CN113185977B - 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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- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 15
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims description 59
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 51
- 238000000227 grinding Methods 0.000 claims description 40
- 238000001816 cooling Methods 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 17
- -1 silicon ion Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 53
- 230000005284 excitation Effects 0.000 abstract description 28
- 238000000695 excitation spectrum Methods 0.000 abstract description 24
- 238000000295 emission spectrum Methods 0.000 description 42
- 238000010586 diagram Methods 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
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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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- C09K11/08—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: k 3 GdSi 2 O 7 xEu, wherein x is more than or equal to 0.002 and less than or equal to 0.2, eu refers to Eu 2+ And Eu 3+ 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 (285-500 nm), 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 Eu 2+ Ultra-wideband red light emission of ions breaks through Eu in most silicate oxide fluorescent powder 2+ 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 as well as 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 Y 3 Al 5 O 12 :Ce 3+ (YAG:Ce 3+ ) 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 light with excellent performance is generally introduced into the white light LEDThe fluorescent powder can obtain higher color rendering index and 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.
Eu 2+ The rare earth ion has excellent luminescence property, shows a broadband fluorescence spectrum (4 f-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 Eu 2+ Ion-doped nitride red phosphors have been commercialized. However, eu 2+ Broadband red emission of ions in oxide matrices is still difficult to achieve. Especially for preparing high-efficiency Eu with prominent optical performance 2+ -Eu 3+ Coexisting silicate-based ultra-wideband (half-peak width)>120 nm) 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 art 2+ -Eu 3+ Coexisting silicate ultra-wideband red phosphor. The fluorescent powder can realize Eu 2+ Ultra-wideband red light emission of ions breaks through Eu in most silicate oxide fluorescent powder 2+ 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+ -Eu 3+ The coexisting silicate red fluorescent powder has the chemical general formula: k 3 GdSi 2 O 7 X is more than or equal to 0.002 and less than or equal to 0.2, eu refers to Eu 2+ And Eu 3+ Ions in which two different chemical valence states coexist.
Another object of the present invention is to provide Eu according to the above technical solution 2+ -Eu 3+ 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 K 3 GdSi 2 O 7 Weighing 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 refers to Eu 2+ And Eu 3+ 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 calcining temperature is 600-1000 ℃, and the calcining 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 Eu 2+ -Eu 3+ Coexisting silicate red phosphor;
preferably, the calcination temperature is 1050-1450 ℃ and the calcination time is 2-12 hours.
Preferably, step (1) contains potassium ion K + The compound of (A) is K 2 CO 3 、KHCO 3 、K 2 One or more of O containing gadolinium ions Gd 3+ Is Gd 2 O 3 、Gd(NO 3 ) 3 One or two of them, containing silicon ions Si 4+ The compound of (A) is SiO 2 Containing europium ion Eu 3+ Is Eu 2 O 3 、Eu(NO 3 ) 3 One or two of them.
Preferably, the reducing atmosphere in step (3) comprises: (1) obtained by burning activated carbon or carbon granules; (2) pure hydrogen; (3) and (4) nitrogen-hydrogen mixed gas.
It is still another object of the present invention to provide a Eu 2+ -Eu 3+ 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 invention 3 GdSi 2 O 7 Eu is realized by xEu fluorescent powder 2+ 500-815 nm ultra-wideband red emission (full width at half maximum) of ions>120 nm), break through Eu in most of oxide fluorescent powder 2+ The limitation that the ions can only emit blue, green or yellow light;
(2) K according to the invention 3 GdSi 2 O 7 xEu has a broadband excitation spectrum (285-500 nm), covers near ultraviolet and blue light regions, and is particularly easy to be efficiently excited by near ultraviolet light;
(3) K according to the invention 3 GdSi 2 O 7 xEu 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 invention 2+ -Eu 3+ 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 the emission spectra obtained at an excitation wavelength of 350nm for 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. 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 is a graph of the excitation spectrum (A) at an emission wavelength of 612nm and an emission spectrum (B) at an excitation wavelength of 393nm of 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, respectively;
FIG. 6 is a contour plot of the emission spectra at 350nm excitation wavelength for a phosphor sample prepared according to example 4 with temperature ramp up and ramp down;
FIG. 7 is a graph of emission spectrum intensity at 350nm excitation wavelength for different test temperatures for phosphor samples prepared according to example 4;
FIG. 8 is a graph of the intensity of the emission spectrum corresponding to temperature cycling between 303K and 523K at an excitation wavelength of 350nm for a phosphor sample prepared according to example 4.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Eu (Eu) 2+ -Eu 3+ The coexisting silicate red fluorescent powder has the chemical general formula: k 3 GdSi 2 O 7 xEu, wherein x is more than or equal to 0.002 and less than or equal to 0.2, eu refers to Eu 2+ And Eu 3+ Ions in which two different chemical valence states coexist.
Eu as described above 2+ -Eu 3+ 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 K 3 GdSi 2 O 7 Weighing 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, eu refers to Eu 2+ And Eu 3+ 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 calcining temperature is 600-1000 ℃, and the calcining time is 2-24 hours;
step (3) fully grinding the mixture calcined in the step (2) again to be uniform, calcining the mixture in a reducing atmosphere, and naturally cooling the calcined mixture to room temperature to obtain the required Eu 2+ -Eu 3+ Coexisting silicate red phosphor;
preferably, the calcination temperature is 1050-1450 ℃ and the calcination time is 2-12 hours.
Preferably, step (1) contains potassium ion K + Is K 2 CO 3 、KHCO 3 、K 2 One or more of O containing gadolinium ions Gd 3+ Is Gd 2 O 3 、Gd(NO 3 ) 3 One or two of them, containing silicon ions Si 4+ The compound of (A) is SiO 2 Containing europium ion Eu 3+ Is Eu 2 O 3 、Eu(NO 3 ) 3 One or two of them.
Preferably, the reducing atmosphere in step (3) comprises: (1) obtained by burning activated carbon or carbon granules; (2) pure hydrogen; (3) a nitrogen-hydrogen mixed gas.
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 K 3 GdSi 2 O 7 :0.002Eu
According to the formula K 3 GdSi 2 O 7 0.002Eu, and respectively weighing K 2 CO 3 ：0.4146g，Gd 2 O 3 ：0.3625g，SiO 2 ：0.2400g，Eu 2 O 3 :0.000704g 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 800 ℃, the calcination time is 6 hours, and the sample is taken out after being naturally cooled to the room temperature. Fully grinding the calcined sample mixture uniformly againCalcining in reducing atmosphere at 1200 deg.C for 4 hr, and naturally cooling to room temperature to obtain target product K 3 GdSi 2 O 7 :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 K 3 GdSi 2 O 7 0.002Eu 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 K 3 GdSi 2 O 7 0.015Eu 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 K 3 GdSi 2 O 7 :0.005Eu
According to the formula K 3 GdSi 2 O 7 0.005Eu, and K is weighed respectively 2 CO 3 ：0.4146g，Gd 2 O 3 ：0.3625g，SiO 2 ：0.2400g，Eu 2 O 3 :0.00176g 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 750 ℃, the calcination time is 10 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 1150 ℃ for 8 hours, and naturally cooling the calcined mixture to room temperature to obtain a target product K 3 GdSi 2 O 7 :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 K 3 GdSi 2 O 7 0.005Eu material.
Referring to b in FIG. 2, the emission spectrum of the phosphor sample prepared according to the embodiment of this example at an excitation wavelength of 350nm 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 K 3 GdSi 2 O 7 0.015Eu 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 K 3 GdSi 2 O 7 :0.01Eu
According to the formula K 3 GdSi 2 O 7 0.01Eu, and respectively weighing K 2 CO 3 ：0.4146g，Gd 2 O 3 ：0.3625g，SiO 2 ：0.2400g，Eu 2 O 3 :0.00352g of the powder is placed in an agate mortar for full grinding, placed in a crucible after being uniformly ground, calcined in the air atmosphere, the calcination temperature is 700 ℃, the calcination time is 14 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 1100 ℃ for 10 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K 3 GdSi 2 O 7 :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 K 3 GdSi 2 O 7 0.01Eu material.
Referring to fig. 5 c, the emission spectrum of the phosphor sample prepared according to the embodiment at 350nm 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 K 3 GdSi 2 O 7 0.015Eu 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 K 3 GdSi 2 O 7 :0.015Eu
According to the formula K 3 GdSi 2 O 7 0.015Eu, respectively weighing K 2 CO 3 ：0.4146g，Gd 2 O 3 ：0.3625g，SiO 2 ：0.2400g，Eu 2 O 3 :0.00528g of the powder, placing the powder in an agate mortar for full grinding, placing the powder in a crucible after uniform grinding, calcining the powder in an air atmosphere at the calcining temperature of 650 ℃ for 18 hours, naturally cooling the powder 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 K 3 GdSi 2 O 7 :0.015Eu。
Referring to d 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 K 3 GdSi 2 O 7 0.015Eu 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 Eu 2+ Ion from ground state (4 f) 7 ) To excited state (4 f) 6 5d 1 ) Caused by an electronic transition of (c); the excitation spectrum covers the whole ultraviolet and blue light regions, and the strongest excitation peak is located 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 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 Eu 2+ Ion at 4f 6 5d 1 →4f 7 Is caused by the electron transition of (a). At the same time, can also see in the emission spectrumThere are two relatively sharp small peaks near 593nm and 612 nm. This is due to the presence of Eu therein 3+ Emission peak of ion, from Eu 3+ Ion is in 5 D 0 → 7 F 1 And 5 D 0 → 7 F 2 is 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 Eu 3+ Ion is at 7 F 0 → 5 L 6 And 7 F 0 → 5 D 2 is 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 is shown at 393nm excitation wavelength. 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 Eu 3+ Caused by electronic transitions of ions; wherein the emission peak at 612nm is most obvious, and Eu 3+ Ion is at 5 D 0 → 7 F 2 Corresponds to the electron transition of (c).
Referring to FIG. 5, there is a CIE diagram of a sample of phosphor prepared according to the protocol of this example at an excitation wavelength of 350nm, the inset is a photograph of the corresponding phosphor in sunlight and UV light, respectively. As can be seen, the chromaticity coordinates are located at (0.6048, 0.3933), which lies well 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 embodiment of the present 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 of the excitation wavelength is shown for different test temperatures. 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 a phosphor sample prepared according to the example embodiment is shown at 350nm excitation wavelength with temperature cycling between 303K 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 K 3 GdSi 2 O 7 :0.02Eu
According to the formula K 3 GdSi 2 O 7 0.02Eu, respectively weighing K 2 CO 3 ：0.4146g，Gd 2 O 3 ：0.3625g，SiO 2 ：0.2400g，Eu 2 O 3 :0.00704g 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 24 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 1250 ℃ for 6 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K 3 GdSi 2 O 7 :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 K 3 GdSi 2 O 7 0.02Eu 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 sample prepared according to the scheme of this example are similar to those of example 4.
Example 6: preparation K 3 GdSi 2 O 7 :0.03Eu
According to the formula K 3 GdSi 2 O 7 0.03Eu, and respectively weighing K 2 CO 3 ：0.4146g，Gd 2 O 3 ：0.3625g，SiO 2 ：0.2400g，Eu 2 O 3 :0.01056g 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 850 ℃, the calcination time is 5 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 1300 ℃ for 5 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K 3 GdSi 2 O 7 :0.03Eu。
Referring to f 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 K 3 GdSi 2 O 7 0.03Eu 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, eu 3+ 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 K 3 GdSi 2 O 7 :0.04Eu
According to the formula K 3 GdSi 2 O 7 0.04Eu, chemical formula of each elementMetering, respectively weighing K 2 CO 3 ：0.4146g，Gd 2 O 3 ：0.3625g，SiO 2 ：0.2400g，Eu 2 O 3 :0.01408g of the powder is placed in an agate mortar for full grinding, placed in a crucible after being uniformly ground, calcined in an air atmosphere at 900 ℃ for 4 hours, naturally cooled to room temperature, and then taken out. 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 K 3 GdSi 2 O 7 :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 K 3 GdSi 2 O 7 0.04Eu material.
Referring to fig. 2, g 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 137nm, the spectral intensity is much lower, eu 3+ 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 K 3 GdSi 2 O 7 :0.05Eu
According to the formula K 3 GdSi 2 O 7 0.05Eu, respectively weighing KHCO according to the stoichiometric ratio of each element 3 ：0.6000g，Gd(NO 3 ) 3 ：0.6865g，SiO 2 ：0.2400g，Eu(NO 3 ) 3 :0.0338g of the powder is placed in an agate mortar to be fully ground, the powder is placed in a crucible after being uniformly ground, the powder is calcined in the air atmosphere, the calcining temperature is 950 ℃, the calcining time is 3 hours, and after the powder is naturally cooled to the room temperature, the sample is taken out. Fully grinding the calcined sample mixture uniformly again, and calcining the mixture in a reducing atmosphere at 1400 ℃ for 3 hoursThen naturally cooling to room temperature to obtain the target product K 3 GdSi 2 O 7 :0.05Eu。
The crystal structure, excitation spectrum, emission spectrum, CIE diagram and thermal stability of the phosphor sample prepared according to the scheme of this example are similar to those of example 4.
Example 9: preparation K 3 GdSi 2 O 7 :0.06Eu
According to the formula K 3 GdSi 2 O 7 0.06Eu, respectively weighing K 2 CO 3 ：0.4146g，Gd 2 O 3 ：0.3625g，SiO 2 ：0.2400g，Eu 2 O 3 :0.02112g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in air atmosphere at the calcining temperature of 1000 ℃ for 2 hours, naturally cooling to room temperature, and taking out the sample. Fully and uniformly grinding the calcined sample mixture again, calcining the mixture in a reducing atmosphere at 1450 ℃ for 2 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K 3 GdSi 2 O 7 :0.06Eu。
Referring to fig. 1, h 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 K 3 GdSi 2 O 7 0.06Eu 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-width is as high as 141nm, the spectral intensity is much lower, and Eu 3+ 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 K 3 GdSi 2 O 7 :0.07Eu
According to the formula K 3 GdSi 2 O 7 0.07Eu as the main componentStoichiometric ratio of elements, respectively weighing K 2 O：0.2826g，Gd(NO 3 ) 3 ：0.6865g，SiO 2 ：0.2400g，Eu(NO 3 ) 3 :0.04732g of the powder is placed in an agate mortar for full grinding, is placed in a crucible after being uniformly ground, is calcined in the air atmosphere, has the calcination temperature of 850 ℃ and the calcination time of 8 hours, and is naturally cooled to the room temperature, and then the sample is taken out. 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 K 3 GdSi 2 O 7 :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 K 3 GdSi 2 O 7 :0.08Eu
According to the formula K 3 GdSi 2 O 7 0.08Eu, respectively weighing K 2 CO 3 ：0.4146g，Gd 2 O 3 ：0.3625g，SiO 2 ：0.2400g，Eu 2 O 3 :0.02816g of the powder is put in an agate mortar for full grinding, the powder is put in a crucible after being uniformly ground, the powder is calcined in the air atmosphere, the calcination temperature is 700 ℃, the calcination time is 12 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 1150 ℃ for 9 hours, and naturally cooling the calcined mixture to room temperature to obtain a target product K 3 GdSi 2 O 7 :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 K 3 GdSi 2 O 7 0.08Eu material.
Referring to fig. 2, i is a spectrum of the emission light obtained by the phosphor sample prepared according to the embodiment at an excitation wavelength of 350 nm. As can be seen from the figure, it can be seen from the figureThe emission spectrum was substantially similar to that of example 4, with a half-width of up to 144nm and much lower spectral intensity, eu 3+ 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 K 3 GdSi 2 O 7 :0.09Eu
According to the formula K 3 GdSi 2 O 7 0.09Eu, and respectively weighing K 2 CO 3 ：0.4146g，Gd(NO 3 ) 3 ：0.6865g，SiO 2 ：0.2400g，Eu(NO 3 ) 3 :0.06084g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in an air atmosphere at the calcining temperature of 600 ℃ for 16 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 11 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K 3 GdSi 2 O 7 :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 K 3 GdSi 2 O 7 :0.1Eu
According to the formula K 3 GdSi 2 O 7 0.1 the stoichiometric ratio of each element in Eu, and respectively weighing K 2 O：0.2826g，Gd 2 O 3 ：0.3625g，SiO 2 ：0.2400g，Eu(NO 3 ) 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 again to uniformity, calcining at 1350 ℃ for 10 hours in a reducing atmosphere, and then automatically calciningThen cooling to room temperature to obtain a target product K 3 GdSi 2 O 7 :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 of K 3 GdSi 2 O 7 :0.15Eu
According to the formula K 3 GdSi 2 O 7 0.15Eu, respectively weighing KHCO according to the stoichiometric ratio of each element 3 ：0.6000g，Gd 2 O 3 ：0.3625g，SiO 2 ：0.2400g，Eu(NO 3 ) 3 :0.1014g, placing in an agate mortar for full grinding, placing in a crucible after uniform grinding, calcining in air atmosphere at the calcining temperature of 600 ℃ for 22 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 7 hours, and naturally cooling the calcined sample mixture to room temperature to obtain a target product K 3 GdSi 2 O 7 :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 K 3 GdSi 2 O 7 :0.2Eu
According to the formula K 3 GdSi 2 O 7 0.2 stoichiometric ratio of each element in Eu, respectively weighing KHCO 3 ：0.6000g，Gd 2 O 3 ：0.3625g，SiO 2 ：0.2400g，Eu 2 O 3 :0.0704g, placing in an agate mortar for full grinding, placing in a crucible after grinding uniformly, 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 K 3 GdSi 2 O 7 :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: k 3 GdSi 2 O 7 xEu, wherein x is more than or equal to 0.002 and less than or equal to 0.2, eu refers to Eu 2+ And Eu 3+ 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), according to the chemical general formula K 3 GdSi 2 O 7 Weighing 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 refers to Eu 2+ And Eu 3+ Ions in which two different chemical valence states coexist;
step (2), mixing and fully grinding the raw materials in the step (1), calcining the mixture in an air atmosphere, and naturally cooling the calcined mixture 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 Eu 2+ -Eu 3+ Coexisting silicate red phosphor.
3. The method according to claim 2, wherein the calcining temperature in step (2) is 600-1000 ℃ and the calcining time is 2-24 hours.
4. The method according to claim 2, wherein the calcining temperature in step (3) is 1050-1450 ℃ and the calcining 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 K 2 CO 3 、KHCO 3 、K 2 One 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 Gd 3+ Is Gd 2 O 3 、Gd(NO 3 ) 3 One or two of them.
7. The method for preparing the europium-doped ultra-wideband red fluorescent material as claimed in claim 2, wherein the step (1) contains silicon ions Si 4+ The compound of (A) is SiO 2 。
8. The method according to claim 2, wherein the step (1) comprises the europium ion Eu 3+ Is Eu 2 O 3 、Eu(NO 3 ) 3 One 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: (1) obtained by burning activated carbon or carbon granules; (2) pure hydrogen; (3) and (4) nitrogen-hydrogen mixed gas.
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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