2 (MoO4) 3: Dy3+ for white light-emitting diodes | |
| CN106544022A (en) | A kind of Eu3+ doped tantalate red phosphor, preparation method and application | |
| CN109988575A (en) | A kind of Eu3+ ion-activated vanadium phosphoniobate red phosphor, preparation method and application thereof | |
| CN112852422A (en) | White LED fluorescent material and preparation method thereof | |
| CN108277001B (en) | Trivalent dysprosium ion doped single-matrix white fluorescent powder applied to W L ED device and preparation method thereof | |
| CN116814263B (en) | Single-phase white light fluorescent material and preparation method and application thereof | |
| CN101473013B (en) | Thulium-containing fluorescent substance for white light-emitting diode and its manufacturing method | |
| CN108893108A (en) | A kind of double-perovskite type silicate blue fluorescent powder and preparation method thereof | |
| CN108690613A (en) | It is a kind of using niobates as samarium doping orange red fluorescent powder of matrix and preparation method thereof | |
| CN108753293A (en) | It is a kind of using niobates as white fluorescent powder of matrix and preparation method thereof | |
| CN103087712A (en) | Single matrix white phosphor and preparation method thereof | |
| CN108048080A (en) | A kind of LED alkaline earth transition Composite borate fluorescent powders and preparation method thereof | |
| CN102876325A (en) | Light color adjustable valence alternation manganese ion doped aluminate luminescent material and preparation method thereof | |
| CN102660265B (en) | A kind of Eu2+ activated borate yellow fluorescent powder and preparation method thereof | |
| CN106554778A (en) | A kind of single-substrate single-doping white luminescent material and preparation method and application | |
| CN101230271B (en) | A kind of red fluorescent powder for LED and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| OL01 | Intention to license declared | ||
| OL01 | Intention to license declared |