CN114196402B - Eu-doped ultrahigh chromogenic borophosphate and preparation method and application thereof - Google Patents
Eu-doped ultrahigh chromogenic borophosphate and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 83
- 239000000126 substance Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 13
- JPTZIXWMJPLBSV-UHFFFAOYSA-N [K].[Sr].[Ca] Chemical compound [K].[Sr].[Ca] JPTZIXWMJPLBSV-UHFFFAOYSA-N 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- 229910001940 europium oxide Inorganic materials 0.000 claims description 12
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 12
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 10
- -1 calcium strontium potassium boron phosphate Chemical compound 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 2
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 239000012856 weighed raw material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000009877 rendering Methods 0.000 abstract description 41
- 230000005284 excitation Effects 0.000 abstract description 30
- 238000005286 illumination Methods 0.000 abstract description 6
- 125000005619 boric acid group Chemical group 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 description 30
- 230000001105 regulatory effect Effects 0.000 description 13
- 238000000227 grinding Methods 0.000 description 11
- 238000011068 loading method Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 9
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 description 9
- 239000006012 monoammonium phosphate Substances 0.000 description 9
- 239000001506 calcium phosphate Substances 0.000 description 8
- 229960001714 calcium phosphate Drugs 0.000 description 8
- 235000011010 calcium phosphates Nutrition 0.000 description 8
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000695 excitation spectrum Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 description 2
- 229910000149 boron phosphate Inorganic materials 0.000 description 2
- 229960005069 calcium Drugs 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000012071 phase Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/774—Borates
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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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
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Abstract
The invention belongs to the technical field of luminescent materials, and particularly relates to a luminescent material applied to semiconductor illumination, and a preparation method and application thereof. The luminescent materialThe chemical expression of (C) is K 2 SrCa(PO 4 ) 2‑x (BO 3 ) x :yEu 2+ Wherein 0 is<x≤0.6，0<y is less than or equal to 0.07. The Eu doped borophosphate luminescent material K is synthesized by a high-temperature solid phase method 2 SrCa(PO 4 ) 2‑x (BO 3 ) x :yEu 2+ Under the excitation of near ultraviolet light, the boric acid group and the phosphoric acid group respectively emit red light and green light, the emission peak covers 420-750 nm of a visible light region, the peak is positioned at 595nm and 455nm, and finally, the white light emission is realized in a single luminescent material. The luminescent material is used in an LED light source device, white light with high color rendering and adjustable color temperature can be obtained, and the preparation method and the process are simple and are suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a luminescent material applied to semiconductor illumination, and a preparation method and application thereof.
Background
The advent of white light LED semiconductor illumination sources has been known as a new revolution in the field of illumination. Compared with the traditional incandescent lamp and fluorescent lamp, the white light LED has the advantages of energy conservation, long service life, high brightness, environmental protection, no pollution and the like, and is suitable for illumination, display, decoration and the like. Currently, the implementation modes of white light LEDs mainly include light conversion type, multicolor combination type, multiple quantum well type, quantum dot type and the like. Based on the factors of technology, cost, state of the art and the like, research emphasis and research interest in various countries in the world are still focused on light conversion, namely, white light emission is realized by coating an LED chip with fluorescent powder.
The following 3 WLED conversion modes are commonly used: (1) fluorescent powder conversion type; (2) a multi-chip combined type; (3) the single-chip multi-quantum well trap type fluorescent powder conversion type is developed into a mature type, and becomes the main stream of white light illumination. Light emitting diode (pc-LED) based on blue GaInN chip and rare earth doped phosphor due to its high efficiency, environmental protection, long operating time and good thermal stabilityIs receiving extensive attention. However, today commercial white LEDs are usually made of yellow emitting phosphor (YAG: ce 3+ ) And a blue GaInN chip, which has poor color rendering index (Ra) due to no red emission in the white light emission spectrum<75). Currently, the best solution to this problem is to fabricate high performance white LEDs by Near Ultraviolet (NUV) LED chips and corresponding red, green, and blue phosphors. However, the three-color (red, green and blue) fluorescent powder has stronger self-absorption effect>20%) and a different thermal quenching behaviour, resulting in a low luminous efficiency and poor color stability. To date, developing a new elemental phosphor that is excited with NUV chips to achieve high quality white light is a good alternative.
However, currently reported single component phosphor based wleds have difficulty in achieving the highest color rendering index (CRI, ra 95) due to the cyan or green cavity around 520nm, limiting the realization of natural white light. At the same time, such systems inevitably suffer from energy loss and emission color instability due to the different levels of energy transfer and luminous efficiency of the different activators, which can be effectively avoided by single hosts and single doped phosphors. Therefore, there is a need to develop a single doped broadband phosphor to achieve tunable CCT and polychromatic emission to suppress energy loss during energy transfer, especially single Eu 2+ The ion doped white light luminescent material has wide prospect.
Disclosure of Invention
The invention aims to provide an Eu-doped ultrahigh color development borophosphate luminescent material which is used for a white light LED, can be excited by near ultraviolet light and emits in a full spectrum, and a preparation method and application thereof.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the invention provides a Eu doped borophosphate luminescent material, which is characterized in that the luminescent material has a chemical formula of K 2 SrCa(PO 4 ) 2-x (BO 3 ) x :yEu 2+ Wherein 0 is<x≤0.6，0<y≤0.07。
In the technical proposalFurther, the luminescent material structure comprises a boric acid group and a phosphoric acid group, and the chemical composition of the boric acid group is (BO 3 ) 3- x The phosphate group has a chemical composition of (PO 4 ) 3- 2-x Wherein 0 is<x≤0.6。
In the above technical scheme, further, the luminescent material has a chemical formula of K 2 SrCa(PO 4 ) 2-x (BO 3 ) x :yEu 2 + Wherein x is more than or equal to 0.4 and less than or equal to 0.6.
In the above technical scheme, further, the luminescent material has a chemical formula of K 2 SrCa(PO 4 ) 2-x (BO 3 ) x :yEu 2 + Wherein x is more than or equal to 0.5 and less than or equal to 0.6.
In the above technical scheme, further, the luminescent material has a chemical formula of K 2 SrCa(PO 4 ) 2-x (BO 3 ) x :yEu 2 + Wherein x is more than or equal to 0.55 and less than or equal to 0.6.
In the above technical solution, further, when excited at 365-400 nm, white light with peak wavelengths at 455nm and 595nm is emitted.
The invention also provides a preparation method of the Eu-doped borophosphate luminescent material, which adopts a high-temperature solid-phase reaction method to prepare the Eu-doped borophosphate calcium strontium potassium luminescent material, and the method comprises the following steps:
(1) According to chemical formula K 2 SrCa(PO 4 ) 2-x (BO 3 ) x :yEu 2+ The stoichiometric ratio of the raw materials is weighed and ground, and the weighed raw materials are calcium dihydrogen phosphate, calcium carbonate, strontium carbonate, potassium carbonate, boric acid and europium oxide respectively;
(2) And (3) placing the precursor powder in the step (1) into a crucible, feeding the crucible into a high-temperature tube furnace, performing heat treatment in a weak reducing atmosphere, and cooling along with the furnace to obtain the Eu-doped calcium strontium potassium boron phosphate luminescent material.
In the above technical solution, further, in the step (2), the heat treatment is: calcining at 1400 ℃ for 4h.
In the above technical scheme, in the step (2), the weak reducing atmosphere is 3% by volume of H 2 With 97% by volume of N 2 Is a mixed gas of (a) and (b).
In a further aspect, the present invention provides an application of the Eu-doped borophosphate luminescent material in white light LEDs.
The Eu-doped calcium strontium potassium borate luminescent material can be used for white light LEDs with different color temperatures and color coordinates when excited by ultraviolet light and ultraviolet chips with the wavelength of 365-400 nm.
The beneficial effects of the invention are as follows:
single Eu obtained by the present invention 2+ When the doped borophosphate luminescent material comprises borate and phosphate groups and is used in an LED light source device, the borate and the phosphate groups respectively have two wide emission peaks in red wave band and cyan wave band under the excitation of near ultraviolet light, and finally white light emission is realized in a single luminescent material; the peak width of the two emission peaks is wider, the visible light region is covered with 420-750 nm, and the peak values are 595nm and 455nm; the emission peak intensity of the red wave band and the cyan wave band can be regulated and controlled by changing the excitation wavelength (365-400 nm), the color temperature of the obtained white light can be regulated within the range of 7400K-4400K, and the preparation method has the advantages of simple process, mature technology and good industrialization prospect and application prospect.
Drawings
FIG. 1 is an X-ray diffraction chart of luminescent materials prepared in example 1, examples 3 to 5 and comparative example 2 of the present invention;
FIG. 2 shows excitation spectra of the luminescent materials prepared in examples 1 and 3-6 of the present invention at detection wavelengths of 455nm and 595nm, where a is 595nm and b is 455nm;
FIG. 3 shows the emission spectra of the luminescent materials prepared in example 1 of the present invention under excitation at 365nm, 380nm and 390nm wavelengths, respectively.
Detailed Description
The present invention will be further described with reference to examples, but the scope of the invention is not limited thereto.
Comparative example 1
| Raw materials | Weight (g) |
| CaCO 3 | 4.75 |
| SrCO 3 | 7.38 |
| NH 4 (H) 2 PO 4 | 10.15 |
| K 2 CO 3 | 6.91 |
| Eu 2 O 3 | 0.44 |
The Eu-doped boron-phosphate luminescent material is synthesized by adopting a traditional high-temperature solid-phase method: grinding the raw materials, mixing, and loading into crucible with volume percentage of 3%H in high temperature tube furnace 2 And 97% N 2 Roasting for 4 hours at 1400 ℃ in the mixed atmosphere, and then cooling to room temperature along with a furnace to obtain K 2 SrCa(PO 4 ) 2 :0.05Eu 2+ Blue luminescent material.
The excitation spectrum of the calcium strontium potassium phosphate blue luminescent material of the comparative example is a broad spectrum, the near ultraviolet and blue light areas (400-470 nm) are covered, and the optimal excitation peak is located near 450 nm.
Comparative example 2
The Eu-doped boron-phosphate luminescent material is synthesized by adopting a traditional high-temperature solid-phase method: grinding the raw materials, mixing, and loading into crucible with volume percentage of 3%H in high temperature tube furnace 2 And 97% N 2 Roasting for 4 hours at 1400 ℃ in the mixed atmosphere, and then cooling to room temperature along with a furnace to obtain K 2 SrCa(PO 4 ) 0.3 (BO 3 ) 0.7 :0.05Eu 2+ Orange luminescent material.
The excitation spectrum of the orange luminescent material of the calcium strontium potassium phosphate of the comparative example is a broad spectrum, which covers a yellow orange light region (570-600 nm), and the optimal excitation peak is located near 595 nm.
Example 1
| Raw materials | Weight (g) |
| CaCO 3 | 4.75 |
| SrCO 3 | 7.38 |
| NH 4 (H) 2 PO 4 | 8.05 |
| K 2 CO 3 | 6.91 |
| Eu 2 O 3 | 0.44 |
| H 3 BO 3 | 1.86 |
A method for preparing a Eu-doped borophosphate luminescent material, comprising the steps of:
according to chemical formula K 2 SrCa(PO 4 ) 1.4 (BO 3 ) 0.6 :0.05Eu 2+ Respectively weighing 7.38g of strontium carbonate, 4.75g of calcium carbonate, 8.05g of monoammonium phosphate, 6.91g of potassium carbonate, 1.86g of boric acid and 0.44g of europium oxide, fully grinding in an agate mortar, loading into a crucible, and placing into a high-temperature tube furnace at a volume percentage of 3%H 2 And 97% N 2 Roasting for 4 hours at 1400 ℃ in the mixed atmosphere, and then cooling to room temperature along with a furnace to obtain calcium strontium potassium borophosphate, so as to obtain the Eu-doped calcium phosphate luminescent material, wherein x=0.6; y=0.05.
The Eu doped borophosphate luminescent material of the embodiment has two wider emission peaks, which cover 420-750 nm of visible light region, and the peak values are located at 455nm and 595nm; the excitation peak covers the near ultraviolet region, and when different excitation wavelengths (365-400 nm) are adopted, the emission peak intensities of the red wave band and the cyan wave band can be regulated and controlled, so that high-color-rendering white light emission is realized. Packaging the luminescent material and a 365nm ultraviolet light chip into an LED, and obtaining white light with a color temperature of 7400K and a color rendering index of 95; packaging with 370nm ultraviolet chip to obtain LED, and obtaining white light with color temperature 6800K and color rendering index 92; and packaging the white light with a 390nm ultraviolet light chip into an LED, wherein the color temperature of the obtained white light is 6500K, and the color rendering index is 87.
Example 2
| Raw materials | Weight (g) |
| CaCO 3 | 4.75 |
| SrCO 3 | 7.38 |
| NH 4 (H) 2 PO 4 | 8.34 |
| K 2 CO 3 | 6.91 |
| Eu 2 O 3 | 0.44 |
| H 3 BO 3 | 1.70 |
A method for preparing a Eu-doped borophosphate luminescent material, comprising the steps of:
according to chemical formula K 2 SrCa(PO 4 ) 1.45 (BO 3 ) 0.55 :0.05Eu 2+ Respectively weighing 7.38g of strontium carbonate, 4.75g of calcium carbonate, 8.34g of monoammonium phosphate, 6.91g of potassium carbonate, 1.70g of boric acid and 0.44g of europium oxide, fully grinding in an agate mortar, loading into a crucible, and placing into a high-temperature tube furnace at a volume percentage of 3%H 2 And 97% N 2 Roasting for 4 hours at 1400 ℃ in the mixed atmosphere, and then cooling to room temperature along with a furnace to obtain calcium strontium potassium borophosphate to obtain Eu doped calcium phosphateA luminescent material, wherein x = 0.55; y=0.05.
The Eu doped borophosphate luminescent material of the embodiment has two wider emission peaks, which cover 420-750 nm of visible light region, and the peak values are located at 455nm and 595nm; the excitation peak covers the near ultraviolet region, and when different excitation wavelengths (365-400 nm) are adopted, the emission peak intensities of the red wave band and the cyan wave band can be regulated and controlled, so that high-color-rendering white light emission is realized. Packaging the luminescent material and a 365nm ultraviolet light chip into an LED, and obtaining white light with a color temperature of 7500K and a color rendering index of 93; packaging with 370nm ultraviolet chip to obtain LED, and obtaining white light with color temperature 7000K and color rendering index 90; and packaging the white light with a 390nm ultraviolet light chip into an LED, and obtaining white light with a color temperature of 6800K and a color rendering index of 84.
Example 3
| Raw materials | Weight (g) |
| CaCO 3 | 4.75 |
| SrCO 3 | 7.38 |
| NH 4 (H) 2 PO 4 | 8.63 |
| K 2 CO 3 | 6.91 |
| Eu 2 O 3 | 0.44 |
| H 3 BO 3 | 1.55 |
A method for preparing a Eu-doped borophosphate luminescent material, comprising the steps of:
according to chemical formula K 2 SrCa(PO 4 ) 1.5 (BO 3 ) 0.5 :0.05Eu 2+ Respectively weighing 7.38g of strontium carbonate, 4.75g of calcium carbonate, 8.63g of monoammonium phosphate, 6.91g of potassium carbonate, 1.55g of boric acid and 0.44g of europium oxide, fully grinding in an agate mortar, loading into a crucible, and placing into a high-temperature tube furnace at a volume percentage of 3%H 2 And 97% N 2 Roasting for 4 hours at 1400 ℃ in the mixed atmosphere, and then cooling to room temperature along with a furnace to obtain calcium strontium potassium borophosphate, so as to obtain the Eu-doped calcium phosphate luminescent material, wherein x=0.5; y=0.05.
The Eu doped borophosphate luminescent material of the embodiment has two wider emission peaks, which cover 420-750 nm of visible light region, and the peak values are located at 455nm and 595nm; the excitation peak covers the near ultraviolet region, and when different excitation wavelengths (365-400 nm) are adopted, the emission peak intensities of the red wave band and the cyan wave band can be regulated and controlled, so that high-color-rendering white light emission is realized. Packaging the luminescent material and a 365nm ultraviolet light chip into an LED, and obtaining white light with a color temperature of 8000K and a color rendering index of 91; packaging with 370nm ultraviolet chip to obtain LED, and obtaining white light with color temperature 7200K and color rendering index 89; and packaging the white light with a 390nm ultraviolet light chip into an LED, and obtaining the white light with a color temperature of 7000K and a color rendering index of 85.
Example 4
| Raw materials | Weight (g) |
| CaCO 3 | 4.75 |
| SrCO 3 | 7.38 |
| NH 4 (H) 2 PO 4 | 9.20 |
| K 2 CO 3 | 6.91 |
| Eu 2 O 3 | 0.44 |
| H 3 BO 3 | 1.25 |
A method for preparing a Eu-doped borophosphate luminescent material, comprising the steps of:
according to chemical formula K 2 SrCa(PO 4 ) 1.6 (BO 3 ) 0.4 :0.05Eu 2+ Respectively weighing 7.38g of strontium carbonate, 4.75g of calcium carbonate, 9.20g of monoammonium phosphate, 6.91g of potassium carbonate, 1.25g of boric acid and 0.44g of europium oxide, fully grinding in an agate mortar, loading into a crucible, and placing into a high-temperature tube furnace at a volume percentage of 3%H 2 And 97% N 2 Roasting for 4 hours at 1400 ℃ in the mixed atmosphere, and then cooling to room temperature along with a furnace to obtain calcium strontium potassium borophosphate, so as to obtain the Eu-doped calcium phosphate luminescent material, wherein x=0.4; y=0.05.
The Eu doped borophosphate luminescent material of the embodiment has two wider emission peaks, which cover 420-750 nm of visible light region, and the peak values are located at 455nm and 595nm; the excitation peak covers the near ultraviolet region, and when different excitation wavelengths (365-400 nm) are adopted, the emission peak intensities of the red wave band and the cyan wave band can be regulated and controlled, so that high-color-rendering white light emission is realized. Packaging the luminescent material and a 365nm ultraviolet light chip into an LED, and obtaining white light with a color temperature of 8500K and a color rendering index of 85; packaging with 370nm ultraviolet chip to obtain LED, and obtaining white light with color temperature of 8000K and color rendering index of 86; and packaging the white light with a 390nm ultraviolet light chip into an LED, and obtaining white light with a color temperature of 7800K and a color rendering index of 83.
Example 5
| Raw materials | Weight (g) |
| CaCO 3 | 4.75 |
| SrCO 3 | 7.38 |
| NH 4 (H) 2 PO 4 | 9.76 |
| K 2 CO 3 | 6.91 |
| Eu 2 O 3 | 0.44 |
| H 3 BO 3 | 0.97 |
A method for preparing a Eu-doped borophosphate luminescent material, comprising the steps of:
according to chemical formula K 2 SrCa(PO 4 ) 1.7 (BO 3 ) 0.3 :0.05Eu 2+ Respectively weighing 7.38g of strontium carbonate, 4.75g of calcium carbonate, 9.76g of monoammonium phosphate, 6.91g of potassium carbonate, 0.97g of boric acid and 0.44g of europium oxide, fully grinding in an agate mortar, loading into a crucible, and placing into a high-temperature tube furnace at a volume percentage of 3%H 2 And 97% N 2 Roasting for 4 hours at 1400 ℃ in the mixed atmosphere, and then cooling to room temperature along with a furnace to obtain calcium strontium potassium borophosphate, so as to obtain the Eu-doped calcium phosphate luminescent material, wherein x=0.3; y=0.05.
The Eu doped borophosphate luminescent material of the embodiment has two wider emission peaks, which cover 420-750 nm of visible light region, and the peak values are located at 455nm and 595nm; the excitation peak covers the near ultraviolet region, and when different excitation wavelengths (365-400 nm) are adopted, the emission peak intensities of the red wave band and the cyan wave band can be regulated and controlled, so that the cold white light emission is realized. Packaging the luminescent material and a 365nm ultraviolet light chip into an LED, and obtaining cold white light with a color temperature of 9000K and a color rendering index of 86; packaging with 370nm ultraviolet chip to obtain LED, and obtaining white light with color temperature 8500K and color rendering index of 85; and packaging the white light with a 390nm ultraviolet light chip into an LED, wherein the color temperature of the obtained white light is 8000K, and the color rendering index is 82.
Example 6
| Raw materials | Weight (g) |
| CaCO 3 | 4.85 |
| SrCO 3 | 7.38 |
| NH 4 (H) 2 PO 4 | 10.32 |
| K 2 CO 3 | 6.91 |
| Eu 2 O 3 | 0.26 |
| H 3 BO 3 | 0.71 |
A method for preparing a Eu-doped borophosphate luminescent material, comprising the steps of:
according to chemical formula K 2 SrCa(PO 4 ) 1.8 (BO 3 ) 0.2 :0.05Eu 2+ Respectively weighing 7.38g of strontium carbonate, 4.85g of calcium carbonate, 10.32g of monoammonium phosphate, 6.91g of potassium carbonate, 0.71g of boric acid and 0.26g of europium oxide, fully grinding in an agate mortar, loading into a crucible, and placing into a high-temperature tube furnace at a volume percentage of 3%H 2 And 97% N 2 Roasting for 4 hours at 1400 ℃ in the mixed atmosphere, and then cooling to room temperature along with a furnace to obtain calcium strontium potassium borophosphate, so as to obtain the Eu-doped calcium phosphate luminescent material, wherein x=0.2; y=0.05.
The Eu doped borophosphate luminescent material of the embodiment has two wider emission peaks, which cover 420-750 nm of visible light region, and the peak values are located at 455nm and 595nm; the excitation peak covers the near ultraviolet region, and when different excitation wavelengths (365-400 nm) are adopted, the emission peak intensities of the red wave band and the cyan wave band can be regulated and controlled, so that the cold white light emission is realized. Packaging the luminescent material and a 365nm ultraviolet chip into an LED, and obtaining cold white light with a color temperature of 9500K and a color rendering index of 78; packaging with 370nm ultraviolet chip to obtain LED, and obtaining white light with color temperature 9000K and color rendering index 82; and packaging the white light with a 390nm ultraviolet light chip into an LED, and obtaining white light with a color temperature of 8800K and a color rendering index of 83.
Example 7
| Raw materials | Weight (g) |
| CaCO 3 | 4.90 |
| SrCO 3 | 7.38 |
| NH 4 (H) 2 PO 4 | 8.05 |
| K 2 CO 3 | 6.91 |
| Eu 2 O 3 | 0.18 |
| H 3 BO 3 | 1.86 |
A method for preparing a Eu-doped borophosphate luminescent material, comprising the steps of:
according to chemical formula K 2 SrCa(PO 4 ) 1.4 (BO 3 ) 0.6 :0.01Eu 2+ Respectively weighing 7.38g of strontium carbonate, 4.90g of calcium carbonate and 8.05g of monoammonium phosphate6.91g of potassium carbonate, 1.86g of boric acid and 0.18g of europium oxide, which are fully ground in an agate mortar and then placed into a crucible, the volume percentage of which is 3%H in a high-temperature tube furnace 2 And 97% N 2 Roasting for 4 hours at 1400 ℃ in the mixed atmosphere, and then cooling to room temperature along with a furnace to obtain calcium strontium potassium borophosphate, so as to obtain the Eu-doped calcium phosphate luminescent material, wherein x=0.6; y=0.01.
The Eu doped borophosphate luminescent material of the embodiment has two wider emission peaks, which cover 420-750 nm of visible light region, and the peak values are located at 455nm and 595nm; the excitation peak covers the near ultraviolet region, and when different excitation wavelengths (365-400 nm) are adopted, the emission peak intensities of the red wave band and the cyan wave band can be regulated and controlled, so that high-color-rendering white light emission is realized. Packaging the luminescent material and a 365nm ultraviolet light chip into an LED, and obtaining white light with a color temperature of 7600K and a color rendering index of 96; packaging with 370nm ultraviolet chip to obtain LED, and obtaining white light with color temperature 6300K and color rendering index 90; and packaging the white light with a 390nm ultraviolet light chip into an LED, and obtaining white light with a color temperature of 5800K and a color rendering index of 88.
Example 8
| Raw materials | Weight (g) |
| CaCO 3 | 4.85 |
| SrCO 3 | 7.38 |
| NH 4 (H) 2 PO 4 | 8.05 |
| K 2 CO 3 | 6.91 |
| Eu 2 O 3 | 0.27 |
| H 3 BO 3 | 1.86 |
A method for preparing a Eu-doped borophosphate luminescent material, comprising the steps of:
according to chemical formula K 2 SrCa(PO 4 ) 1.4 (BO 3 ) 0.6 :0.02Eu 2+ Respectively weighing 7.38g of strontium carbonate, 4.85g of calcium carbonate, 8.05g of monoammonium phosphate, 6.91g of potassium carbonate, 1.86g of boric acid and 0.27g of europium oxide, fully grinding in an agate mortar, loading into a crucible, and placing into a high-temperature tube furnace at a volume percentage of 3%H 2 And 97% N 2 Roasting for 4 hours at 1400 ℃ in the mixed atmosphere, and then cooling to room temperature along with a furnace to obtain calcium strontium potassium borophosphate, so as to obtain the Eu-doped calcium phosphate luminescent material, wherein x=0.6; y=0.02.
The Eu doped borophosphate luminescent material of the embodiment has two wider emission peaks, which cover 420-750 nm of visible light region, and the peak values are located at 455nm and 595nm; the excitation peak covers the near ultraviolet region, and when different excitation wavelengths (365-400 nm) are adopted, the emission peak intensities of the red wave band and the cyan wave band can be regulated and controlled, so that high-color-rendering white light emission is realized. Packaging the luminescent material and a 365nm ultraviolet light chip into an LED, and obtaining white light with a color temperature of 7500K and a color rendering index of 96; packaging with 370nm ultraviolet chip to obtain LED, and obtaining white color temperature 6200K and color rendering index 91; and packaging the white light with a 390nm ultraviolet light chip into an LED, wherein the color temperature of the obtained white light is 5700K, and the color rendering index is 89.
Example 9
| Raw materials | Weight (g) |
| CaCO 3 | 4.80 |
| SrCO 3 | 7.38 |
| NH 4 (H) 2 PO 4 | 8.05 |
| K 2 CO 3 | 6.91 |
| Eu 2 O 3 | 0.35 |
| H 3 BO 3 | 1.86 |
A method for preparing a Eu-doped borophosphate luminescent material, comprising the steps of:
according to chemical formula K 2 SrCa(PO 4 ) 1.4 (BO 3 ) 0.6 :0.03Eu 2+ Respectively weighing 7.38g of strontium carbonate, 4.90g of calcium carbonate, 8.05g of monoammonium phosphate, 6.91g of potassium carbonate, 1.86g of boric acid and 0.18g of europium oxide, fully grinding in an agate mortar, loading into a crucible, and placing into a high-temperature tube furnace at a volume percentage of 3%H 2 And 97% N 2 Roasting for 4 hours at 1400 ℃ in the mixed atmosphere, and then cooling to room temperature along with a furnace to obtain calcium strontium potassium borophosphate to obtain Eu doped calcium phosphorusAn acid salt luminescent material, wherein x=0.6; y=0.03.
The Eu doped borophosphate luminescent material of the embodiment has two wider emission peaks, which cover 420-750 nm of visible light region, and the peak values are located at 455nm and 595nm; the excitation peak covers the near ultraviolet region, and when different excitation wavelengths (365-400 nm) are adopted, the emission peak intensities of the red wave band and the cyan wave band can be regulated and controlled, so that high-color-rendering white light emission is realized. Packaging the luminescent material and a 365nm ultraviolet light chip into an LED, and obtaining white light with a color temperature of 7500K and a color rendering index of 95; packaging with 370nm ultraviolet chip to obtain LED, and obtaining white light color temperature 6100K, color rendering index 92; and packaging the white light with a 390nm ultraviolet light chip into an LED, wherein the color temperature of the obtained white light is 5800K, and the color rendering index is 90.
Example 10
| Raw materials | Weight (g) |
| CaCO 3 | 4.75 |
| SrCO 3 | 7.38 |
| NH 4 (H) 2 PO 4 | 8.05 |
| K 2 CO 3 | 6.91 |
| Eu 2 O 3 | 0.44 |
| H 3 BO 3 | 1.86 |
A method for preparing a Eu-doped borophosphate luminescent material, comprising the steps of:
according to chemical formula K 2 SrCa(PO 4 ) 1.4 (BO 3 ) 0.6 :0.04Eu 2+ Respectively weighing 7.38g of strontium carbonate, 4.90g of calcium carbonate, 8.05g of monoammonium phosphate, 6.91g of potassium carbonate, 1.86g of boric acid and 0.18g of europium oxide, fully grinding in an agate mortar, loading into a crucible, and placing into a high-temperature tube furnace at a volume percentage of 3%H 2 And 97% N 2 Roasting for 4 hours at 1400 ℃ in the mixed atmosphere, and then cooling to room temperature along with a furnace to obtain calcium strontium potassium borophosphate, so as to obtain the Eu-doped calcium phosphate luminescent material, wherein x=0.6; y=0.04.
The Eu doped borophosphate luminescent material of the embodiment has two wider emission peaks, which cover 420-750 nm of visible light region, and the peak values are located at 455nm and 595nm; the excitation peak covers the near ultraviolet region, and when different excitation wavelengths (365-400 nm) are adopted, the emission peak intensities of the red wave band and the cyan wave band can be regulated and controlled, so that high-color-rendering white light emission is realized. Packaging the luminescent material and a 365nm ultraviolet light chip into an LED, and obtaining white light with a color temperature of 7300K and a color rendering index of 95; packaging with 370nm ultraviolet chip to obtain LED, and obtaining white light with color temperature of 6000K and color rendering index of 93; and packaging the white light with a 390nm ultraviolet light chip into an LED, wherein the color temperature of the obtained white light is 5700K, and the color rendering index is 91.
Fig. 1 is an X-ray diffraction chart of the luminescent materials prepared in example 1, examples 3 to 5 and comparative example 2 according to the present invention, and it can be seen from fig. 1 that the process used in the present invention obtains XRD diffraction peaks of the luminescent materials at a preparation temperature of 1400 ℃ for different boric acid ion concentrations, the diffraction peaks corresponding to diamond phases.
FIG. 2 shows excitation spectra of luminescent material samples prepared in examples 1 and 3-6 of the present invention at detection wavelengths of 455nm and 595nm, from which it can be seen that the excitation peaks cover the ultraviolet, violet and blue regions, and that the relative intensities of the cyan and red emission peaks can be varied when different excitation wavelengths are used.
FIG. 3 shows the emission spectra of the luminescent material samples prepared in example 1 of the present invention under excitation at 365nm, 380nm, 390 and 400nm wavelengths, respectively, from which it can be seen that the emission peaks cover 420-750 nm in the visible region, and the peak values are located at 455nm and 595nm; when different excitation wavelengths (365-400 nm) are adopted, the emission peak intensities of the red wave band and the cyan wave band can be regulated.
The above embodiments are provided for illustrating the present invention, and the scope of the present invention is not limited thereto, but any equivalent changes or modifications made to the present invention within the spirit of the present invention and the scope of the appended claims should be construed as falling within the scope of the present invention.
Claims (5)
1. A Eu doped borophosphate luminescent material is characterized in that the luminescent material has a chemical formula of K 2 SrCa(PO 4 ) 2-x (BO 3 ) x :yEu 2+ Wherein x is more than or equal to 0.55 and less than or equal to 0.6,0<y≤0.07；
When excited at 365-400 nm, emits white light with peak wavelengths at 455nm and 595 nm.
2. A method for preparing the Eu-doped borophosphate luminescent material of claim 1, wherein the Eu-doped borophosphate calcium strontium potassium luminescent material is prepared by a high temperature solid phase reaction method, the method comprising the steps of:
(1) According to chemical formula K 2 SrCa(PO 4 ) 2-x (BO 3 ) x :yEu 2+ The stoichiometric ratio of the raw materials is weighed and ground, and the weighed raw materials are calcium dihydrogen phosphate, calcium carbonate, strontium carbonate, potassium carbonate, boric acid and europium oxide respectively;
(2) And (3) placing the precursor powder in the step (1) into a crucible, feeding the crucible into a high-temperature tube furnace, performing heat treatment in a weak reducing atmosphere, and cooling along with the furnace to obtain the Eu-doped calcium strontium potassium boron phosphate luminescent material.
3. The method for producing Eu-doped borophosphate luminescent material of claim 2, wherein: in the step (2), the heat treatment is as follows: calcining at 1400 ℃ for 4h.
4. The method for producing Eu-doped borophosphate luminescent material of claim 2, wherein: in the step (2), the weak reducing atmosphere is H with the volume percentage of 3 percent 2 With 97% by volume of N 2 Is a mixed gas of (a) and (b).
5. Use of the Eu-doped borophosphate luminescent material of claim 1 in white LEDs.
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