CN113185977A - Europium-doped ultra-wideband red fluorescent material and preparation method and application thereof - Google Patents
Europium-doped ultra-wideband red fluorescent material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910005715 GdSi2 Inorganic materials 0.000 claims abstract description 67
- 150000002500 ions Chemical class 0.000 claims abstract description 25
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 51
- 238000001354 calcination Methods 0.000 claims description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 49
- 238000000227 grinding Methods 0.000 claims description 49
- 238000001816 cooling Methods 0.000 claims description 32
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- 229910052681 coesite Inorganic materials 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 229910052682 stishovite Inorganic materials 0.000 claims description 18
- 229910052905 tridymite Inorganic materials 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 17
- -1 silicon ion Chemical class 0.000 claims description 16
- 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 15
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(III) nitrate Inorganic materials [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-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
- 239000002245 particle Substances 0.000 claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 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
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000005284 excitation Effects 0.000 abstract description 30
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- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 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
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
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Abstract
The invention discloses a europium-doped ultra-wideband red fluorescent material and a preparation method and application thereof. The chemical general formula is as follows: k3GdSi2O7xEu, wherein x is more than or equal to 0.002 and less than or equal to 0.2, and Eu refers to Eu2+And Eu3+Ions in which two different chemical valence states coexist. By changing the doping concentration and the excitation wavelength of Eu, the controllable adjustment of the chromaticity of the fluorescent powder in a red light range can be realized. The fluorescent powder provided by the invention has broadband excitation spectra in ultraviolet and blue light regions (285- & ltSUB & gt 500nm), and can be packaged on a high-brightness near ultraviolet LED chip to prepare a warm white LED lighting device; has ultra-wideband emission in the wavelength range of 500-815 nm, has the full width at half maximum of more than 120nm, and can realize Eu2+Ultra-wideband red light emission of ions breaks through Eu in most silicate oxide fluorescent powder2+The limitation that the ions can only emit blue, green or yellow light.
Description
Technical Field
The invention belongs to the field of luminescent materials for solid-state lighting, and particularly relates to an europium-doped ultra-wideband red fluorescent material and a preparation method and application thereof.
Background
A fluorescent conversion white Light Emitting Diode (LED) has been gradually replacing conventional incandescent lamps and fluorescent lamps and has become the mainstream lighting source because of its advantages of high luminous efficiency, low energy consumption, long service life, small volume, environmental protection, no pollution, etc. The commercialized white light LED is mainly composed of InGaN blue light chip and Y3Al5O12:Ce3+(YAG:Ce3+) And combining yellow fluorescent powder. However, the white light LED has a low color rendering index and a high correlated color temperature due to the lack of red light component in the emission spectrum, which restricts the further application of the white light LED in the solid-state lighting field. In order to overcome the defects of the existing commercial white light LED, a red phosphor with excellent performance is generally introduced into the white light LED to obtain a higher color rendering index and a moderate correlated color temperature. Nevertheless, the blue light component in the emission spectrum of such white light LED based on blue light excitation is much higher than natural light, which may have a certain influence on the biorhythm and vision of human body. Therefore, researchers are turning to the development of ultraviolet excited base phosphors, which use a near ultraviolet chip in combination with broadband emission tri-phosphor to obtain LED light sources closer to the solar spectrum.
At present, mature blue and green fluorescent powder with broadband emission exists in the market, but the red fluorescent powder is less, and only some nitride-based fluorescent powder can realize broadband red light emission under the excitation of ultraviolet light. However, the preparation conditions of the nitride-based phosphor are relatively harsh, and the raw materials are expensive, which hinders the further application of the nitride-based phosphor in white light LEDs. Therefore, the development of the oxide-based broadband red fluorescent powder which can be excited by near ultraviolet light and has excellent performance has important significance for the development of white light LEDs.
Eu2+The rare earth ion has excellent luminescence property, shows a broadband fluorescence spectrum (4f-5d transition) in a plurality of matrixes, and can realize luminescence conversion from blue light to red light through regulation and control of a crystal structure of the matrixes. Broadband emissive Eu2+Ion-doped nitride red phosphors have been commercialized. However, Eu2+Broadband red emission of ions in oxide matrices is still difficult to achieve. Especially for preparing high-efficiency Eu with prominent optical performance2+-Eu3+Coexisting silicate-based ultra-wideband (half-peak width)>120nm) red fluorescent material.
Disclosure of Invention
It is an object of the present invention to provide a novel Eu in view of the above-mentioned problems of the prior art2+-Eu3+Coexisting silicate ultra-wideband red phosphor. The fluorescent powder can realize Eu2+Ultra-wideband red light emission of ions breaks through Eu in most silicate oxide fluorescent powder2+The limitation that the ions can only emit blue, green or yellow light; in addition, the adjustment and control of the chromaticity of the fluorescent powder in a red light range can be realized by changing the doping concentration of Eu and the wavelength of an excitation light source.
The invention adopts a technical scheme that: eu (Eu)2+-Eu3+The coexisting silicate red fluorescent powder has the chemical general formula: k3GdSi2O7xEu, wherein x is more than or equal to 0.002 and less than or equal to 0.2, and Eu refers to Eu2+And Eu3+Ions in which two different chemical valence states coexist.
Another object of the present invention is to provide Eu according to the above technical solution2+-Eu3+The preparation method of coexisting silicate red fluorescent powder adopts a high-temperature solid phase method, and comprises the following basic steps of:
step (1), according to the chemical general formula K3GdSi2O7Weighing the following raw materials in stoichiometric ratio of corresponding elements in xEu: a potassium ion-containing compound, a gadolinium ion-containing compound, a silicon ion-containing compound, and a europium ion-containing compound; wherein x is more than or equal to 0.002 and less than or equal to 0.2, and Eu is Eu2+And Eu3+Ions in which two different chemical valence states coexist;
step (2), mixing and fully grinding the raw materials in the step (1), calcining in an air atmosphere, and naturally cooling to normal temperature;
preferably, the calcination temperature is 600-1000 ℃, and the calcination time is 2-24 hours;
step (3) fully grinding the mixture calcined in the step (2) again to be uniform, then calcining the mixture in a reducing atmosphere, and naturally cooling the calcined mixture to room temperature to obtain the required Eu2+-Eu3+Coexisting silicate red phosphor;
preferably, the calcination temperature is 1050-.
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 europium ion Eu3+Is Eu2O3、Eu(NO3)3One or two of them.
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 Eu2+-Eu3+The application of the coexisting silicate red fluorescent powder is specifically that the obtained fluorescent powder and blue-green fluorescent powder are adjusted and combined according to a certain proportion and packaged on a high-brightness near ultraviolet LED chip to prepare a white light LED lighting device.
The invention has the beneficial effects that:
(1) k according to the invention3GdSi2O7Eu is realized by xEu fluorescent powder2+500-815 nm ultra-wideband red emission (full width at half maximum) of ions>120nm), break through Eu in most of oxide fluorescent powder2+The limitation that the ions can only emit blue, green or yellow light;
(2) k according to the invention3GdSi2O7xEu has a broadband excitation spectrum (285-;
(3) k according to the invention3GdSi2O7xEu can realize the fine adjustment of the chromaticity of the fluorescent powder in a red light range by changing the doping concentration of Eu and the wavelength of an excitation light source;
(4) eu prepared by the invention2+-Eu3+The coexisting silicate fluorescent powder has high luminous efficiency, good stability, simple synthesis method, low price of the required raw materials and environment-friendly and pollution-free preparation process.
Drawings
FIG. 1 is an X-ray diffraction pattern of phosphor samples prepared according to examples 1-7, 9, 11 (a-g for examples 1-7, h for example 9, i for example 11);
FIG. 2 shows emission spectra obtained at an excitation wavelength of 350nm for phosphor samples prepared according to examples 1-7, 9, 11 (examples 1-7 for a-g, example 9 for h, and example 11 for i);
FIG. 3 shows the excitation spectrum (A) at an emission wavelength of 650nm and the emission spectrum (B) at an excitation wavelength of 350nm of a phosphor sample prepared according to example 4;
FIG. 4 shows the excitation spectrum (A) at an emission wavelength of 612nm and the emission spectrum (B) at an excitation wavelength of 393nm for a phosphor sample prepared according to example 4;
FIG. 5 is a CIE diagram of a phosphor sample prepared according to example 4 at an excitation wavelength of 350nm, the inset being a photograph of the corresponding phosphor in sunlight and ultraviolet light, respectively;
FIG. 6 is a contour plot of the emission spectra at an excitation wavelength of 350nm for a phosphor sample prepared according to example 4 with temperature ramp up and ramp down;
FIG. 7 shows the emission spectrum intensity at 350nm excitation wavelength for different test temperatures for phosphor samples prepared according to example 4;
FIG. 8 shows the emission spectrum intensity of the phosphor sample prepared in example 4 at an excitation wavelength of 350nm corresponding to temperature cycling between 303 and 523K.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Eu (Eu)2+-Eu3+The coexisting silicate red fluorescent powder has the chemical general formula: k3GdSi2O7xEu, wherein x is more than or equal to 0.002 and less than or equal to 0.2, and Eu refers to Eu2+And Eu3+Ions in which two different chemical valence states coexist.
Eu as described above2+-Eu3+The preparation method of coexisting silicate red fluorescent powder adopts a high-temperature solid phase method, and comprises the following basic steps of:
step (1), according to the chemical general formula K3GdSi2O7Weighing the following raw materials in stoichiometric ratio of corresponding elements in xEu: a potassium ion-containing compound, a gadolinium ion-containing compound, a silicon ion-containing compound, and a europium ion-containing compound; wherein x is more than or equal to 0.002 and less than or equal to 0.2, and Eu is Eu2+And Eu3+Ions in which two different chemical valence states coexist;
step (2), mixing and fully grinding the raw materials in the step (1), calcining in an air atmosphere, and naturally cooling to normal temperature;
preferably, the calcination temperature is 600-1000 ℃, and the calcination time is 2-24 hours;
step (3) fully grinding the mixture calcined in the step (2) again to be uniform, then calcining the mixture in a reducing atmosphere, and naturally cooling the calcined mixture to room temperature to obtain the required Eu2+-Eu3+Coexisting silicate red phosphor;
preferably, the calcination temperature is 1050-.
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 europium ion Eu3+Is Eu2O3、Eu(NO3)3One or two of them.
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 invention and any modifications and variations that may be made to the invention are within the scope of the invention
Example 1: preparation K3GdSi2O7:0.002Eu
According to the formula K3GdSi2O70.002Eu, and respectively weighing K2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，Eu2O3: 0.000704g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in air atmosphere at 800 ℃ for 6 hours, naturally cooling to room temperature, and taking out the sample. Fully grinding the calcined sample mixture uniformly again, calcining the mixture in a reducing atmosphere at 1200 ℃ for 4 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K3GdSi2O7:0.002Eu。
Referring to a in FIG. 1, the X-ray diffraction pattern of the phosphor sample prepared according to the embodiment is shown. XRD test results show that the main phase of the prepared material is K3GdSi2O70.002Eu material.
Referring to a in FIG. 2, the emission spectrum of the phosphor sample prepared according to the embodiment at 350nm excitation wavelength is shown. As can be seen from the figure, the emission spectrum of the material does not change along with the increase of the doping concentration, the half-peak width of the material is as high as 146nm, and the luminous intensity is higher than the optimal doping concentration K3GdSi2O70.015Eu is much lower.
The excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
Example 2: preparation K3GdSi2O7:0.005Eu
According to the formula K3GdSi2O70.005Eu, and K is weighed respectively2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，Eu2O3: 0.00176g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in air atmosphere at 750 ℃ for 10 hours, naturally cooling to room temperature, and taking out the sample. Fully grinding the calcined sample mixture uniformly again, calcining the mixture in a reducing atmosphere at 1150 ℃ for 8 hours, and naturally cooling the calcined mixture to room temperature to obtain a target product K3GdSi2O7:0.005Eu。
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. XRD test results show that the main phase of the prepared material is K3GdSi2O70.005Eu material.
Referring to b in FIG. 2, the emission spectrum of the phosphor sample prepared according to the embodiment at 350nm excitation wavelength is shown. As can be seen from the graph, the emission spectrum does not change with the increase of the doping concentration, the half-peak width is as high as 127nm, and the luminous intensity ratio is better than that of the best embodiment K3GdSi2O70.015Eu slightly lower.
The excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
Example 3: preparation K3GdSi2O7:0.01Eu
According to the formula K3GdSi2O70.01Eu, and respectively weighing K2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，Eu2O3: 0.00352g, fully grinding in an agate mortar, uniformly grinding, placing in a crucible, and calcining in air atmosphereAnd (3) sintering at 700 ℃ for 14 hours, naturally cooling to room temperature, and taking out the sample. Fully grinding the calcined sample mixture uniformly again, calcining the mixture in a reducing atmosphere at 1100 ℃ for 10 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K3GdSi2O7:0.01Eu。
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 K3GdSi2O70.01Eu material.
Referring to fig. 5 c, the emission spectrum of the phosphor sample prepared according to the embodiment at 350nm excitation wavelength is shown. As can be seen from the graph, the emission spectrum does not change with the increase of the doping concentration, the half-peak width is as high as 129nm, and the luminous intensity ratio is better than that of the best embodiment K3GdSi2O70.015Eu slightly lower.
The excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
Example 4: preparation K3GdSi2O7:0.015Eu
According to the formula K3GdSi2O70.015Eu, respectively weighing K2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，Eu2O3: 0.00528g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in air atmosphere at the calcining temperature of 650 ℃ for 18 hours, naturally cooling to room temperature, and taking out the sample. Fully grinding the calcined sample mixture uniformly again, calcining the mixture in a reducing atmosphere at 1050 ℃ for 12 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K3GdSi2O7:0.015Eu。
Referring to d in FIG. 1, there is shown an X-ray diffraction pattern of a phosphor sample prepared according to the scheme of this exampleSpectra. XRD test results show that the main phase of the prepared material is K3GdSi2O70.015Eu material.
Referring to FIG. 3, A is a graph of the excitation spectrum obtained at 650nm emission wavelength for a phosphor sample prepared according to the protocol of this example. As can be seen from the figure, the excitation spectrum shows a broad excitation band from 285 to 500nm, which is determined by Eu2+Ion from ground state (4 f)7) To excited state (4 f)65d1) Caused by an electronic transition of (a); the excitation spectrum covers the whole ultraviolet and blue light regions, and the strongest excitation peak is at 350nm, which shows that the excitation spectrum can be packaged on a high-brightness near ultraviolet/blue light LED chip to prepare a white light LED lighting device.
Referring to FIG. 3B, the emission spectrum of the phosphor sample prepared according to the embodiment at 350nm excitation wavelength is shown. As can be seen from the figure, the emission spectrum contains a broad-band emission peak of red light from 500 to 815nm, with a full width at half maximum of 130nm, which is measured by Eu2+Ion at 4f65d1→4f7Is caused by the electron transition of (a). Meanwhile, two relatively sharp small peaks near 593nm and 612nm can be seen in the emission spectrum. This is due to the presence of Eu therein3+Emission peak of ion, from Eu3+Ion is at5D0→7F1And5D0→7F2is caused by the electron transition of (a).
Referring to FIG. 4, A is a graph of the excitation spectrum obtained at 612nm emission wavelength for a phosphor sample prepared according to the scheme of this example. As can be seen from the figure, the excitation spectrum has some sharp excitation peaks in the wavelength range of 350 to 500nm, wherein the peaks at 393 and 465nm are particularly intense, mainly due to Eu3+Ion is at7F0→5L6And7F0→5D2is precisely matched with the wavelength of the near ultraviolet and blue light LED chips.
Referring to FIG. 4B, the emission spectrum of the phosphor sample prepared according to the embodiment at 393nm excitation wavelength is shown. As can be seen from the figure, there are some sharp emission peaks in the wavelength range of 550 to 750nm in the emission spectrum, which are mainly composed of Eu3+Caused by electronic transitions of ions; wherein the emission peak at 612nm is most obvious, and Eu3+Ion is at5D0→7F2Corresponds to the electron transition of (c).
Referring to FIG. 5, a CIE diagram of a sample phosphor prepared according to the protocol of this example at an excitation wavelength of 350nm is shown, and the inset is a photograph of the corresponding phosphor in sunlight and ultraviolet light, respectively. As can be seen, the chromaticity coordinates are located at (0.6048,0.3933), lying exactly between the orange and red regions of the CIE diagram. In addition, bright orange red light can be obtained under 350nm excitation, which indicates that the fluorescent material can be used as a potential fluorescent material for broadband emission of red light in a white light LED device.
Referring to FIG. 6, there is shown a contour plot of emission spectra of phosphor samples prepared according to the scheme of this example as the temperature increases and decreases at an excitation wavelength of 350 nm. As can be seen from the graph, the emission spectrum intensity of the sample has a significant downward trend in the temperature rising process, and has a significant upward trend in the subsequent temperature lowering process; the emission spectrum intensity of the sample can be maintained above 44% at room temperature at a test temperature of 423K.
Referring to FIG. 7, the emission spectrum intensity of the phosphor samples prepared according to the embodiment of the present invention at 350nm excitation wavelength and different test temperatures is shown. As can be seen from the figure, in the cyclic process of temperature rise and temperature drop, the luminescence property of the phosphor can be repeated under different temperature conditions, which shows that the thermal stability of the prepared phosphor is outstanding.
Referring to FIG. 8, the emission intensity of the phosphor samples prepared according to the embodiment is measured at 350nm excitation wavelength and temperature cycling between 303 and 523K. As can be seen from the figure, the original luminous intensity can be still maintained after multiple 303K/523K temperature cycles, which shows that the prepared sample has good performance reversibility.
Example 5: preparation K3GdSi2O7:0.02Eu
According to the formula K3GdSi2O70.02Eu, and respectively weighing K2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，Eu2O3: 0.00704g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in air atmosphere at 600 ℃ for 24 hours, naturally cooling to room temperature, and taking out the sample. Fully grinding the calcined sample mixture uniformly again, calcining the mixture in a reducing atmosphere at 1250 ℃ for 6 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K3GdSi2O7:0.02Eu。
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 K3GdSi2O70.02Eu material.
Referring to fig. 2, e is a spectrum of the emission light obtained from the phosphor sample prepared according to the embodiment at an excitation wavelength of 350 nm. It can be seen from the figure that the emission spectrum is roughly similar to that of example 4, the half-peak width is as high as 132nm, and the spectral intensity is low.
The excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
Example 6: preparation K3GdSi2O7:0.03Eu
According to the formula K3GdSi2O70.03Eu, and respectively weighing K2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，Eu2O3: 0.01056g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in air atmosphere at 850 ℃ for 5 hours, naturally cooling to room temperature, and taking out the sample. Fully grinding the calcined sample mixture uniformly again, calcining at 1300 ℃ in a reducing atmosphereThe time is 5 hours, and then the mixture is naturally cooled to room temperature to obtain a target product K3GdSi2O7:0.03Eu。
Referring to fig. 1, f 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 K3GdSi2O70.03Eu material.
Referring to fig. 2, f is a spectrum of the emission light obtained from the phosphor sample prepared according to the embodiment at an excitation wavelength of 350 nm. As can be seen from the figure, the emission spectrum is approximately similar to that of example 4, the half-peak width is as high as 136nm, the spectral intensity is much lower, Eu3+The characteristic emission peak of the ion becomes gradually apparent.
The excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
Example 7: preparation K3GdSi2O7:0.04Eu
According to the formula K3GdSi2O70.04Eu, and respectively weighing K2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，Eu2O3: 0.01408g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in an air atmosphere at 900 ℃ for 4 hours, naturally cooling to room temperature, and taking out the sample. Fully grinding the calcined sample mixture uniformly again, calcining the mixture in a reducing atmosphere at 1350 ℃ for 4 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K3GdSi2O7:0.04Eu。
Referring to FIG. 1, g 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 K3GdSi2O70.04Eu material.
Referring to FIG. 2, g is the excitation wavelength at 350nm of a phosphor sample prepared according to the protocol of this exampleThe emission spectrum obtained below. As can be seen from the figure, the emission spectrum is approximately similar to that of example 4, the half-peak width is as high as 137nm, the spectral intensity is much lower, Eu3+The characteristic emission peak of the ion is more pronounced.
The excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
Example 8: preparation K3GdSi2O7:0.05Eu
According to the formula K3GdSi2O70.05Eu, respectively weighing KHCO according to the stoichiometric ratio of each element3：0.6000g，Gd(NO3)3：0.6865g，SiO2：0.2400g，Eu(NO3)3: 0.0338g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in air atmosphere at 950 ℃ for 3 hours, naturally cooling to room temperature, and taking out the sample. Fully grinding the calcined sample mixture uniformly again, calcining the mixture in a reducing atmosphere at 1400 ℃ for 3 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K3GdSi2O7:0.05Eu。
The crystal structure, excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
Example 9: preparation K3GdSi2O7:0.06Eu
According to the formula K3GdSi2O70.06Eu, respectively weighing K2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，Eu2O3: 0.02112g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in air atmosphere at 1000 ℃ for 2 hours, naturally cooling to room temperature, and taking out the sample. Fully grinding the calcined sample mixture again to be uniform, calcining the mixture in a reducing atmosphere at the calcining temperature ofCalcining at 1450 ℃ for 2 hours, and naturally cooling to room temperature to obtain a target product K3GdSi2O7:0.06Eu。
Referring to fig. 1, h is an X-ray diffraction pattern of a phosphor sample prepared according to the scheme of this example. XRD test results show that the main phase of the prepared material is K3GdSi2O70.06Eu material.
Referring to h in FIG. 2, the emission spectrum of the phosphor sample prepared according to the embodiment at 350nm excitation wavelength is shown. As can be seen from the figure, the emission spectrum is approximately similar to that of example 4, the half-peak width is as high as 141nm, the spectral intensity is much lower, Eu3+The characteristic emission peak of the ion is more pronounced.
The excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
Example 10: preparation K3GdSi2O7:0.07Eu
According to the formula K3GdSi2O70.07Eu, respectively weighing K2O：0.2826g，Gd(NO3)3：0.6865g，SiO2：0.2400g，Eu(NO3)3: 0.04732g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in air atmosphere at 850 ℃ for 8 hours, naturally cooling to room temperature, and taking out the sample. Fully grinding the calcined sample mixture uniformly again, calcining the mixture in a reducing atmosphere at 1300 ℃ for 7 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K3GdSi2O7:0.07Eu。
The crystal structure, excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
Example 11: preparation K3GdSi2O7:0.08Eu
According to the formula K3GdSi2O70.08Eu, and respectively weighing K2CO3：0.4146g，Gd2O3：0.3625g，SiO2：0.2400g，Eu2O3: 0.02816g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in air atmosphere at 700 ℃ for 12 hours, naturally cooling to room temperature, and taking out the sample. Fully grinding the calcined sample mixture uniformly again, calcining the mixture in a reducing atmosphere at 1150 ℃ for 9 hours, and naturally cooling the calcined mixture to room temperature to obtain a target product K3GdSi2O7:0.08Eu。
Referring to fig. 1, i is an X-ray diffraction pattern of a phosphor sample prepared according to the scheme of this example. XRD test results show that the main phase of the prepared material is K3GdSi2O70.08Eu material.
Referring to fig. 2, i is a spectrum of the emission light obtained from the phosphor sample prepared according to the embodiment at an excitation wavelength of 350 nm. As can be seen from the figure, the emission spectrum is substantially similar to that of example 4, the half-width of the peak is as high as 144nm, the spectral intensity is much lower, Eu3+The characteristic emission peak of the ion is more pronounced.
The excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
Example 12: preparation K3GdSi2O7:0.09Eu
According to the formula K3GdSi2O70.09Eu, and respectively weighing K2CO3：0.4146g，Gd(NO3)3：0.6865g，SiO2：0.2400g，Eu(NO3)3: 0.06084g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in an air atmosphere at 600 ℃ for 16 hours, naturally cooling to room temperature, and taking out the sample. Fully grinding the calcined sample mixture again to be uniformThen calcining the mixture in a reducing atmosphere at 1100 ℃ for 11 hours, and naturally cooling the mixture to room temperature to obtain the target product K3GdSi2O7:0.09Eu。
The crystal structure, excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
Example 13: preparation K3GdSi2O7:0.1Eu
According to the formula K3GdSi2O70.1 the stoichiometric ratio of each element in Eu, and respectively weighing K2O：0.2826g，Gd2O3：0.3625g，SiO2：0.2400g，Eu(NO3)3: 0.0676g of the powder is placed in an agate mortar for full grinding, the powder is placed in a crucible after being uniformly ground, the powder is calcined in the air atmosphere, the calcination temperature is 900 ℃, the calcination time is 20 hours, and the sample is taken out after being naturally cooled to the room temperature. Fully grinding the calcined sample mixture uniformly again, calcining the mixture in a reducing atmosphere at 1350 ℃ for 10 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K3GdSi2O7:0.1Eu。
The crystal structure, excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
Example 14: preparation K3GdSi2O7:0.15Eu
According to the formula K3GdSi2O70.15Eu, respectively weighing KHCO according to the stoichiometric ratio of each element3：0.6000g，Gd2O3：0.3625g，SiO2：0.2400g，Eu(NO3)3: 0.1014g of the powder is placed in an agate mortar for full grinding, the powder is placed in a crucible after being uniformly ground, the powder is calcined in the air atmosphere, the calcination temperature is 600 ℃, the calcination time is 22 hours, and the sample is taken out after being naturally cooled to the room temperature. Fully grinding the calcined sample mixture again uniformly, calcining at 1200 ℃ in a reducing atmosphereThe time is 7 hours, and then the mixture is naturally cooled to room temperature to obtain a target product K3GdSi2O7:0.15Eu。
The crystal structure, excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
Example 15: preparation K3GdSi2O7:0.2Eu
According to the formula K3GdSi2O70.2 stoichiometric ratio of each element in Eu, respectively weighing KHCO3：0.6000g，Gd2O3：0.3625g，SiO2：0.2400g，Eu2O3: 0.0704g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in air atmosphere at 750 ℃ for 17 hours, naturally cooling to room temperature, and taking out the sample. Fully grinding the calcined sample mixture uniformly again, calcining the mixture in a reducing atmosphere at 1300 ℃ for 9 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K3GdSi2O7:0.2Eu。
The crystal structure, excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor samples prepared according to the scheme of this example are similar to those of example 4.
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. An europium-doped ultra-wideband red fluorescent material is characterized by having a chemical general formula as follows: k3GdSi2O7xEu, wherein x is more than or equal to 0.002 and less than or equal to 0.2, and Eu refers to Eu2+And Eu3+Ions in which two different chemical valence states coexist.
2. A preparation method of an europium-doped ultra-wideband red fluorescent material is characterized by comprising the following steps:
step (1), pressingGeneral formula K3GdSi2O7Weighing the following raw materials in stoichiometric ratio of corresponding elements in xEu: a potassium ion-containing compound, a gadolinium ion-containing compound, a silicon ion-containing compound, and a europium ion-containing compound; wherein x is more than or equal to 0.002 and less than or equal to 0.2, and Eu is Eu2+And Eu3+Ions in which two different chemical valence states coexist;
step (2), mixing and fully grinding the raw materials in the step (1), calcining in an air atmosphere, and naturally cooling to normal temperature;
step (3) fully grinding the mixture calcined in the step (2) again to be uniform, then calcining the mixture in a reducing atmosphere, and naturally cooling the calcined mixture to room temperature to obtain the required Eu2+-Eu3+Coexisting silicate red phosphor.
3. The method according to claim 2, wherein the calcination temperature in step (2) is 600-1000 ℃, and the calcination time is 2-24 hours.
4. The method according to claim 2, wherein the calcination temperature in step (3) is 1050-1450 ℃, and the calcination time is 2-12 hours.
5. The method for preparing the europium-doped ultra-wideband red fluorescent material as claimed in claim 2, wherein the step (1) contains potassium ion K+The compound of (A) is K2CO3、KHCO3、K2One or more of O.
6. The method for preparing the europium-doped ultra-wideband red fluorescent material as claimed in claim 2, wherein the step (1) contains gadolinium ions Gd3+Is Gd2O3、Gd(NO3)3One or two of them.
7. According to the claimsThe preparation method of the europium-doped ultra-wideband red fluorescent material in claim 2 is characterized in that the silicon ion Si is contained in the step (1)4+The compound of (A) is SiO2。
8. The method according to claim 2, wherein the step (1) comprises the europium ion Eu3+Is Eu2O3、Eu(NO3)3One or two of them.
9. The method for preparing the europium-doped ultra-wideband red fluorescent material according to claim 2, wherein the reducing atmosphere in the step (3) is any one of the following: 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. The use of the europium-doped ultra-wideband red fluorescent material of claim 1 in the preparation of white light LED lighting devices.
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