A Eu 2+ Activated narrowband deep blue phosphor, its preparation method and application

Abstract

The present invention discloses a Eu 2+ -activated narrow-band deep blue light phosphor, its preparation method and application, relating to the technical field of fluorescent materials. The Eu 2+ -activated narrow-band deep blue light phosphor has the chemical formula: Ba (1‑x) XY2:xEu 2+ , where X is Hf and / or Zr, Y is BO3 3‑ or PO4 3‑ , and 0 < x ≤ 1. The Eu 2+ -activated narrow-band deep blue light phosphor has a relatively wide excitation range and can be effectively excited by near-ultraviolet light and violet light, and can generate deep blue light emission covering 385 - 440 nm. Moreover, the half-peak width of the phosphor is very narrow, the color purity is relatively high, the color coordinates are located in the blue light edge region of the CIE chromaticity diagram, and the color gamut is relatively wide. And the luminescence intensity of this phosphor is high, meeting the current demand for the vacancy in the dark blue region, and can be widely applied to the field of backlight display LEDs.

Description

Technical Field

[0001] This invention relates to the field of fluorescent materials technology, and more specifically, to an Eu... 2+ Activated narrowband deep blue phosphor, its preparation method and application. Background Technology

[0002] Phosphorescent white light-emitting diodes (pc-WLEDs), with their advantages of high efficiency, low energy consumption, environmental friendliness, and durability, are gradually replacing traditional fluorescent lamps as the ideal backlight source for modern liquid crystal displays (LCDs). For the increasingly thinner and lighter LCDs, obtaining clear images with high color saturation is currently a hot research topic. The vibrancy of LCD colors is usually described by the color gamut, which is the size of the triangular area enclosed by the red, green, and blue (RGB) colors emitted by the backlight component on the CIE chromaticity diagram. Blue phosphors, as an indispensable component of the three primary color phosphors, can significantly improve luminous efficiency and visual quality. Therefore, developing high-quality narrowband blue phosphors with stable chemical properties and high color purity is of great significance.

[0003] Generally, the emission peak position and full width at half maximum (FWHM) of a phosphor directly affect the color gamut and color purity of the material. A narrower emission band results in a higher color gamut and higher color purity. Currently, the most representative commercially available blue phosphor is BaMgAl. 10 O 17 Eu 2+ (BAM:Eu 2+ This phosphor, known for its high luminous efficiency and central wavelength of 452 nm, has been widely used in fluorescent and plasma displays. However, BAM:Eu... 2+ Its chemical stability is poor, and the luminescent center Eu 2+ It is easily oxidized to Eu. 3+ This severely affects its luminous efficiency. BAM:Eu 2+ The phosphor exhibits a wide full width at half maximum (FWHM ≈ 55 nm) and cannot be well excited under near-ultraviolet (n-UV) light, hindering its application in n-UV LED devices. In 2018, Xia Zhiguo et al. reported an ultranarrow-band blue phosphor, RbNa3(Li3SiO4)4:Eu... 2+ (RNLSO:Eu 2+ Its full width at half maximum (FWHM) is only 22.4 nm, and its center wavelength is located at 471 nm. However, RNLSO:Eu 2+Problems such as low quantum efficiency and poor chemical stability still exist. Furthermore, most reported blue phosphors typically emit wavelengths in the longer blue light wavelength range (440-480 nm), resulting in a color gap in the deep blue (400-430 nm) region. Therefore, developing novel narrowband deep blue phosphors with high color purity and improving their luminescent properties (peak position and FWHM) has been a major challenge for backlighting LED applications.

[0004] The prior art discloses a divalent europium-doped yttrium strontium triborate-based blue phosphor and its preparation method. The general chemical formula of the phosphor is Sr. 3-x Y(BO3)3:xEu, where 0.01≤x≤0.15, the phosphor emits blue light under near-ultraviolet excitation, with an excitation spectrum of 200–400 nm and a main excitation peak near 232 nm. Its emission spectrum is 400–650 nm, with a main peak near 465 nm. However, this blue phosphor has a wide emission range but lacks high color purity, and does not improve the color purity and luminescence characteristics of existing blue phosphors. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings and deficiencies of existing blue phosphors, such as wide emission bandwidth, insufficient color purity, and narrow color gamut, and to provide a Eu... 2+ Activated narrowband deep blue phosphor.

[0006] Another object of the present invention is to provide a Eu 2+ A method for preparing activated narrowband deep blue phosphor.

[0007] Another object of the present invention is to provide a Eu 2+ Application of activated narrowband deep blue phosphor in backlight display LEDs.

[0008] The above-mentioned objective of this invention is achieved through the following technical solution:

[0009] A Eu 2+ The activated narrowband deep blue phosphor has the chemical formula: Ba (1-x) XY2:xEu 2+ Where X is Hf and / or Zr, and Y is BO3 3- Or PO4 3- 0 <x≤1。

[0010] It should be noted that:

[0011] The Eu of the present invention 2+ Eu in activated narrowband deep blue phosphor 2+ It is an activator that has 4f symmetry allowed. 6 5d 1-4f 7 The (5d-4f) transition makes its luminescence properties highly susceptible to the influence of the crystal field environment. 2+ Typically exhibiting broadband emission, it can range from ultraviolet to near-infrared light, depending on changes in the matrix lattice environment and external environmental factors such as temperature, pressure, and excitation wavelength position. Ba(Hf,Zr)(BO3)2, Ba(Hf,Zr)(PO4)2, or a mixture thereof are used as the matrix, with Eu... 2+ With Ba in the matrix 2+ With the same valence state and similar ionic radius, Eu 2+ Ba tends to enter the matrix 2+ The cell position yields Eu. 2+ The activated phosphor can be effectively excited by 250-395nm violet or near-ultraviolet light to produce deep blue light emission covering 385-440nm. Its main peak is located at about 402nm, the half-peak width can be 27nm, the color coordinates are (0.1655, 0.0272), and the color purity can reach up to 95.0%, which meets the current demand for the deep blue (400-430nm) region.

[0012] In a specific embodiment, the Eu of the present invention 2+ The activated narrowband deep blue phosphor can have the chemical formula Ba 0.90 Hf(BO3)2:0.10Eu 2+ ;or

[0013] Eu 2+ The activated narrowband deep blue phosphor can have the chemical formula Ba 0.94 Hf(BO3)2:0.06Eu 2+ ;or

[0014] Eu 2+ The activated narrowband deep blue phosphor can have the chemical formula Ba 0.96 Hf(BO3)2:0.04Eu 2+ ;or

[0015] Eu 2+ The activated narrowband deep blue phosphor can have the chemical formula Ba 0.98 Hf(PO4)2:0.02Eu 2+ ;or

[0016] Eu 2+ The activated narrowband deep blue phosphor can have the chemical formula Ba 0.85 Hf(BO3)2:0.15Eu 2+ ;or

[0017] Eu 2+ The activated narrowband deep blue phosphor can have the chemical formula Ba 0.8Hf(PO4)2:0.2Eu 2+ ;or

[0018] Eu 2+ The activated narrowband deep blue phosphor can have the chemical formula Ba 0.98 Hf 0.5 Zr 0.5 (BO3)2:0.02Eu 2+ ;or

[0019] Eu 2+ The activated narrowband deep blue phosphor can have the chemical formula Ba 0.82 Zr(PO4)2:0.18Eu 2+ .

[0020] Preferably, x is 0.02 to 0.1.

[0021] Due to Eu 2+ At higher concentrations, concentration quenching occurs, and the luminescence intensity of the phosphor decreases with increasing Eu. 2+ The decrease is due to the increase in doping concentration, which weakens Eu. 2+ The luminous efficiency. When the Eu 2+ Activated narrowband deep blue phosphor Eu 2+ When the doping concentration is 0.02≤x≤0.1, the luminescence effect is excellent.

[0022] More preferably, X is Hf and Y is BO3. 3- When the Eu 2+ In the activated narrowband deep blue phosphor, X is Hf hafnium and Y is BO3. 3- The light emission effect is better at that time.

[0023] Preferably, the excitation spectrum of the phosphor is 250–395 nm, the emission spectrum is 385–440 nm, and the main peak is located at around 402 nm.

[0024] This invention also specifically protects a Eu 2+ The preparation method of activated narrowband deep blue phosphor includes the following steps:

[0025] A compound containing Ba, a compound containing Hf or Zr, a compound containing europium, boric acid, or a phosphate are mixed uniformly according to stoichiometric ratios and calcined under a reducing atmosphere to obtain Eu. 2+ Activated narrowband deep blue phosphor.

[0026] The Eu of the present invention 2+ The activated narrowband deep blue phosphor is prepared by a high-temperature solid-state synthesis method, which has the advantages of simple preparation process and ease of operation. It uses inexpensive metal ion-containing oxides or salts as raw materials, and adjusts the Eu content in the compound... 2+Eu was directly synthesized by sintering under mild conditions and a reducing atmosphere, according to the ratio of other metal ions. 2+ Activated narrowband deep blue phosphor.

[0027] The reducing atmosphere of the present invention can be a CO reducing atmosphere.

[0028] The compounds containing Ba, Hf or Zr, europium, boric acid or phosphate described in this invention can be mixed evenly by thorough grinding in a mortar, or by any other mixing method in the art.

[0029] To further improve product purity and reduce impurity content, preferably, the calcination temperature is 800–1600℃, the heating rate is 2–50℃ / min, and the holding time is 2–10h.

[0030] More preferably, the calcination temperature is 1100-1300℃, the heating rate is 5-20℃ / min, and the holding time is 4-8h.

[0031] In a specific embodiment, the Hf-containing compound of the present invention is hafnium oxide and / or hafnium carbonate, and the Zr-containing compound is zirconium oxide and / or zirconium carbonate.

[0032] In specific embodiments, the Ba-containing compounds of the present invention are selected from one or more of barium oxide, barium carbonate, barium nitrate, barium oxalate, and barium acetate.

[0033] In specific embodiments, the europium-containing compounds of the present invention are mainly selected from one or more of europium oxide, europium carbonate, europium nitrate, europium oxalate, and europium acetate.

[0034] This invention also specifically protects a Eu 2+ Application of activated narrowband deep blue phosphor in backlight LED displays.

[0035] The Eu of the present invention 2+ Activated narrowband deep blue phosphors can significantly improve luminous efficiency and visual quality when applied to backlight LEDs.

[0036] Compared with the prior art, the beneficial effects of the present invention are:

[0037] The Eu of the present invention 2+The activated narrowband deep blue phosphor has a wide excitation range, effectively excited by near-ultraviolet and violet light, with an excitation spectrum covering 250–395 nm, and a main peak around 375 nm. Under excitation at 300 nm and 375 nm, this phosphor can produce deep blue light emission covering 385–440 nm, with the strongest emission peak around 402 nm. This phosphor has a very narrow half-width at half-maximum (FWHM) and high color purity, reaching up to 95.0%; its chromaticity coordinates are (0.1655, 0.0272), located in the blue light edge region of the CIE chromaticity diagram, indicating a wide color gamut.

[0038] In addition, this phosphor has high luminous intensity, which meets the current demand for the deep blue (400-430nm) region and can be widely used in the field of backlight display LED. Attached Figure Description

[0039] Figure 1 for Figure 1 Eu in Examples 1-3 2+ X-ray powder diffraction pattern of activated narrowband deep blue phosphor.

[0040] Figure 2 Ba prepared in Example 1 0.90 Hf(BO3)2:0.10Eu 2+ Fluorescence excitation spectrum of deep blue phosphor.

[0041] Figure 3 Ba prepared in Example 1 0.90 Hf(BO3)2:0.10Eu 2+ Fluorescence emission spectrum of deep blue phosphor.

[0042] Figure 4 Ba prepared in Example 1 0.90 Hf(BO3)2:0.10Eu 2+ CIE color coordinates of deep blue phosphor.

[0043] Figure 5 Ba prepared in Example 2 0.94 Hf(BO3)2:0.06Eu 2+ Fluorescence excitation spectrum of deep blue phosphor.

[0044] Figure 6 Ba prepared in Example 2 0.94 Hf(BO3)2:0.06Eu 2+ Fluorescence emission spectrum of deep blue phosphor.

[0045] Figure 7 Ba prepared in Example 2 0.94 Hf(BO3)2:0.06Eu2+ Quantum efficiency of deep blue phosphor.

[0046] Figure 8 Ba prepared in Example 2 0.94 Hf(BO3)2:0.06Eu 2+ CIE color coordinates of deep blue phosphor.

[0047] Figure 9 Ba prepared in Example 4 0.98 Hf(PO4)2:0.02Eu 2+ Fluorescence excitation spectrum of deep blue phosphor.

[0048] Figure 10 Ba prepared in Example 4 0.98 Hf(PO4)2:0.02Eu 2+ Fluorescence emission spectrum of deep blue phosphor.

[0049] Figure 11 Ba prepared in Example 4 0.98 Hf(PO4)2:0.02Eu 2+ CIE color coordinates of deep blue phosphor.

[0050] Figure 12 Ba prepared in Example 5 0.98 Hf 0.5 Zr 0.5 (BO3)2:0.02Eu 2+ Fluorescence excitation spectrum of deep blue phosphor.

[0051] Figure 13 Ba prepared in Example 5 0.98 Hf 0.5 Zr 0.5 (BO3)2:0.02Eu 2+ Fluorescence emission spectrum of deep blue phosphor.

[0052] Figure 14 Ba prepared in Example 5 0.98 Hf 0.5 Zr 0.5 (BO3)2:0.02Eu 2+ CIE color coordinates of deep blue phosphor. Detailed Implementation

[0053] The present invention will be further described below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise stated, the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.

[0054] Example 1

[0055] A Eu 2+ The activated narrowband deep blue phosphor has the chemical formula: Ba 0.9 Hf(BO3)2:0.10Eu 2+ .

[0056] Eu in Example 1 2+ Activated narrowband deep blue phosphor Ba 0.9 Hf(BO3)2:0.10Eu 2+ The preparation method is as follows:

[0057] The raw materials were weighed according to the elemental molar ratio Ba:Hf:B:Eu = 0.90:1:2:0.10, and the contents of the weighed raw materials were as follows:

[0058] Barium carbonate (BaCO3) 0.3552g, hafnium oxide (HfO2) 0.4210g, boric acid (H3BO3) 0.2473g, europium oxide (Eu2O3) 0.0352g.

[0059] The above raw materials were added to an agate mortar and ground evenly. The mixture was then transferred to a corundum crucible, which was placed in a high-temperature furnace and calcined at 1300℃ with a heating rate of 10℃ / min for 8 hours. After the reaction was complete, the mixture was allowed to cool naturally to room temperature and then ground evenly to obtain the final product.

[0060] The X-ray powder diffraction results of the product are as follows: Figure 1 As shown, all diffraction peaks correspond to the peaks in the standard card BaHf(BO3)2 (ICSD#252646), indicating that the preparation method of this patent will not affect the phase.

[0061] The fluorescence excitation and emission spectra of the product are as follows: Figure 2 , 3 As shown, when monitoring a wavelength of 402 nm, its excitation spectrum covers a relatively wide ultraviolet and near-ultraviolet region of 250–395 nm, with strong excitation near 330–380 nm. When the excitation wavelength is at 375 nm, its emission spectrum covers deep blue emission of 385–440 nm, with the strongest emission peak at around 402 nm and a very narrow half-width of 27 nm.

[0062] The color purity of this product is 94.1%, and the CIE color coordinates are as follows: Figure 4 As shown, the blue light edge region located at (0.1651, 0.0310) can form a wide color gamut. Since the product does not emit significant light beyond 550nm, the spectral test only measured up to 550nm, and the wavelength range selected for color purity calculation was 380–550nm.

[0063] Example 2

[0064] A Eu 2+ The activated narrowband deep blue phosphor has the chemical formula: Ba 0.94 Hf(BO3)2:0.06Eu 2+ .

[0065] Eu in Example 2 2+ Activated narrowband deep blue phosphor Ba 0.94 Hf(BO3)2:0.06Eu 2+ The preparation method is as follows:

[0066] The raw materials were weighed according to the elemental molar ratio Ba:Hf:B:Eu = 0.94:1:2:0.06. The contents of the weighed raw materials are as follows:

[0067] Barium carbonate (BaCO3) 0.3710g, hafnium oxide (HfO2) 0.4210g, boric acid (H3BO3) 0.2473g, europium oxide (Eu2O3) 0.0211g were added to an agate mortar and ground evenly. The mixture was then transferred to a corundum crucible and calcined in a high-temperature furnace at 1100℃, a heating rate of 5℃ / min, and a holding time of 6 hours. After the reaction was complete, the mixture was allowed to cool naturally to room temperature and then ground evenly to obtain the final product.

[0068] The fluorescence excitation and emission spectra of the product are as follows: Figure 5 , 6 As shown, when monitoring a wavelength of 402 nm, its excitation spectrum covers a relatively wide ultraviolet and near-ultraviolet region of 250–395 nm, with strong excitation near 330–380 nm. When the excitation wavelength is at 375 nm, its emission spectrum covers deep blue emission of 385–440 nm, with the strongest emission peak at around 402 nm and a very narrow half-width of 27 nm.

[0069] The quantum efficiency of this phosphor is as follows: Figure 7 As shown, it reaches 23.4%, and Eu in other embodiments 2+ The quantum efficiency of activated narrowband deep blue phosphors is slightly lower than this value.

[0070] The color purity of this product is 95.0%, and the CIE color coordinates are as follows: Figure 8 As shown, the blue light edge region located at (0.1655, 0.0272) can form a wide color gamut. Since this product does not emit significant light beyond 550nm, the wavelength range selected for color purity calculation was 380–550nm for comparison with Example 1.

[0071] Example 3

[0072] A Eu2+ The activated narrowband deep blue phosphor has the chemical formula: Ba 0.96 Hf(BO3)2:0.04Eu 2+ .

[0073] Eu in Example 3 2+ Activated narrowband deep blue phosphor Ba 0.96 Hf(BO3)2:0.04Eu 2+ The preparation method is as follows:

[0074] The raw materials were weighed according to the elemental molar ratio Ba:Hf:B:Eu = 0.96:1:2:0.04. The contents of the weighed raw materials are as follows:

[0075] Barium carbonate (BaCO3) 0.3789g, hafnium oxide (HfO2) 0.4210g, boric acid (H3BO3) 0.2473g, europium oxide (Eu2O3) 0.0141g.

[0076] The above raw materials were added to an agate mortar and ground evenly. The mixture was then transferred to a corundum crucible, which was placed in a high-temperature furnace and calcined at 1100℃ with a heating rate of 10℃ / min for 6 hours. After the reaction was complete, the mixture was allowed to cool naturally to room temperature and then ground evenly to obtain the final product.

[0077] The product's CIE color coordinates are located at (0.1653, 0.0309) in the blue light edge region, allowing for a wide color gamut. Color purity is high, reaching 94.1%. Since the product does not emit significant light beyond 550 nm, the wavelength range selected for color purity calculation was 380–550 nm for comparison with Example 1.

[0078] Example 4

[0079] A Eu 2+ The activated narrowband deep blue phosphor has the chemical formula: Ba 0.98 Hf(PO4)2:0.02Eu 2+ .

[0080] Eu in Example 4 2+ Activated narrowband deep blue phosphor Ba 0.98 Hf(PO4)2:0.02Eu 2+ The preparation method is as follows:

[0081] The raw materials were weighed according to the elemental molar ratio Ba:Hf:P:Eu = 0.98:1:2:0.02. The contents of the weighed raw materials are as follows:

[0082] Barium carbonate (BaCO3) 0.3868g, hafnium oxide (HfO2) 0.4210g, ammonium dihydrogen phosphate (NH4H2PO4)

[0083] 0.4610g, europium oxide (Eu₂O₃) 0.0070g,

[0084] The above raw materials were added to an agate mortar and ground evenly. The mixture was then transferred to a corundum crucible, which was placed in a high-temperature furnace and calcined at 1100℃ with a heating rate of 5℃ / min for 5 hours. After the reaction was complete, the mixture was allowed to cool naturally to room temperature and then ground evenly to obtain the final product.

[0085] The fluorescence excitation and emission spectra of the product are as follows: Figure 9 and 10 As shown, when monitoring a wavelength of 432 nm, its excitation spectrum covers a relatively wide ultraviolet and near-ultraviolet region of 250–380 nm, with strong excitation near 330–380 nm. When the excitation wavelength is at 375 nm, its emission spectrum covers deep blue light emission of 385–505 nm, with the strongest emission peak at 432 nm and a full width at half maximum (FWHM) of 44 nm.

[0086] The product's CIE color coordinates are as follows Figure 11 As shown, the blue light edge region located at (0.1723, 0.0564) has a color purity of 86.6%. The wavelength range selected for color purity calculation is 370–700 nm.

[0087] Example 5

[0088] A Eu 2+ The activated narrowband deep blue phosphor has the following chemical formula:

[0089] Ba 0.98 Hf 0.5 Zr 0.5 (BO3)2:0.02Eu 2+ .

[0090] Eu in Example 5 2+ Activated narrowband deep blue phosphor Ba 0.98 Hf 0.5 Zr 0.5 (BO3)2:0.02Eu 2+ The preparation method is as follows:

[0091] The raw materials were weighed according to the elemental molar ratio Ba:Hf:Zr:B:Eu = 0.98:0.5:0.5:2:0.02. The contents of the weighed raw materials are as follows: barium carbonate (BaCO3) 0.3868g, hafnium oxide (HfO2) 0.2105g, zirconium oxide (ZrO2) 0.1232g, boric acid (H3BO3) 0.2473g, europium oxide (Eu2O3) 0.0070g.

[0092] The above raw materials were added to an agate mortar and ground evenly. The mixture was then transferred to a corundum crucible, which was placed in a high-temperature furnace and calcined at 1200℃ with a heating rate of 5℃ / min for 7 hours. After the reaction was complete, the mixture was allowed to cool naturally to room temperature and then ground evenly to obtain the final product.

[0093] The fluorescence excitation and emission spectra of the product are as follows: Figure 12 and 13 As shown, when monitoring a wavelength of 407 nm, its excitation spectrum covers a relatively wide ultraviolet and near-ultraviolet region of 250–395 nm, with strong excitation near 330–385 nm. When the excitation wavelength is at 375 nm, its emission spectrum covers deep blue emission of 395–450 nm, with the strongest emission peak at 407 nm and a full width at half maximum (FWHM) of 34 nm.

[0094] The product's CIE chromaticity diagram is as follows Figure 14 As shown, the chromaticity coordinates are located at (0.2183, 0.0721) in the blue light edge region, with a color purity of 76.6%. The wavelength range selected for color purity calculation is 395–700 nm.

[0095] Example 6

[0096] A Eu 2+ The activated narrowband deep blue phosphor has the chemical formula: Ba 0.85 Hf(BO3)2:0.15Eu 2+ .

[0097] Eu in Example 1 2+ Activated narrowband deep blue phosphor BaHf(BO3)2:0.15Eu 2+ The preparation method is basically the same as in Example 1, except that:

[0098] The raw materials used in this embodiment are barium nitrate Ba(NO3)2, hafnium carbonate 2HfO2·CO2·xH2O, boric acid H3BO3, and europium carbonate Eu2(CO3)3, with the molar ratio of the elements Ba:Hf:B:Eu = 0.85:1:2:0.15.

[0099] Eu in Example 6 2+The activated narrow-band deep blue phosphor had a lower purity and slightly lower color purity than in Example 2.

[0100] Example 7

[0101] A Eu 2+ The activated narrowband deep blue phosphor has the chemical formula: Ba 0.8 Hf(PO4)2:0.2Eu 2+ .

[0102] Eu in Example 7 2+ Activated narrowband deep blue phosphor Ba 0.8 Hf(PO4)2:0.2Eu 2+ The preparation method is basically the same as in Example 4, except that:

[0103] The raw materials used in this embodiment are barium acetate (CH3COO)2Ba, hafnium oxide HfO2, diammonium hydrogen phosphate (NH4)2HPO4, and europium nitrate Eu(NO3)3, with the molar ratio of the elements Ba:Hf:P:Eu = 0.8:1:2:0.2.

[0104] Eu in Example 7 2+ The activated narrowband deep blue phosphor product is essentially the same as that in Example 4.

[0105] Example 8

[0106] A Eu 2+ The activated narrowband deep blue phosphor has the chemical formula: Ba 0.82 Zr(PO4)2:0.18Eu 2+ .

[0107] Eu in Example 8 2+ Activated narrowband deep blue phosphor Ba 0.82 Zr(PO4)2:0.18Eu 2+ The preparation method is as follows:

[0108] The raw materials were weighed according to the molar ratio of the elements Ba:Zr:P:Eu = 0.82:1:2:0.18. The weighed raw materials were: barium acetate (CH3COO)2Ba, zirconium oxide ZrO2, diammonium hydrogen phosphate (NH4)2HPO4, and europium carbonate Eu2(CO3)3.

[0109] The above raw materials were added to an agate mortar and ground evenly. The mixture was then transferred to a corundum crucible, which was placed in a high-temperature furnace and calcined at 1600℃ with a heating rate of 30℃ / min for 7 hours. After the reaction was complete, the mixture was allowed to cool naturally to room temperature and then ground evenly to obtain the final product.

[0110] Eu in Example 8 2+ The activated narrow-band deep blue phosphor had a lower purity and slightly lower color purity than in Example 2.

[0111] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A Eu 2+ activated narrow-band deep-blue phosphor, characterized in that, Ba (1-x) XY2:xEu 2+ wherein X is Hf, Y is BO3 3- or PO4 3- and x is 0.02 to 0.

2.

2. The Eu of claim 1 2+ The activated narrow-band deep blue phosphor is characterized in that, x is between 0.02 and 0.

1.

3. The Eu of claim 1 2+ The activated narrow-band deep blue phosphor is characterized by, X is Hf, Y is BO3 3- .

4. The Eu as described in any one of claims 1 to 3 2+ The activated narrowband deep blue phosphor is characterized by, The excitation spectrum of the phosphor is 250~395nm, the emission spectrum is 385~440nm, and the main peak is located at 402nm.

5. A Eu as described in any one of claims 1 to 4 2+ A method for preparing activated narrowband deep blue phosphor, characterized in that, Includes the following steps: A Ba-containing compound, a Hf-containing compound, a Eu-containing compound, boric acid or a phosphate salt are mixed in stoichiometric ratio and calcined under a reducing atmosphere to obtain Eu 2+ Activated narrow-band deep blue phosphor.

6. The preparation method according to claim 5, characterized in that, The calcination temperature is 800~1600℃, the heating rate is 2~50℃ / min, and the holding time is 2~10h.

7. The preparation method according to claim 6, characterized in that, The calcination temperature is 1100~1300℃, the heating rate is 5~20℃ / min, and the holding time is 4~8h.

8. The preparation method according to claim 7, characterized in that, The Hf-containing compound is hafnium oxide and / or hafnium carbonate.

9. The preparation method according to claim 7, characterized in that, The Ba-containing compound is selected from one or more of barium oxide, barium carbonate, barium nitrate, barium oxalate, and barium acetate.

10. A Eu according to any one of claims 1 to 4, wherein the Eu is Eu 2+ Use of the activated narrow-band deep-blue phosphor in backlit display LEDs.

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