A red fluorescent powder, a preparation method and application thereof

Abstract

This invention discloses a red phosphor, its preparation method, and its application. Its general chemical formula is aMO·bN₂O·cR₂O₃·TO·(1-x)WO₃:xMn. 4+ Where M is selected from at least one of Ca, Sr, and Ba; N is selected from at least one of Li, Na, K, Rb, and Cs; R is selected from at least one of Sc, Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Bi; T is selected from at least one of Zn or Mg, and 0 ≤ a ≤ 2, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.5, 0

Description

Technical Field

[0001] This invention belongs to the field of luminescent materials technology, and particularly relates to a red phosphor, its preparation method and application. Background Technology

[0002] Red phosphors have wide applications in lighting, displays, plant growth lights, light-converting agricultural films, and solar cells. They are a key component in improving the performance of these optoelectronic devices, and these materials have always been a research focus and challenge in the field of luminescent materials.

[0003] According to the type of luminescent center, red phosphors can be roughly divided into three categories: (1) those with Eu 3+ 、Sm 3+ and Pr 3+ Narrowband red phosphors activated by trivalent rare earth ions, represented by Eu, have high purity, but due to their characteristic ff transition being a forbidden transition, the phosphors mainly absorb ultraviolet light and their excitation efficiency by visible light is usually low, which is not conducive to their application in blue LED chips and other visible light conversion optoelectronic devices. (2) Eu 2+ Activated sulfide, nitride, and oxynitride phosphors have broadband blue-green absorption peaks and tunable broadband red emission peaks, but these materials have harsh synthesis conditions and high costs. (3) Transition metal ions Mn 4+ Activated phosphor, with d 3 Electronic configuration, Mn 4+ It exhibits broadband ultraviolet + visible light dual-spectrum excitation and tunable broadband red-far-red light emission properties. Compared to the previous two types of rare-earth phosphors, the transition metal Mn... 4+ Phosphors are readily available and inexpensive, and their superior spectral properties and wider applicability have made them a focus of attention in the field of luminescent materials in recent years.

[0004] Mn 4+ The excitation spectrum of activated phosphors typically includes two broadband bands, one from Mn and the other from the other from the other. 4+ of 4 A2→ 4 T1 and 4 A2→ 4 The T2 transition occurs in the near-ultraviolet and blue-green regions, respectively; the red light emission of the phosphor originates from... 2 E→ 4 A2 transition. Mn 4+ Red phosphors are mainly classified into two types: fluorides and oxides. In Mn... 4+ Fluoride phosphors, such as K2SiF6:Mn 4+ Etc., Mn-F coordination provides a strong crystal field, Mn 4+Exhibiting dual excitations in the ultraviolet and blue regions and ~620 nm red emission properties, it has been commercialized in the application of blue-chip white LED lighting. However, fluoride phosphors are difficult to synthesize, generate a large amount of fluoride-containing wastewater, and the fluoride red phosphors have poor stability and complex post-treatment processes. In contrast, Mn 4+ oxide phosphors have a simple synthesis process, low cost, no pollution, and a wider spectral tunability range. Mn 4+ oxide phosphors have strong ultraviolet absorption, the excitation peak in the visible light region can be tuned in the blue-green range, and the emission peak can be tuned in the red-dark red (630 - 730 nm) range. Therefore, it has good application prospects in white lighting, plant supplementary lights, light conversion agricultural films, and solar cells, etc. However, oxide phosphors also have deficiencies. In the oxide, 4 A2→ 4 the T2 transition probability is low, so the absorption rate in the visible light region is low, which hinders the application of such materials with good spectral position matching in blue-chip optoelectronic devices and solar energy conversion devices. Therefore, improving the excitation intensity of Mn 4+ oxide phosphors in the visible light region is the key to solving the application bottleneck problem of such materials. Summary of the Invention

[0005] In order to overcome the problems in the prior art, the present invention provides a red phosphor, its preparation method and application, which improve the 4+ of 4 Mn 4 A2→ 4 Mn 2 T2 probability, and even break the spin-forbidden 4+ A2→

[0006] T2 transition, thereby overcoming the problems of narrow excitation spectrum in the visible light region and low blue-green light excitation efficiency of Mn

[0007] The present invention provides a red phosphor, and the chemical composition general formula of the red phosphor is aMO·bN2O·cR2O3·TO·(1 - x)WO3:xMn 4+ , where M is selected from at least one of Ca, Sr, and Ba, N is selected from at least one of Li, Na, K, Rb, and Cs, R is selected from at least one of Sc, Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Bi, T is selected from at least one of Zn or Mg, and 0 ≤ a ≤ 2, 0 ≤ b ≤ 0.5, 0 ≤ c ≤ 0.5, 0 < x ≤ 0.1, and the sum of a, 2b, and 2c is 2.0, and all values are mole fractions.

[0008] The red phosphor prepared in this invention has the chemical composition aMO·bN2O·cR2O3·TO·(1-x)WO3:xMn 4 + By adding N + and R 3+ , making Mn 4+ The probability of energy level transitions at the W lattice site changes, thus improving the excitation efficiency in the visible light region.

[0009] As an optional implementation, in the red phosphor provided by the present invention, the red phosphor emits red light when excited by visible light in the wavelength range of 380-650 nm.

[0010] As an optional implementation, in the red phosphor provided by the present invention, the red phosphor emits red light when excited by ultraviolet light in the wavelength range of 250-380nm.

[0011] As an optional implementation, in the red phosphor provided by the present invention, the red light wavelength range of the red phosphor is 635-800nm.

[0012] As an optional implementation, in the red phosphor provided by the present invention, N is selected from at least one of Li, Na, K and Cs, and R is selected from at least one of Sc, Y, La, Sm, Eu, Gd and Bi.

[0013] Based on the same technical concept, the present invention also provides a method for preparing the above-mentioned red phosphor that can be excited by visible light, comprising the following steps:

[0014] S1. Weigh out an oxygen-containing compound containing M, N, R, T, and W and a manganese source according to the molar ratio of each element in the general chemical formula, and mix them evenly to obtain a mixture.

[0015] S2. The mixture obtained in step S1 is placed in an alumina crucible and sintered at high temperature in a muffle furnace at a reaction temperature of 900-1200℃ for 3-10 hours to obtain the red phosphor.

[0016] As an optional implementation, in the preparation method provided by the present invention, the oxygen-containing compound containing M, N, R, T, and W is selected from one of oxides, carbonates, acetates, oxalates, nitrates, tungstates, or hydroxides.

[0017] As an optional implementation, in the preparation method provided by the present invention, the manganese source is selected from one or more of manganese oxide, manganese carbonate, or manganese chloride.

[0018] As an optional implementation, in the preparation method provided by this invention, the oxygen-containing compound containing M is a Sr compound, the oxygen-containing compound containing N is a K compound, the oxygen-containing compound containing R is a La compound, and the oxygen-containing compound containing T is a Zn compound. The red phosphor prepared from the above oxygen-containing compounds has the following composition: 1.3SrO·0.175K2O·0.175La2O3·ZnO·0.97WO3:0.03Mn 4+ The device exhibits a wide ultraviolet-visible excitation spectrum, covering the range of 280-630 nm, with the main excitation peaks located at 393 nm and 500 nm. The red phosphor also exhibits a wide emission spectrum in the red region, covering the range of 640-800 nm, with the main emission peak located at 694 nm. It also demonstrates high visible light excitation efficiency.

[0019] As an optional implementation, in the preparation method provided by this invention, the oxygen-containing compound containing M is a Sr compound, the oxygen-containing compound containing N is a K compound, the oxygen-containing compound containing R is a Bi compound, and the oxygen-containing compound containing T is a Zn compound. The red phosphor prepared from the above oxygen-containing compounds has the following composition: SrO·0.25K2O·0.25Bi2O3·ZnO·0.985WO3:0.015Mn 4+ The phosphor exhibits a dual broadband continuous excitation spectrum in the ultraviolet and visible regions, ranging from 260-410 nm and 410-650 nm, with the ultraviolet excitation peak at 343 nm and the visible excitation peaks at 468 nm and 555 nm. The red phosphor also possesses a broadband emission spectrum in the red region, covering the range of 690-800 nm, with the main emission peak at 730 nm. It exhibits high visible light excitation efficiency.

[0020] Based on the same technical concept, the present invention also provides the application of the above-mentioned red phosphor in near-ultraviolet and blue light chip LED optoelectronic devices, as well as light-converting agricultural films and solar cell devices.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] The red phosphor provided by this invention overcomes the limitations of Mn 4+ Overcoming the limitations of narrow excitation peaks and low excitation efficiency in the visible light region of oxide phosphors, this device exhibits a broadband excitation peak in the near-ultraviolet to yellow-green region, enabling it to be effectively excited by visible light and emit red light. This marks the first successful realization of Mn... 4+ It exhibits a wide-bandwidth excitation spectrum in the visible light region and high blue-green light excitation efficiency. The phosphor can be applied to near-ultraviolet and blue light chip LED optoelectronic devices, as well as to light-converting agricultural films and solar cell devices, improving solar energy utilization and promoting sustainable development. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0024] Figure 1 The composition is SrO·0.25Li₂O·0.25La₂O₃·ZnO·0.991WO₃:0.009Mn. 4+ Fluorescence spectrum of phosphor;

[0025] Figure 2 The composition is 1.4SrO·0.15Na2O·0.15La2O3·ZnO·0.986WO3:0.014Mn. 4+ Fluorescence spectrum of phosphor;

[0026] Figure 3 is 1.3SrO·0.175K2O·0.175La2O3·ZnO·0.97WO3:0.03Mn 4+ Fluorescence spectrum of phosphor;

[0027] Figure 4 The composition is SrO·0.25Cs2O·0.25La2O3·ZnO·0.98WO3:0.02Mn. 4+ Fluorescence spectrum of phosphor;

[0028] Figure 5 The composition is SrO·0.25K2O·0.25Sm2O3·ZnO·0.92WO3:0.08Mn. 4+ Fluorescence spectrum of phosphor;

[0029] Figure 6 The composition is SrO·0.25K2O·0.25Eu2O3·ZnO·0.99WO3:0.01Mn. 4+ Fluorescence spectrum of phosphor;

[0030] Figure 7 The composition is SrO·0.25Li2O·0.25Gd2O3·ZnO·0.975WO3:0.025Mn. 4+ Fluorescence spectrum of phosphor;

[0031] Figure 8 The composition is SrO·0.25Na2O·0.25Gd2O3·ZnO·0.94WO3:0.06Mn. 4+ Fluorescence spectrum of phosphor;

[0032] Figure 9 The composition is SrO·0.25K2O·0.25Gd2O3·ZnO·0.992WO3:0.008Mn. 4+ Fluorescence spectrum of phosphor;

[0033] Figure 10 The composition is SrO·0.25Na2O·0.25Y2O3·ZnO·0.996WO3:0.004Mn. 4+ Fluorescence spectrum of phosphor;

[0034] Figure 11 The composition is SrO·0.25K2O·0.25Y2O3·ZnO·0.966WO3:0.034Mn. 4+ Fluorescence spectrum of phosphor;

[0035] Figure 12 The composition is SrO·0.25K2O·0.25Sc2O3·ZnO·0.996WO3:0.004Mn. 4+ Fluorescence spectrum of phosphor;

[0036] Figure 13 The composition is BaO·0.25K2O·0.25La2O3·ZnO·0.99WO3:0.01Mn. 4+ Fluorescence spectrum of phosphor;

[0037] Figure 14 The composition is SrO·0.25K2O·0.25La2O3·MgO·0.993WO3:0.007Mn. 4+ Fluorescence spectrum of phosphor;

[0038] Figure 15 The composition is SrO·0.25K2O·0.25Bi2O3·ZnO·0.985WO3:0.015Mn. 4+ Fluorescence spectrum of phosphor;

[0039] Figure 16 The composition is CaO·0.25K2O·0.25La2O3·ZnO·0.99WO3:0.01Mn. 4+ Fluorescence spectrum of phosphor. Detailed Implementation

[0040] To facilitate understanding of the present invention, the present invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments.

[0041] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0042] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0043] Example 1

[0044] In this embodiment, the phosphor composition is SrO·0.25Li₂O·0.25La₂O₃·ZnO·0.991WO₃:0.009Mn. 4+ Luminescent properties such as Figure 1 As shown, its excitation spectrum consists of three continuous broadband bands covering 250-600 nm, with the main excitation peaks located at 340, 400 and 490 nm, respectively; its emission spectrum covers 650-800 nm, with the main emission peak located at 694 nm.

[0045] The preparation method is as follows:

[0046] Weigh 0.2953g SrCO3, 0.0369g Li2CO3, 0.1629g La2O3, 0.4390g Zn(CH3COO)2·2H2O, 0.5055g(NH4) 10 W 12 O 41 ·H2O and 0.0036g MnCl2·4H2O were added to the raw material mixture in a mortar and ground thoroughly for 30 minutes. After the material was mixed evenly, it was transferred to an alumina crucible and placed in a muffle furnace for high-temperature sintering at 1200℃ for 4 hours. After the reaction was completed, the product was taken out and ground evenly to obtain the phosphor.

[0047] Example 2

[0048] In this embodiment, the phosphor composition is 1.4SrO·0.15Na2O·0.15La2O3·ZnO·0.986WO3:0.014Mn 4 + Luminescent properties such as Figure 2 As shown, its excitation spectrum is a wide ultraviolet-visible spectrum, covering the range of 250-620 nm, with the main excitation peaks located at 350 nm, 390 nm and 515 nm; its emission spectrum covers the range of 640-800 nm, with the main emission peak located at 700 nm.

[0049] The preparation method is as follows:

[0050] Weigh 0.4134g SrCO3, 0.0318g Na2CO3, 0.0977g La2O3, 0.1628g ZnO, 0.5029g (NH4) 10 W 12 O 41 ·H2O and 0.0024g MnO2 are added to the raw material mixture in a mortar and ground thoroughly for 30 minutes. After the material is mixed evenly, it is transferred to an alumina crucible and placed in a muffle furnace for high-temperature sintering at 1100℃ for 3 hours. After the reaction is completed, the product is taken out and ground evenly to obtain the phosphor.

[0051] Example 3

[0052] In this embodiment, the phosphor composition is 1.3SrO·0.175K2O·0.175La2O3·ZnO·0.97WO3:0.03Mn. 4+ Luminescent properties such as Figure 3 As shown, its excitation spectrum is a wide ultraviolet-visible spectrum, covering the range of 280-630 nm, with the main excitation peaks at 393 and 500 nm; its emission spectrum covers the range of 640-800 nm, with the main emission peak at 694 nm.

[0053] The preparation method is as follows:

[0054] Weigh out 0.3838g SrCO3, 0.0645g K2C2O4·H2O, 0.3031g La(NO3)3·6H2O, 0.4390g Zn(CH3COO)2·2H2O, 0.4498g WO3 and 0.0069g MnCO3, place the raw material mixture in a mortar and grind it thoroughly for 30 minutes; after the materials are mixed evenly, transfer them to an alumina crucible and place them in a muffle furnace for high-temperature sintering, calcining at 1150℃ for 3 hours; after the reaction is completed, take out the product, grind it evenly to obtain the phosphor.

[0055] Example 4

[0056] In this embodiment, the phosphor composition is SrO·0.25Cs2O·0.25La2O3·ZnO·0.98WO3:0.02Mn. 4+ Luminescent properties such as Figure 4 As shown, its excitation spectrum is a wide ultraviolet-visible spectrum, covering the range of 250-620 nm, with the main excitation peaks at 363, 397, and 505 nm; its emission spectrum covers the range of 640-800 nm, with the main emission peak at 697 nm.

[0057] The preparation method is as follows:

[0058] Weigh 0.2953g SrCO3, 0.1629g Cs2CO3, 0.4330g La(NO3)3·6H2O, 0.4390gZn(CH3COO)2·2H2O, 0.4999g(NH4) 10 W 12 O 41 ·H2O and 0.0046g MnCO3 were added to the raw material mixture in a mortar and ground thoroughly for 30 minutes. After the material was mixed evenly, it was transferred to an alumina crucible and placed in a muffle furnace for high-temperature sintering at 1100℃ for 4 hours. After the reaction was completed, the product was taken out and ground evenly to obtain the phosphor.

[0059] Example 5

[0060] In this embodiment, the phosphor composition is SrO·0.25K2O·0.25Sm2O3·ZnO·0.92WO3:0.08Mn 4+ Luminescent properties such as Figure 5 As shown, its excitation spectrum consists of three sets of continuous excitation broadband covering 250-630 nm, with the main excitation peaks located at 355, 385 and 525 nm; its emission spectrum covers 650-800 nm, with the main emission peak located at 706 nm.

[0061] The preparation method is as follows:

[0062] Weigh 0.3513g SrC2O4, 0.0691g K2CO3, 0.1744g Sm2O3, 0.4390g Zn(CH3COO)2·2H2O, 0.4693g(NH4) 10 W 12 O 41 ·H2O and 0.0139g MnO2 were added to the raw material mixture in a mortar and ground thoroughly for 30 minutes. After the material was mixed evenly, it was transferred to an alumina crucible and placed in a muffle furnace for high-temperature sintering at 1200℃ for 6 hours. After the reaction was completed, the product was taken out and ground evenly to obtain the phosphor.

[0063] Example 6

[0064] In this embodiment, the phosphor composition is SrO·0.25K2O·0.25Eu2O3·ZnO·0.99WO3:0.01Mn. 4+ Luminescent properties such as Figure 6 As shown, its excitation spectrum consists of three sets of continuous excitation broadband covering 250-630 nm, with the main excitation peaks at 350, 390 and 535 nm; its emission spectrum covers 635-800 nm, with the main emission peak at 697 nm.

[0065] The preparation method is as follows:

[0066] Weigh 0.2953g SrCO3, 0.0921g K2C2O4·H2O, 0.1760g Eu2O3, 0.4390g Zn(CH3COO)2·2H2O, 0.5050g(NH4) 10 W 12 O 41 ·H2O and 0.0023g MnCO3 were added to the raw material mixture in a mortar and ground thoroughly for 30 minutes. After the material was mixed evenly, it was transferred to an alumina crucible and placed in a muffle furnace for high-temperature sintering at 1150℃ for 3 hours. After the reaction was completed, the product was taken out and ground evenly to obtain the phosphor.

[0067] Example 7

[0068] In this embodiment, the phosphor composition is SrO·0.25Li₂O·0.25Gd₂O₃·ZnO·0.975WO₃:0.025Mn. 4+ Luminescent properties such as Figure 7 As shown, its excitation spectrum consists of three continuous broadband bands covering 250-620 nm, with the main excitation peaks located at 333, 400 and 493 nm; its emission spectrum covers 640-800 nm, with the main emission peak located at 706 nm.

[0069] The preparation method is as follows:

[0070] Weigh out 0.2953g SrCO3, 0.0369g Li2CO3, 0.1813g Gd2O3, 0.4390g Zn(CH3COO)2·2H2O, 0.4521g WO3 and 0.0043g MnO2, place the raw material mixture in a mortar and grind it thoroughly for 30 minutes; after the materials are mixed evenly, transfer them to an alumina crucible and place them in a muffle furnace for high-temperature sintering, calcining at 1200℃ for 5 hours; after the reaction is completed, take out the product, grind it evenly to obtain the phosphor.

[0071] Example 8

[0072] In this embodiment, the phosphor composition is SrO·0.25Na2O·0.25Gd2O3·ZnO·0.94WO3:0.06Mn 4+ Luminescent properties such as Figure 8 As shown, its excitation spectrum consists of three continuous broadband bands covering 250-630 nm, with the main excitation peaks located at 345, 390 and 526 nm, respectively; its emission spectrum covers 650-800 nm, with the main emission peak located at 700 nm.

[0073] The preparation method is as follows:

[0074] Weigh out 0.2953g SrCO3, 0.0530g Na2CO3, 0.1813g Gd2O3, 0.4390g Zn(CH3COO)2·2H2O, 0.4359g WO3 and 0.0138g MnCO3, place the raw material mixture in a mortar and grind it thoroughly for 30 minutes; after the materials are mixed evenly, transfer them to an alumina crucible and place them in a muffle furnace for high-temperature sintering, calcining at 1000℃ for 6 hours; after the reaction is completed, take out the product, grind it evenly to obtain the phosphor.

[0075] Example 9

[0076] In this embodiment, the phosphor composition is SrO·0.25K2O·0.25Gd2O3·ZnO·0.992WO3:0.008Mn. 4+ Luminescent properties such as Figure 9 As shown, its excitation spectrum consists of three continuous broadband bands covering 250-630 nm, with the main excitation peaks located at 340, 390 and 528 nm, respectively; its emission spectrum covers 640-800 nm, with the main emission peak located at 700 nm.

[0077] The preparation method is as follows:

[0078] Weigh out 0.3513g SrC2O4, 0.0921g K2C2O4·H2O, 0.1813g Gd2O3, 0.1628g ZnO, 0.4600g WO3 and 0.0032g MnCl2·4H2O, place the raw material mixture in a mortar and grind it thoroughly for 30 minutes; after the materials are mixed evenly, transfer them to an alumina crucible and place them in a muffle furnace for high-temperature sintering, calcining at 1200℃ for 4 hours; after the reaction is completed, take out the product, grind it evenly to obtain the phosphor.

[0079] Example 10

[0080] In this embodiment, the phosphor composition is SrO·0.25Na2O·0.25Y2O3·ZnO·0.996WO3:0.004Mn. 4+ Luminescent properties such as Figure 10 As shown, its excitation spectrum consists of three sets of continuous broadband wavelengths covering 260-630 nm, with the main excitation peaks at 334, 396, and 528 nm; its emission spectrum covers 640-760 nm, with the main emission peak at 700 nm.

[0081] The preparation method is as follows:

[0082] Weigh 0.2953g SrCO3, 0.0530g Na2CO3, 0.1129g Y2O3, 0.1628g ZnO, 0.5080g (NH4) 10 W 12 O 41 ·H2O and 0.0009g MnCO3 were added to the raw material mixture in a mortar and ground thoroughly for 30 minutes. After the material was mixed evenly, it was transferred to an alumina crucible and placed in a muffle furnace for high-temperature sintering at 1100℃ for 3 hours. After the reaction was completed, the product was taken out and ground evenly to obtain the phosphor.

[0083] Example 11

[0084] In this embodiment, the phosphor composition is SrO·0.25K2O·0.25Y2O3·ZnO·0.966WO3:0.034Mn 4+ Luminescent properties such as Figure 11 As shown, its excitation spectrum consists of three sets of continuous broadband wavelengths covering 250-610 nm, with the main excitation peaks at 333, 393 and 528 nm; its emission spectrum covers 650-780 nm, with the main emission peak at 705 nm.

[0085] The preparation method is as follows:

[0086] Weigh 0.2953g SrCO3, 0.0691g K2CO3, 0.1129g Y2O3, 0.1628g ZnO, 0.4927g (NH4) 10 W 12 O 41 ·H2O and 0.0135g MnCl2·4H2O were added to the raw material mixture in a mortar and ground thoroughly for 30 minutes. After the material was mixed evenly, it was transferred to an alumina crucible and placed in a muffle furnace for high-temperature sintering at 1200℃ for 3 hours. After the reaction was completed, the product was taken out and ground evenly to obtain the phosphor.

[0087] Example 12

[0088] In this embodiment, the phosphor composition is SrO·0.25K2O·0.25Sc2O3·ZnO·0.996WO3:0.004Mn. 4+ Luminescent properties such as Figure 12 As shown, its excitation spectrum consists of three sets of continuous broadband wavelengths covering 250-625 nm, with the main excitation peaks at 345, 395, and 523 nm; its emission spectrum covers 640-800 nm, with the main emission peak at 707 nm.

[0089] The preparation method is as follows:

[0090] Weigh 0.3513g SrC2O4, 0.0691g K2CO3, 0.0690g Sc2O3, 0.4390g Zn(CH3COO)2·2H2O, 0.5080g(NH4) 10 W 12 O 41 ·H2O and 0.0009g MnCO3 were added to the raw material mixture in a mortar and ground thoroughly for 30 minutes. After the material was mixed evenly, it was transferred to an alumina crucible and placed in a muffle furnace for high-temperature sintering at 1150℃ for 4 hours. After the reaction was completed, the product was taken out and ground evenly to obtain the phosphor.

[0091] Example 13

[0092] In this embodiment, the phosphor composition is BaO·0.25K2O·0.25La2O3·ZnO·0.99WO3:0.01Mn 4+ Luminescent properties such as Figure 13 As shown, its excitation spectrum consists of three sets of continuous broadband wavelengths covering 250-630 nm, with the main excitation peaks at 355, 395 and 521 nm; its emission spectrum covers 650-800 nm, with the main emission peak at 706 nm.

[0093] The preparation method is as follows:

[0094] Weigh 0.3947g BaCO3, 0.0691g K2CO3, 0.4330g La(NO3)3·6H2O, 0.4390gZn(CH3COO)2·2H2O, 0.5050g(NH4) 10 W 12 O 41 ·H2O and 0.0023g MnCO3 were added to the raw material mixture in a mortar and ground thoroughly for 30 minutes. After the material was mixed evenly, it was transferred to an alumina crucible and placed in a muffle furnace for high-temperature sintering at 1200℃ for 10 hours. After the reaction was completed, the product was taken out and ground evenly to obtain the phosphor.

[0095] Example 14

[0096] In this embodiment, the phosphor composition is SrO·0.25K2O·0.25La2O3·MgO·0.993WO3:0.007Mn. 4+ Luminescent properties such as Figure 14 As shown, its excitation spectrum consists of two continuous broadband bands covering 250-600 nm, with the main excitation peaks at 342 and 495 nm; its emission spectrum covers 640-800 nm, with the main emission peak at 697 nm.

[0097] The preparation method is as follows:

[0098] Weigh 0.2953g SrCO3, 0.0691g K2CO3, 0.1629g La2O3, 0.1943g 4MgCO3·Mg(OH)2·5H2O, 0.5065g(NH4) 10 W 12 O 41 ·H2O and 0.0016g MnCO3 were added to the raw material mixture in a mortar and ground thoroughly for 30 minutes. After the material was mixed evenly, it was transferred to an alumina crucible and placed in a muffle furnace for high-temperature sintering at 1100℃ for 3 hours. After the reaction was completed, the product was taken out and ground evenly to obtain the phosphor.

[0099] Example 15

[0100] In this embodiment, the phosphor composition is SrO·0.25K2O·0.25Bi2O3·ZnO·0.985WO3:0.015Mn. 4+ Luminescent properties such as Figure 15 As shown, the phosphor has a dual broadband continuous excitation spectrum in the ultraviolet and visible regions, located in the range of 260-410 nm and 410-650 nm, with the ultraviolet excitation peak at 343 nm and the visible excitation peaks at 468 nm and 555 nm. Its emission spectrum range covers 690-800 nm, with the emission peak at 730 nm.

[0101] The preparation method is as follows:

[0102] Weigh 0.3513g SrC2O4, 0.0691g K2CO3, 0.2330g Bi2O3, 0.4390g Zn(CH3COO)2·2H2O, 0.5024g(NH4) 10 W 12 O 41 ·H2O and 0.0034g MnCO3 were added to the raw material mixture in a mortar and ground thoroughly for 30 minutes. After the material was mixed evenly, it was transferred to an alumina crucible and placed in a muffle furnace for high-temperature sintering at 1200℃ for 3 hours. After the reaction was completed, the product was taken out and ground evenly to obtain the phosphor.

[0103] Example 16

[0104] In this embodiment, the phosphor composition is CaO·0.25K2O·0.25La2O3·ZnO·0.99WO3:0.01Mn 4+ Luminescent properties such as Figure 16As shown, its excitation spectrum consists of three continuous broadband bands covering 270-610 nm, with the main excitation peaks located at 335, 396 and 494 nm, respectively; its emission spectrum covers 650-800 nm, with the main emission peak located at 712 nm.

[0105] The preparation method is as follows:

[0106] Weigh 0.2562g CaC2O4, 0.0691g K2CO3, 0.4330g La(NO3)3·6H2O, 0.4390gZn(CH3COO)2·2H2O, 0.5050g(NH4) 10 W 12 O 41 ·H2O and 0.0023g MnCO3 were added to the raw material mixture in a mortar and ground thoroughly for 30 minutes. After the material was mixed evenly, it was transferred to an alumina crucible and placed in a muffle furnace for high-temperature sintering at 1050℃ for 5 hours. After the reaction was completed, the product was taken out and ground evenly to obtain the phosphor.

[0107] The above description, in conjunction with specific preferred embodiments, provides a further detailed explanation of the present invention. However, it should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, various simple deductions or substitutions can be made without departing from the concept of the present invention, and all such modifications and substitutions should be considered within the scope of protection of the present invention.

Claims

1. A red phosphor, characterized by, The chemical composition of the red fluorescent powder is generally represented by a SrO· b K2O· c Bi2O3·ZnO·(1- x )WO3: x Mn 4+ , and 0 < a < 2, 0 < b ≤ 0.5, 0 < c ≤ 0.5, 0 < x ≤0.1, the sum of a, 2b, and 2c is 2.0, and all the values are molar fractions.

2. A red phosphor, characterized by, The chemical composition of the red fluorescent powder is generally represented by a SrO· b K2O· c La2O3·ZnO·(1- x )WO3: x Mn 4+ , or a SrO· b Cs2O· c La2O3·ZnO·(1- x )WO3: x Mn 4+ , and 0 a < 2, 0 b ≤ 0.5, 0 c ≤ 0.5, 0 x ≤ 0.1, the sum of a, 2b, and 2c is 2.0, and all the values are molar fractions.

3. The red phosphor of claim 1 or 2, wherein, The red phosphor emits red light under excitation of visible light with a wavelength range of 380-650 nm; or the red phosphor emits red light under excitation of ultraviolet light with a wavelength range of 250-380 nm.

4. The red phosphor of claim 1 or 2, wherein, The red light wavelength range of the red phosphor is 635-800 nm.

5. A method for preparing the red phosphor according to any one of claims 1 to 4, characterized by, The method comprises the following steps: S1, taking oxygen-containing compounds containing Sr, K or Cs, Bi or La, Zn, W and a manganese source according to the molar ratio of each element in the chemical formula, and mixing uniformly to obtain a mixture; S2, placing the mixture obtained in step S1 into an alumina crucible, and performing high-temperature sintering in a muffle furnace, the reaction temperature is 900-1200 ℃, and the reaction time is 3-10 h to obtain the red phosphor.

6. The production method according to claim 5, wherein The oxygen-containing compounds containing Sr, K or Cs, Bi or La, Zn, W are selected from one of oxides, carbonates, acetates, oxalates, nitrates, tungstates or hydroxides.

7. The preparation method according to claim 5, characterized in that, The manganese source is selected from one or more of manganese oxide, manganese carbonate or manganese chloride.

8. The red phosphor according to any one of claims 1-4 for use in near-ultraviolet and blue light chip LED optoelectronic devices, light conversion agricultural films or solar cell devices.

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