CN113201342A - Ce3+Activated silicate broadband green fluorescent powder and preparation method and application thereof - Google Patents
Ce3+Activated silicate broadband green fluorescent powder and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 150000004760 silicates Chemical class 0.000 title claims abstract description 24
- 108010043121 Green Fluorescent Proteins Proteins 0.000 title claims abstract description 22
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 43
- 229910005715 GdSi2 Inorganic materials 0.000 claims abstract description 43
- 150000002500 ions Chemical class 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 57
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 238000000227 grinding Methods 0.000 claims description 31
- 238000001354 calcination Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- -1 silicon ion Chemical class 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 12
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(III) nitrate Inorganic materials [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims description 6
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- 239000010703 silicon Substances 0.000 claims description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- RJOJUSXNYCILHH-UHFFFAOYSA-N gadolinium(3+) Chemical compound [Gd+3] RJOJUSXNYCILHH-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000000695 excitation spectrum Methods 0.000 abstract description 16
- 238000000295 emission spectrum Methods 0.000 abstract description 15
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- 230000009286 beneficial effect Effects 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention discloses Ce3+An activated silicate broadband green fluorescent powder, a preparation method and application thereof. The chemical general formula is as follows: k3GdSi2O7:xmol％Ce3+Wherein x is doped Ce3+The mole percentage of the ions is more than or equal to 0.5 and less than or equal to 20. By adjusting Ce3+The doping concentration of the ions can realize broadband green light emission. The fluorescent powder provided by the invention has broadband excitation spectrum in the whole ultraviolet region (300-; the broadband green light emission spectrum is in the wavelength range of 430-700 nm, and the full width at half maximum reaches 122 nm. Meanwhile, the fluorescent powder provided by the invention has the advantages of high luminous efficiency, good chemical stability and the like, and the preparation method is simple, the raw materials are low in price, and the fluorescent powder is environment-friendly and pollution-free.
Description
Technical Field
The invention belongs to the field of luminescent materials for solid-state lighting, and particularly relates to Ce3+An activated silicate broadband green fluorescent powder, a preparation method and application thereof.
Background
Following incandescent lamps, fluorescent lamps and energy saving lamps, white Light Emitting Diodes (LEDs) have gradually become mainstream illumination sources in the market due to their small size, long life, low energy consumption, good stability, and environmental friendliness. Among them, the phosphor-converted white LED is most widely used, and its performance varies greatly with the change of the phosphor performance. The fluorescent powder is a common solid luminescent material, and determines the properties of a white light LED lighting device, such as luminescent color, luminescent efficiency, correlated color temperature, color rendering index and the like.
At present, the mainstream white light LED in the market is mainly composed of an InGaN blue light chip and Y3Al5O12:Ce3+(YAG:Ce3+) And combining yellow fluorescent powder. However, the blue light component in the emission spectrum of such a white light LED based on blue light excitation is much higher than that of natural light, which may have a certain effect on the biorhythm and vision of the human body. Therefore, researchers are turning to the development of near-uv or uv-excited based phosphors, which utilize a combination of a near-uv/uv chip and a broadband emitting tri-phosphor to obtain LED light sources closer to the solar spectrum. Such LED illumination light sources usually have a high color rendering index, which is advantageous in practical applications. However, the efficiency of white LEDs is reduced due to the problem of re-absorption between different phosphors. Therefore, in order to obtain a high-efficiency white LED, the three-primary-color phosphors must have high light conversion efficiency. In order to solve the problem, the development of the fluorescent powder with broadband emission and absorption has great research significance.
Aiming at characteristic peak linear emission generated by f-f transition of most rare earth ion activated luminescent materials, low luminous efficiency and narrow spectrum absorption rangeAnd the like, based on the d-f transition, with wide-band emission and absorption of Ce3+And Eu2+Ions are generally the preferred luminescent centers. Wherein, as a common rare earth ion, Ce3+The ion luminescence is generated by the transition between 4f-5d, and the energy level is easily influenced by the crystal field of the substrate and the coordination environment. Ce3+In a strong crystal field environment, the splitting of the 5d track is increased, and the energy band is widened. Thus, Ce can be realized by changing the composition and crystal structure of the matrix3+The ion luminescence property is regulated and controlled, and an ideal (from blue light to red light) fluorescent material suitable for an LED device is obtained. Therefore, the present inventors have developed a novel Ce3+An activated silicate broad band green phosphor.
Disclosure of Invention
It is an object of the present invention to provide a novel Ce compound in view of the above-mentioned problems of the prior art3+An activated silicate broad band green phosphor. The fluorescent powder can realize Ce3+The ultra-wideband green light emission of the ions can reach more than 122nm in full width at half maximum, and the excitation spectrum of the ultra-wideband green light emission can be well matched with the excitation wavelength of the near ultraviolet/ultraviolet LED chip.
The invention adopts a technical scheme that: ce3+The activated silicate broadband green fluorescent powder has a chemical general formula as follows: k3GdSi2O7:xmol％Ce3+Wherein x is doped Ce3+X is more than or equal to 0.5 and less than or equal to 20 in the molar percentage of ions, and Ce is adjusted3+The doping concentration of the ions can realize good broadband green light emission.
Another object of the present invention is to provide the novel Ce of the above technical means3+The preparation method of the activated silicate broadband green fluorescent powder adopts a high-temperature solid phase method and comprises the following basic steps:
step (1), according to the chemical general formula K3GdSi2O7:xmol％Ce3+Weighing the following raw materials in stoichiometric ratio of corresponding elements: a potassium ion-containing compound, a gadolinium ion-containing compound, a silicon ion-containing compound, a cerium ion-containing compound; wherein x is the mole percent of doped cerium ions, 0.5≤x≤20；
Fully grinding and uniformly mixing the raw materials in the step (1), placing the mixture in a crucible for presintering in air atmosphere, and naturally cooling to normal temperature;
preferably, the pre-sintering temperature is 550-1050 ℃, and the time is 4-24 hours;
and (3) sufficiently grinding and uniformly mixing the mixture subjected to the pre-sintering in the step (2) again, calcining in a reducing atmosphere, and naturally cooling to normal temperature to obtain the required Ce3+Activated silicate broad band green phosphor;
preferably, the calcination temperature is 1100-1500 ℃, and the calcination time is 3-12 hours.
Preferably, step (1) contains potassium ion K+The compound of (A) is K2CO3、KHCO3、K2One or more of O containing gadolinium ions Gd3+Is Gd2O3、Gd(NO3)3One or two of them, containing silicon ions Si4+The compound of (A) is SiO2Containing cerium ion Ce3+The compound of (A) is CeO2。
Preferably, the reducing atmosphere in step (3) comprises: firstly, the active carbon or carbon particles are burnt to obtain the active carbon or carbon particles; hydrogen gas; ③ mixed gas of nitrogen and hydrogen.
It is still another object of the present invention to provide a novel Ce3+The application of the activated silicate broadband green fluorescent powder is that the obtained fluorescent powder, red fluorescent powder and blue fluorescent powder are combined according to a certain proportion and packaged on a high-brightness near ultraviolet/ultraviolet LED chip, and a white light LED device can be prepared and applied to the field of solid-state lighting.
The invention has the beneficial effects that:
(1) k according to the invention3GdSi2O7:Ce3+The green fluorescent powder has a broadband excitation spectrum (300-;
(2) k according to the invention3GdSi2O7:Ce3+The green fluorescent powder has a 430-700 nm broadband emission spectrum, the full width at half maximum can reach over 122nm, and energy is easily released in a light form;
(3) k according to the invention3GdSi2O7:Ce3+The green fluorescent powder can be packaged on a high-brightness near ultraviolet/ultraviolet LED chip and combined with red and blue fluorescent powder according to a certain proportion, so that a white light LED device can be prepared and applied to the field of solid-state illumination;
(4) k according to the invention3GdSi2O7:Ce3+The green fluorescent powder has high luminous efficiency, good chemical stability, simple preparation method and low price of raw materials.
Drawings
FIG. 1 is an X-ray diffraction pattern of phosphor samples prepared according to examples 1-3, 6, 7 (a-c are examples 1-3, d is example 6, and e is example 7);
FIG. 2 shows the excitation spectrum (A) at the detection wavelength of 515nm and the emission spectrum (B) at the excitation wavelength of 321nm of a phosphor sample prepared according to example 2;
FIG. 3 is a CIE diagram of a phosphor sample prepared according to example 2 at an excitation wavelength of 321nm, the inset being a photograph of the corresponding phosphor in sunlight and ultraviolet light;
FIG. 4 shows the emission spectra obtained at 321nm excitation wavelength for the phosphor samples prepared according to examples 1-3, 6, 7 (examples 1-3 for a. c, example 6 for d, and example 7 for e).
Detailed Description
The invention is further illustrated below with reference to specific examples.
Ce3+The activated silicate green fluorescent powder has a chemical general formula as follows: k3GdSi2O7:xmol％Ce3+Wherein x is doped Ce3+The mole percentage of the ions is more than or equal to 0.5 and less than or equal to 20. By adjusting Ce3+The doping concentration of the ions can realize broadband green light emission with good luminous performance.
A Ce as described above3+Activated silicate green fluorescenceThe preparation method of the optical powder adopts a high-temperature solid phase method, and comprises the following basic steps:
step (1), according to the chemical general formula K3GdSi2O7:xmol％Ce3+Weighing the following raw materials in stoichiometric ratio of corresponding elements: a potassium ion-containing compound, a gadolinium ion-containing compound, a silicon ion-containing compound, a cerium ion-containing compound; wherein x is the mol percentage of doped cerium ions, and is more than or equal to 0.5 and less than or equal to 20;
fully grinding and uniformly mixing the raw materials in the step (1), placing the mixture in a crucible for presintering in air atmosphere, and naturally cooling to normal temperature;
preferably, the pre-sintering temperature is 550-1050 ℃, and the time is 4-24 hours;
and (3) sufficiently grinding and uniformly mixing the mixture subjected to the pre-sintering in the step (2) again, calcining in a reducing atmosphere, and naturally cooling to normal temperature to obtain the required Ce3+Activated silicate broad band green phosphor;
preferably, the calcination temperature is 1100-1500 ℃, and the calcination time is 3-12 hours.
Preferably, step (1) contains potassium ion K+The compound of (A) is K2CO3、KHCO3、K2One or more of O containing gadolinium ions Gd3+Is Gd2O3、Gd(NO3)3One or two of them, containing silicon ions Si4+The compound of (A) is SiO2Containing cerium ion Ce3+The compound of (A) is CeO2。
Preferably, the reducing atmosphere in step (3) comprises: firstly, the active carbon or carbon particles are burnt to obtain the active carbon or carbon particles; hydrogen gas; ③ mixed gas of nitrogen and hydrogen.
The following examples are intended to illustrate the present invention and any modifications and variations made on the basis of the present invention are within the scope of the present invention.
Example 1: preparation K3GdSi2O7:0.5mol％Ce3+
According to the formula K3GdSi2O7:0.5mol％Ce3+The stoichiometric ratio of each element in the composition is measured by respectively weighing K2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，CeO2: 0.00172g, placing the powder in an agate mortar for full grinding, placing the powder in a crucible after being ground uniformly, presintering the powder in the air atmosphere at the presintering temperature of 800 ℃ for 6 hours, naturally cooling the powder to room temperature, then fully grinding the presintering powder sample uniformly again, calcining the powder in the reducing atmosphere at the calcining temperature of 1200 ℃ for 4 hours, and naturally cooling the powder to room temperature to obtain the target product K3GdSi2O7:0.5mol％Ce3+。
Referring to a in FIG. 1, the X-ray diffraction pattern of the phosphor sample prepared according to the embodiment is shown. The result shows that the main phase of the prepared material is K3GdSi2O7。
Referring to a in FIG. 4, the emission spectrum of the phosphor sample prepared according to the embodiment at 321nm is shown. As can be seen, the emission spectrum is substantially similar to that of example 2, with a full width at half maximum of up to 120nm and a lower emission intensity.
The excitation spectrum and CIE diagram of the phosphor samples prepared according to this example are similar to those of example 2.
Example 2: preparation K3GdSi2O7:1.0mol％Ce3+
According to the formula K3GdSi2O7:1.0mol％Ce3+The stoichiometric ratio of each element in the composition is measured by respectively weighing K2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，CeO2: 0.00344g, placing the powder in an agate mortar for full grinding, placing the powder in a crucible after being ground uniformly, presintering the powder in the air atmosphere at the presintering temperature of 900 ℃ for 4 hours, naturally cooling the powder to room temperature, then fully grinding the presintering powder sample uniformly again, calcining the powder in the reducing atmosphere at the calcining temperature of 1100 ℃ for 12 hours, and naturally cooling the powder to room temperature to obtain the target product K3GdSi2O7:1.0mol％Ce3+。
Referring to b in FIG. 1, the X-ray diffraction pattern of the phosphor sample prepared according to the embodiment of this example is shown. The result shows that the main phase of the prepared material is K3GdSi2O7。
Referring to FIG. 2, A is a diagram of the excitation spectrum obtained at 515nm emission wavelength for a phosphor sample prepared according to the scheme of this example. As can be seen from the figure, the excitation spectrum contains two narrow excitation bands in the wavelength range of 300-415nm, the peak values are 321nm and 387nm respectively, which are caused by Ce3+Ion from ground state (4 f)1) To excited state (4 f)05d1) Caused by an electronic transition of (a); the excitation spectrum covers the whole ultraviolet light area, and shows that the excitation spectrum can be packaged on a high-brightness near ultraviolet LED chip to prepare a white light LED device, and the white light LED device is applied to the field of solid-state lighting.
Referring to FIG. 2B, the emission spectrum of the phosphor sample prepared according to the embodiment at 321nm is shown. As can be seen from the figure, the emission spectrum contains a green broadband emission peak from 430 to 700nm, the peak is at 515nm, the full width at half maximum is up to 122nm, which is formed by Ce3+Ion at 4f05d1→4f1Is caused by the electron transition of (a).
Referring to FIG. 3, a CIE diagram of a sample phosphor prepared according to the protocol of this example at an excitation wavelength of 321nm is shown, and the inset is a photograph of the corresponding phosphor in sunlight and ultraviolet light, respectively. As can be seen from the figure, the chromaticity coordinates are located at (0.3106,0.4615), lying exactly between the green regions in the CIE diagram. In addition, bright green light can be obtained under 365nm excitation, which shows that the fluorescent material can be used as a fluorescent material with broadband green light emission and has potential application in white light LED devices.
Example 3: preparation K3GdSi2O7:2.0mol％Ce3+
According to the formula K3GdSi2O7:2.0mol％Ce3+The stoichiometric ratio of each element in the composition is measured by respectively weighing K2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，CeO2: 0.00688g, placing the powder in an agate mortar for full grinding, placing the powder in a crucible after being ground uniformly, presintering the powder in the air atmosphere at 1050 ℃ for 12 hours, naturally cooling the powder to room temperature, then fully grinding the presintered powder sample again uniformly, calcining the powder in a reducing atmosphere at 1500 ℃ for 3 hours, and naturally cooling the powder to room temperature to obtain the target product K3GdSi2O7。
Referring to fig. 1, c is an X-ray diffraction pattern of a phosphor sample prepared according to the embodiment. XRD test results show that the main phase of the prepared material is K3GdSi2O7:2.0mol％Ce3+A material.
Referring to fig. 4 c, the emission spectrum of the phosphor sample prepared according to the embodiment at 321nm is shown. As can be seen from the figure, the emission spectrum was substantially similar to that of example 2, the full width at half maximum was as high as 125nm, and the emission intensity was low.
The excitation spectrum and CIE diagram of the phosphor samples prepared according to this example are similar to those of example 2.
Example 4: preparation K3GdSi2O7:3.0mol％Ce3+
According to the formula K3GdSi2O7:3.0mol％Ce3+Respectively weighing KHCO according to the stoichiometric ratio of the elements3：0.6000g，Gd(NO3)3：0.6865g，SiO2：0.2400g，CeO2: 0.01033g, placing the mixture in an agate mortar for full grinding, placing the mixture in a crucible after uniform grinding, presintering the mixture in the air atmosphere at the presintering temperature of 550 ℃ for 24 hours, naturally cooling the mixture to room temperature, then fully grinding the presintered sample mixture again uniformly, calcining the mixture in the reducing atmosphere at the calcining temperature of 1300 ℃ for 8 hours, and naturally cooling the mixture to room temperature to obtain the target product K3GdSi2O7:3.0mol％Ce3+。
The crystal structure, excitation spectrum, emission spectrum and CIE diagram of the phosphor sample prepared according to the scheme of this example are similar to those of example 2, and the full width at half maximum is up to 127 nm.
Example 5: preparation K3GdSi2O7:4.0mol％Ce3+
According to the formula K3GdSi2O7:4.0mol％Ce3+The stoichiometric ratio of each element in the composition is measured by respectively weighing K2O：0.2826g，Gd(NO3)3：0.6865g，SiO2：0.2400g，CeO2: 0.01377g, placing the mixture in an agate mortar for full grinding, placing the mixture in a crucible after uniform grinding, presintering the mixture in the air atmosphere at the presintering temperature of 700 ℃ for 18 hours, naturally cooling the mixture to room temperature, then fully grinding the presintered sample mixture again uniformly, calcining the mixture in the reducing atmosphere at the calcining temperature of 1400 ℃ for 10 hours, and then naturally cooling the mixture to room temperature to obtain the target product K3GdSi2O7:4.0mol％Ce3+。
The crystal structure, excitation spectrum, emission spectrum and CIE diagram of the phosphor sample prepared according to the scheme of this example are similar to those of example 2, and the full width at half maximum is up to 128 nm.
Example 6: preparation K3GdSi2O7:5.0mol％Ce3+
According to the formula K3GdSi2O7:5.0mol％Ce3+The stoichiometric ratio of each element in the composition is measured by respectively weighing K2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，CeO2: 0.01721g, placing the mixture in an agate mortar for full grinding, placing the mixture in a crucible after uniform grinding, presintering the mixture in the air atmosphere at the presintering temperature of 600 ℃ for 14 hours, naturally cooling the mixture to room temperature, then fully grinding the presintered sample mixture again for uniform grinding, calcining the mixture in the reducing atmosphere at the calcining temperature of 1250 ℃ for 9 hours, and then naturally cooling the mixture to room temperature to obtain the target product K3GdSi2O7:5.0mol％Ce3+。
Referring to d in FIG. 1, the X-ray diffraction pattern of the phosphor sample prepared according to the protocol of this exampleAnd (4) mapping. The result shows that the main phase of the prepared material is K3GdSi2O7。
Referring to d in FIG. 4, the emission spectrum of the phosphor sample prepared according to the embodiment at 321nm is shown. As can be seen from the figure, the emission spectrum was substantially similar to that of example 2, the full width at half maximum was as high as 130nm, and the emission intensity was much lower.
The excitation spectrum and CIE diagram of the phosphor samples prepared according to this example are similar to those of example 2.
Example 7: preparation K3GdSi2O7:10.0mol％Ce3+
According to the formula K3GdSi2O7:10.0mol％Ce3+The stoichiometric ratio of each element in the composition is measured by respectively weighing K2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，CeO2: 0.03442g, placing the mixture in an agate mortar for full grinding, placing the mixture in a crucible after uniform grinding, presintering the mixture in the air atmosphere at the presintering temperature of 1000 ℃ for 21 hours, naturally cooling the mixture to room temperature, then fully grinding the presintered sample mixture again uniformly, calcining the mixture in the reducing atmosphere at the calcining temperature of 1350 ℃ for 5 hours, and then naturally cooling the mixture to room temperature to obtain the target product K3GdSi2O7:10.0mol％Ce3+。
Referring to FIG. 1, e is an X-ray diffraction pattern of a phosphor sample prepared according to the protocol of this example. XRD test results show that the main phase of the prepared material is K3GdSi2O7。
Referring to fig. 4, e is a graph showing the emission spectrum of the phosphor sample prepared according to the embodiment at 321nm excitation wavelength. As can be seen from the figure, the emission spectrum was substantially similar to that of example 2, the full width at half maximum was as high as 155nm, and the emission intensity was much lower.
The excitation spectrum and CIE diagram of the phosphor samples prepared according to this example are similar to those of example 2.
Example 8: preparation K3GdSi2O7:15.0mol％Ce3+
According to the formula K3GdSi2O7:15.0mol％Ce3+Respectively weighing KHCO according to the stoichiometric ratio of the elements3：0.6000g，Gd2O3：0.3625g，SiO2：0.2400g，CeO2: 0.05163g, placing the mixture in an agate mortar for full grinding, placing the mixture in a crucible after uniform grinding, presintering the mixture in the air atmosphere at the presintering temperature of 650 ℃ for 7 hours, naturally cooling the mixture to room temperature, then fully grinding the presintered sample mixture again uniformly, calcining the mixture in the reducing atmosphere at the calcining temperature of 1450 ℃ for 7 hours, and then naturally cooling the mixture to room temperature to obtain the target product K3GdSi2O7:15.0mol％Ce3+。
The crystal structure, excitation spectrum, emission spectrum, and CIE diagram of the phosphor samples prepared according to this example are similar to those of example 2.
Example 9: preparation K3GdSi2O7:20.0mol％Ce3+
According to the formula K3GdSi2O7:20.0mol％Ce3+The stoichiometric ratio of each element in the composition is measured by respectively weighing K2CO3：0.4146g，Gd(NO3)3：0.6865g，SiO2：0.2400g，CeO2: 0.06884g, placing the mixture in an agate mortar for full grinding, placing the mixture in a crucible after uniform grinding, presintering the mixture in the air atmosphere at the presintering temperature of 950 ℃ for 8 hours, naturally cooling the mixture to room temperature, then fully grinding the presintered sample mixture again uniformly, calcining the mixture in the reducing atmosphere at the calcining temperature of 1150 ℃ for 6 hours, and then naturally cooling the mixture to room temperature to obtain the target product K3GdSi2O7:20.0mol％Ce3+。
The crystal structure, excitation spectrum, emission spectrum, and CIE diagram of the phosphor samples prepared according to this example are similar to those of example 2.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and all embodiments are within the scope of the present invention as long as the requirements of the present invention are met.
Claims (10)
1. Ce3+The activated silicate broadband green fluorescent powder is characterized in that the chemical general formula of the fluorescent powder is as follows: k3GdSi2O7:xmol％Ce3+Wherein x is doped Ce3+The mole percentage of the ions is that x is more than or equal to 0.5 and less than or equal to 20.
2. Ce3+The preparation method of the activated silicate broadband green fluorescent powder is characterized by comprising the following steps of:
step (1), according to the chemical general formula K3GdSi2O7:xmol％Ce3+Weighing the following raw materials in stoichiometric ratio of corresponding elements: a potassium ion-containing compound, a gadolinium ion-containing compound, a silicon ion-containing compound, a cerium ion-containing compound; wherein x is the mol percentage of doped cerium ions, and is more than or equal to 0.5 and less than or equal to 20;
fully grinding and uniformly mixing the raw materials in the step (1), placing the mixture in an air atmosphere for presintering, and then naturally cooling to normal temperature;
and (3) fully grinding and uniformly mixing the mixture subjected to pre-sintering in the step (2) again, calcining the mixture in a reducing atmosphere, and naturally cooling to normal temperature to obtain the required Ce3+An activated silicate broad band green phosphor.
3. Ce according to claim 13+The preparation method of the activated silicate broadband green fluorescent powder is characterized in that the presintering temperature in the step (2) is 550-1050 ℃, and the time is 4-24 hours.
4. Ce according to claim 13+The preparation method of the activated silicate broadband green fluorescent powder is characterized in that the calcination temperature in the step (3) is 1100-1500 ℃, and the calcination time is 3-12 hours.
5. Ce according to claim 13+The preparation method of the activated silicate broadband green fluorescent powder is characterized in that the step (1) contains potassium ions K+The compound of (A) is K2CO3、KHCO3、K2One or more of O.
6. Ce according to claim 13+The preparation method of the activated silicate broadband green fluorescent powder is characterized in that the step (1) contains gadolinium ions Gd3+Is Gd2O3、Gd(NO3)3One or two of them.
7. Ce according to claim 13+The preparation method of the activated silicate broadband green fluorescent powder is characterized in that the step (1) contains silicon ions Si4+The compound of (A) is SiO2。
8. Ce according to claim 13+The preparation method of the activated silicate broadband green fluorescent powder is characterized in that the cerium ion Ce is contained in the step (1)3+The compound of (A) is CeO2。
9. Ce according to claim 13+The preparation method of the activated silicate broadband green fluorescent powder is characterized in that the reducing atmosphere in the step (3) comprises the following steps: firstly, the active carbon or carbon particles are burnt to obtain the active carbon or carbon particles; hydrogen gas; ③ mixed gas of nitrogen and hydrogen.
10. A Ce as claimed in claim 13+The application of the activated silicate broadband green fluorescent powder in preparing white light LED devices.
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