Ce < 3 + >-activated nitrogen oxide cyan fluorescent powder as well as preparation method and application thereof

Abstract

The invention provides Ce < 3 + > activated nitrogen oxide cyan fluorescent powder as well as a preparation method and application thereof. The cyan fluorescent powder material can be effectively excited by near ultraviolet light, is high in color purity, can emit bright cyan light under excitation of an n-UV LED chip, shows excellent thermal stability and long afterglow characteristics, and can keep 97% of initial emission intensity at 150 DEG C. Meanwhile, the luminescent temperature measurement material is simple in preparation process operation, low in raw material and equipment cost, environment-friendly, stable in product chemical property and suitable for being widely popularized and used.

Description

Technical Field

[0001] This invention belongs to the field of luminescent materials technology, specifically relating to a Ce... 3+ Activated nitrogen oxide cyan phosphor, its preparation method and application. Background Technology

[0002] With the development and advancement of technology, people are paying increasing attention to vision protection and indoor lighting, leading to a growing demand for full-spectrum light sources. Currently, white light-emitting diodes (WLEDs), as a new generation of solid-state lighting devices, are widely used in display, backlighting, and general lighting fields due to their advantages such as high efficiency, energy saving, and environmental friendliness.

[0003] Commercial WLEDs primarily use blue light chips to excite yellow phosphors (such as YAG:Ce). 3+ To achieve white light emission, this approach results in an excessively high proportion of high-energy blue light, which is harmful to the eyes. Furthermore, this method suffers from insufficient spectral intensity in the cyan band (470~500 nm) and lacks a red band, leading to a low color rendering index (CRI) (typically <80) and a high color temperature (CCT>6000 K), making it difficult to meet the needs of high-end lighting and wide color gamut displays. In addition, LED devices generate a large amount of heat during high-power operation, causing thermal quenching of the phosphor material, severely affecting luminous efficiency and device lifespan. At high temperatures, lattice expansion and interfacial reactions of the phosphor exacerbate luminous efficiency decay; existing materials generally retain less than 85% of their efficiency at 150℃.

[0004] Therefore, developing cyan phosphors with high quantum efficiency and excellent thermal stability has become one of the key research directions for improving LED performance, and is of great significance for realizing healthy lighting. Summary of the Invention

[0005] In view of this, the object of the present invention is to provide a Ce 3+ Activated cyan oxynitride phosphor, its preparation method, and its applications. This cyan phosphor can be effectively excited by near-ultraviolet light to achieve cyan emission and exhibits excellent thermal stability, maintaining high luminescence intensity even after repeated use.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a Ce 3+ The activated cyan phosphor of nitrogen oxides has the following general formula:

[0008] A 1-x AlSi5N7O2:xCe 3+ ;

[0009] Where A is any one or more of the elements Ba, Sr, or Ca, such as a single Ba, Sr, or Ca; or a combination of Ba and Sr, Sr and Ca, Ba and Ca; or a combination of Ba, Sr, and Ca.

[0010] x is Ce 3+ The number of moles of dopant is preferably x = 0~0.3, and is not 0. Specifically, it can be 0.01, 0.03, 0.06, 0.09, 0.12, 0.15, 0.18, 0.21, 0.24, 0.27 or 0.3, etc.

[0011] In some embodiments of the present invention, the Ce 3+ The activated nitrogen oxide cyan phosphor can be selected from any of the following formulas:

[0012] Ba 0.99 AlSi5N7O2:0.01Ce 3+ Ba 0.97 AlSi5N7O2:0.03Ce 3+ Ba 0.94 AlSi5N7O2:0.06Ce 3+ Ba 0.91 AlSi5N7O2:0.09Ce 3+ Ba 0.88 AlSi5N7O2:0.12Ce 3+ Ba 0.85 AlSi5N7O2:0.15Ce 3+ Ba 0.82 AlSi5N7O2:0.18Ce 3+ Ba 0.79 AlSi5N7O2:0.21Ce 3+ Ba 0.76 AlSi5N7O2:0.24Ce 3+ Ba 0.73 AlSi5N7O2:0.27Ce 3+ Ba 0.7 AlSi5N7O2:0.3Ce 3+ ;Ca 0.99 AlSi5N7O2:0.01Ce 3+ ;Sr 0.99 AlSi5N7O2:0.01Ce 3+ .

[0013] The cyan phosphor provided by this invention, in the form of A 1-x Using AlSi5N7O2 as a matrix can increase the thermal and chemical stability of phosphors; using Ce...3+ As a luminescent center, compared to other luminescent ions (such as Eu), 2+ Pr 3+ In terms of near-ultraviolet light, it has the advantage of being excited by near-ultraviolet light and emitting wavelengths in the cyan range. The cyan phosphor material provided by the present invention can be effectively excited by near-ultraviolet light, has high color purity, and can emit bright cyan light under n-UV LED chip excitation. The phosphor exhibits excellent thermal stability and long afterglow characteristics, and can maintain 97% of the initial emission intensity at 150°C.

[0014] The present invention also provides the above-mentioned Ce 3+ A method for preparing activated cyan nitride phosphor includes the following steps:

[0015] S1: Mix the cerium source, the metal source containing element A, the aluminum source, the silicon source, and the nitrogen source to obtain a raw material mixture;

[0016] S2: Sinter the raw material mixture obtained in step S1 to obtain Ce 3+ Activated nitrogen oxide cyan phosphor.

[0017] According to the present invention, a cerium source, an A-containing metal source, an aluminum source, a silicon source, and a nitrogen source are first mixed in a certain proportion to obtain a raw material mixture.

[0018] In this invention, the cerium source includes any one or a combination of at least two of cerium-containing oxides, carbonates, nitrides, oxalates, acetates or nitrates, preferably Ce2O3.

[0019] The metal source containing element A includes any one or a combination of at least two of the following: oxides, carbonates, nitrides, oxalates, acetates, or nitrates containing element A, preferably BaO.

[0020] The aluminum source includes any one or a combination of at least two of aluminum-containing oxides, carbonates, nitrides, oxalates, acetates, or nitrates, preferably AlN.

[0021] The silicon source includes any one or a combination of at least two of silicon-containing oxides, carbonates, nitrides, oxalates, acetates, or nitrates, preferably Si3N4.

[0022] The nitrogen source includes any one or a combination of at least two of nitrogen-containing oxides, carbonates, nitrides, oxalates, acetates or nitrates, preferably Si3N4 and / or AlN.

[0023] This invention does not impose any special restrictions on the source of the above-mentioned raw materials; any commercially available product with a purity of 99% or higher is acceptable.

[0024] In some embodiments of the present invention, the preferred molar ratio among Ba (or Sr, or Ca), Al, Si, Al, and Ce is: 0.99:1.1:0.7:0.01:0.01; 0.97:1.1:0.7:0.01:0.03; 0.94:1.1:0.7:0.01:0.06; 0.91:1.1:0.7:0.01:0.09; 0.88:1.1:0.7:0.01:0.12; 0.85:1.1:0.7:0.01:0.15; 0.82:1.1:0.7:0.01:0.18; 0.79:1.1:0.7:0.01:0.21; 0.76:1.1:0.7:0.01:0.24; 0.73:1.1:0.7:0.01:0.27;

[0035] 0.7:1.1:0.7:0.01:0.3.

[0036] In some embodiments of the present invention, it is preferable to perform a grinding process after the above mixing is completed. The grinding time is 5 to 120 minutes, for example: 5 minutes, 10 minutes, 20 minutes, 30 minutes, 50 minutes, 80 minutes, 100 minutes, or 120 minutes. The grinding device is an agate mortar.

[0037] After obtaining the raw material mixture, according to the present invention, the raw material mixture obtained in step S1 is sintered to obtain Ce. 3+ Activated nitrogen oxide cyan phosphor.

[0038] The sintering temperature is 1000~1600℃, for example: 1000℃, 1100℃, 1200℃, 1300℃, 1400℃, 1500℃ or 1600℃, etc.; the time is 2~10 h, for example: 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h, etc.

[0039] In this invention, the sintering is preferably carried out under a reducing atmosphere in order to control the oxygen partial pressure, stabilize the nitrogen content in the matrix, and maintain the designed stoichiometric ratio.

[0040] The reducing atmosphere is selected from any one or a combination of at least two of the following: a carbon monoxide reducing atmosphere, a gaseous atmosphere produced by the combustion of carbon particles or activated carbon in air, a mixed atmosphere of hydrogen and nitrogen, or a mixed atmosphere of hydrogen and argon.

[0041] In some embodiments of the present invention, the reducing atmosphere is selected from a mixture of hydrogen and nitrogen. The volume ratio of hydrogen to nitrogen is (3~10):(90~98), preferably (5~8):(93~95). In some specific embodiments of the present invention, the reducing atmosphere is 5 vol% H2 / 95 vol% N2.

[0042] In some preferred embodiments of the present invention, after sintering in step S2, the obtained product is preferably cooled to room temperature and then subjected to secondary grinding. The secondary grinding time is 5 to 120 minutes, for example: 5 minutes, 10 minutes, 20 minutes, 30 minutes, 50 minutes, 80 minutes, 100 minutes, or 120 minutes. The apparatus for secondary grinding is an agate mortar.

[0043] The preparation method provided by this invention is simple, has low raw material and equipment costs, and is environmentally friendly, making it suitable for widespread use.

[0044] Thirdly, the present invention also provides a white LED device, which comprises Ce involved in the above-mentioned technical solution. 3+ Activated nitrogen oxide cyan phosphor, red commercial powder CaAlSiN3:Eu²⁺, and green commercial powder Lu3Al5O 12 :Ce 3+ It is obtained by combining and packaging.

[0045] In summary, this invention has developed a cyan phosphor with high quantum efficiency and excellent thermal stability. It is a high thermal stability cyan phosphor that can be effectively excited by near-ultraviolet light, which is of great significance for realizing healthy lighting.

[0046] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0047] The Ce provided by this invention 3+ Activated cyan phosphor material with Ce 3+ Using ions as luminescent centers, the cyan phosphor material in this system can be effectively excited by near-ultraviolet light, exhibiting high color purity. When excited by an n-UV LED chip, it emits bright cyan light. This phosphor demonstrates excellent thermal stability and long afterglow characteristics, maintaining 97% of its initial emission intensity at 150℃. Furthermore, the preparation process of this luminescent thermometric material is simple, with low raw material and equipment costs, environmentally friendly characteristics, and stable chemical properties, making it suitable for widespread application. Attached Figure Description

[0048] Figure 1 Ce prepared for this invention 3+ X-ray diffraction (XRD) spectrum of activated cyan nitride phosphor material;

[0049] Figure 2 Ce prepared in Example 7 of this invention 3+ Excitation and emission spectra of activated cyan oxynitride phosphor materials at room temperature;

[0050] Figure 3 Ce prepared in Example 7 of this invention 3+ Emission spectra of activated cyan oxynitride phosphor materials at different temperatures;

[0051] Figure 4 The cyan phosphor, red commercial powder CaAlSiN3:Eu²⁺, and green commercial powder Lu3Al5O prepared for this invention 12 :Ce 3+ The emission spectrum of the white LED device assembled and packaged together;

[0052] Figure 5 The excitation and emission spectra of the phosphor obtained in Comparative Example 1 at room temperature are shown.

[0053] Figure 6 The excitation and emission spectra of the phosphor obtained in Comparative Example 2 at room temperature are shown. Detailed Implementation

[0054] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0055] To further illustrate the present invention, the following embodiments provide a detailed description. The experimental materials used in the following embodiments of the present invention are all commercially available products.

[0056] Example 1

[0057] The starting materials were BaO (99.5%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and CeO2 (99.99%), with a molar ratio of 0.99:1.1:0.7:0.01:0.01. The materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours at 1400℃ in a horizontal tube furnace under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground for 10 minutes to obtain CeO2. 3+ Activated nitrogen oxide cyan phosphor. The resulting phosphor is a white powder with the molecular formula Ba. 0.99 AlSi5N7O2:0.01Ce 3+ .

[0058] Example 2

[0059] The starting materials were BaO (99.5%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and CeO2 (99.99%), with a molar ratio of 0.97:1.1:0.7:0.01:0.03. The materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground for 10 minutes to obtain CeO2. 3+ Activated nitrogen oxide cyan phosphor. The resulting phosphor is a white powder with the molecular formula Ba. 0.97 AlSi5N7O2:0.03Ce 3+ .

[0060] Example 3

[0061] The starting materials were BaO (99.5%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and CeO2 (99.99%), with a molar ratio of 0.94:1.1:0.7:0.01:0.06. The materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground for 10 minutes to obtain CeO2. 3+ Activated nitrogen oxide cyan phosphor. The resulting phosphor is a white powder with the molecular formula Ba. 0.94 AlSi5N7O2:0.06Ce 3+ .

[0062] Example 4

[0063] The starting materials were BaO (99.5%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and CeO2 (99.99%), with a molar ratio of 0.91:1.1:0.7:0.01:0.09. The materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground for 10 minutes to obtain CeO2. 3+ Activated nitrogen oxide cyan phosphor. The resulting phosphor is a white powder with the molecular formula Ba. 0.91 AlSi5N7O2:0.09Ce 3+ .

[0064] Example 5

[0065] The starting materials were BaO (99.5%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and CeO2 (99.99%), with a molar ratio of 0.88:1.1:0.7:0.01:0.12. The materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground for 10 minutes to obtain CeO2. 3+ Activated nitrogen oxide cyan phosphor. The resulting phosphor is a white powder with the molecular formula Ba. 0.88 AlSi5N7O2:0.12Ce 3+ .

[0066] Example 6

[0067] The starting materials were BaO (99.5%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and CeO2 (99.99%), with a molar ratio of 0.85:1.1:0.7:0.01:0.15. The materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground for 10 minutes to obtain CeO2. 3+ Activated nitrogen oxide cyan phosphor. The resulting phosphor is a white powder with the molecular formula Ba. 0.85 AlSi5N7O2:0.15Ce 3+ .

[0068] Example 7

[0069] The starting materials were BaO (99.5%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and CeO2 (99.99%), with a molar ratio of 0.82:1.1:0.7:0.01:0.18. The materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground for 10 minutes to obtain CeO2. 3+ Activated nitrogen oxide cyan phosphor. The resulting phosphor is a white powder with the molecular formula Ba. 0.82 AlSi5N7O2:0.18Ce 3+ .

[0070] Example 8

[0071] The starting materials were BaO (99.5%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and CeO2 (99.99%), with a molar ratio of 0.79:1.1:0.7:0.01:0.21. The materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground for 10 minutes to obtain CeO2. 3+ Activated nitrogen oxide cyan phosphor. The resulting phosphor is a white powder with the molecular formula Ba. 0.79 AlSi5N7O2:0.21Ce 3+ .

[0072] Example 9

[0073] The starting materials were BaO (99.5%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and CeO2 (99.99%), with a molar ratio of 0.76:1.1:0.7:0.01:0.24. The materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground for 10 minutes to obtain CeO2. 3+ Activated nitrogen oxide cyan phosphor. The resulting phosphor is a white powder with the molecular formula Ba. 0.76 AlSi5N7O2:0.24Ce3+ .

[0074] Example 10

[0075] The starting materials were BaO (99.5%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and CeO2 (99.99%), with a molar ratio of 0.73:1.1:0.7:0.01:0.27. The materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground for 10 minutes to obtain CeO2. 3+ Activated nitrogen oxide cyan phosphor. The resulting phosphor is a white powder with the molecular formula Ba. 0.73 AlSi5N7O2:0.27Ce 3+ .

[0076] Example 11

[0077] The starting materials were BaO (99.5%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and CeO2 (99.99%), with a molar ratio of 0.7:1.1:0.7:0.01:0.3. The materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground for 10 minutes to obtain CeO2. 3+ Activated nitrogen oxide cyan phosphor. The resulting phosphor is a white powder with the molecular formula Ba. 0.7 AlSi5N7O2:0.3Ce 3+ .

[0078] Example 12

[0079] The only difference between this embodiment and Example 1 is that the barium source compound (BaO) is replaced with BaCO3; all other conditions and parameters are exactly the same as in Example 1. XRD characterization showed that no pure phase was synthesized in this embodiment.

[0080] Example 13

[0081] The only difference between this embodiment and Example 1 is that the aluminum source compound (AlN) is replaced with Al2O3; all other conditions and parameters are exactly the same as in Example 1. XRD characterization showed that no pure phase was synthesized in this embodiment.

[0082] Example 14

[0083] The only difference between this embodiment and Example 1 is that the silicon source compound (Si3N4) is SiO2; all other conditions and parameters are exactly the same as in Example 1. XRD characterization showed that a pure phase was not synthesized in this embodiment.

[0084] Example 15

[0085] The only difference between this embodiment and Example 1 is that the sintering temperature is 1300℃; all other conditions and parameters are exactly the same as in Example 1. XRD characterization showed that a pure phase was not synthesized in this embodiment.

[0086] Example 16

[0087] The only difference between this embodiment and Example 1 is that the sintering time is 8 hours; all other conditions and parameters are exactly the same as in Example 1. XRD characterization showed that this embodiment synthesized a pure phase, but the maximum luminescence intensity of the sample decreased.

[0088] Example 17

[0089] The only difference between this embodiment and Example 1 is that the grinding time is 20 minutes per cycle; all other conditions and parameters are exactly the same as in Example 1. XRD characterization showed that this embodiment synthesized a pure phase, with no significant difference from the results of Example 1, indicating that further increasing the grinding time has no impact on the experimental results.

[0090] Example 18

[0091] The only difference between this embodiment and Example 1 is that the purity of AlF3 in the starting material is 99%, while all other conditions and parameters are exactly the same as in Example 1. XRD characterization revealed that the sample in this embodiment contained a small amount of impurities.

[0092] Example 19

[0093] The only difference between this embodiment and Example 1 is that AlF3 in the raw materials is replaced with NH4F; all other conditions and parameters are exactly the same as in Example 1. XRD characterization showed that this embodiment did not synthesize a pure phase.

[0094] Example 20

[0095] The only difference between this embodiment and Example 1 is that the sintering temperature is 1500℃; all other conditions and parameters are exactly the same as in Example 1. The mixed raw materials were placed in an alumina crucible and sintered for 6 h in a horizontal tube furnace at 1500℃ under a 5% H2 / 95% N2 atmosphere. After cooling, the sample was ground to obtain the final product. XRD characterization showed that a pure phase was not synthesized in this embodiment.

[0096] Example 21

[0097] The only difference between this embodiment and Example 1 is that the sintering time is 4 hours; all other conditions and parameters are exactly the same as in Example 1. XRD characterization showed that a pure phase was not synthesized in this embodiment.

[0098] Example 22

[0099] The starting materials were SrO (99.9%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and CeO2 (99.99%), with a molar ratio of 0.99:1.1:0.7:0.01:0.01. The raw materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground. The resulting phosphor was a white powder with the molecular formula SrO. 0.99 AlSi5N7O2:0.01Ce 3+ XRD characterization showed that no pure phase was synthesized in this example.

[0100] Example 23

[0101] The starting materials were CaCO3 (99.9%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and CeO2 (99.99%), with a molar ratio of 0.99:1.1:0.7:0.01:0.01. The raw materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground. The resulting phosphor was a white powder with the molecular formula Ca. 0.99 AlSi5N7O2:0.01Ce 3+ XRD characterization showed that no pure phase was synthesized in this example.

[0102] Comparative Example 1

[0103] The starting materials were BaO (99.5%), AlN(AR), Si3N4 (99.99%), AlF3 (99.9%), and Eu2O3 (99.99%), with a molar ratio of 0.99:1.1:0.7:0.01:0.01. The materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for approximately 10 minutes. The mixture was then placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground for 10 minutes to obtain Eu2O3. 2+ Activated nitrogen oxide green phosphor. The resulting phosphor is a white powder with the molecular formula Ba.0.99 AlSi5N7O2:0.01Eu 2+ .

[0104] The spectrum of Comparative Example 1 cannot be effectively excited by the near-ultraviolet LED chip.

[0105] Comparative Example 2.

[0106] The starting materials were BaO (99.5%), AlN (AR), Si3N4 (99.99%), AlF3 (99.9%), and Pr6O. 11 (99.99%), the molar ratio between raw materials is 0.99:1.1:0.7:0.01:0.01. The raw materials were weighed according to this ratio, mixed evenly in an agate mortar, and ground for about 10 minutes. Then, the mixture was placed in an alumina crucible and sintered for 6 hours in a horizontal tube furnace at 1400℃ under a 5% H2 / 95% N2 atmosphere. After natural cooling, the sample was removed and carefully ground for 10 minutes to obtain Pr. 3+ Activated oxynitride red phosphor. The resulting phosphor is a white powder with the molecular formula Ba. 0.99 AlSi5N7O2:0.01Pr 3+ .

[0107] Performance testing

[0108] X-ray diffraction was performed on the cyan phosphors prepared in Examples 1-11, and the results are as follows: Figure 1 As shown in the figure, the results indicate that the diffraction peaks of all samples are consistent with the standard diffraction peaks of AlBaSi5O2N7 (ICSD-97-024-0276), indicating that a pure phase was synthesized in the samples.

[0109] The cyan phosphor prepared in Example 7 was subjected to spectral testing. The excitation and emission spectra of this cyan phosphor material at room temperature are as follows: Figure 2 As shown, a broadband absorption peak centered at 271, 303, and 363 nm is observed in the 250 nm to 450 nm range. The excitation peak can be convolved to form a peak at 36900 cm⁻¹. -1 33003 cm -1 27548 cm -1 The three Gaussian peaks at Ce 3+ The 5d orbital undergoes energy level splitting in the crystal field, resulting in multiple characteristic peaks in its excitation spectrum, corresponding to Ce. 3 + The 4f-5d transition occurs. Under 366 nm excitation, there is a emission band centered at 479 nm in the 395 nm~700 nm range, belonging to Ce. 3+ The 5d-4f transition.

[0110] The cyan phosphor prepared in Example 7 was subjected to spectral testing at different temperatures. The emission spectra of the cyan phosphor material at different temperatures are as follows: Figure 3 As shown, it can be seen that Ba 0.82 AlSi5N7O2:0.18Ce 3+ The PL strength at 423 K remains at 94% of that at 273 K, indicating that the material has good thermal stability.

[0111] The cyan phosphor prepared in Example 7 was mixed with red commercial powder CaAlSiN3:Eu²⁺ and green commercial powder Lu3Al5O. 12 :Ce 3+ Combined packaging, including cyan phosphor, red commercial powder CaAlSiN3:Eu²⁺, and green commercial powder Lu3Al5O 12 :Ce 3+ A white LED device was obtained with a mass ratio of 5:3:2. Spectral testing was performed on this white LED device using the following method:

[0112] The electroluminescence (EL) spectral characteristics of the fabricated WLED devices were evaluated using a HAAS 2000 photoelectric measurement system (350~1100 nm, Everfine, China).

[0113] The results are as follows Figure 4 As shown, the spectrum of the pc-LED measured under current driving conditions of 10 mA to 120 mA can be seen. By exciting the cyan phosphor, a bright cyan light can be generated, which effectively makes up for the missing part of the spectrum of ordinary LEDs. The LED exhibits good warm white light [high Ra=94.2, low CCT=4044K, chromaticity coordinates (0385, 0.400)]. Under the low current driving condition of 10 mA, the WLED device has high luminous efficiency and stable chromaticity coordinates. As the current increases to 120 mA, the luminous intensity increases significantly, but the chromaticity coordinates only shift slightly, indicating that the WLED device has good current stability.

[0114] The phosphors prepared in Comparative Examples 1 and 2 were subjected to spectral testing. The excitation and emission spectra of the phosphor materials in Comparative Examples 1 and 2 at room temperature are as follows: Figure 5 and Figure 6 As shown. Among them, by Figure 5 The spectrum of Comparative Example 1 shows that the phosphor material in Comparative Example 1 cannot be effectively excited by the near-ultraviolet LED chip; Figure 6 The spectrum of Comparative Example 2 shows that the phosphor material of Comparative Example 2 cannot be excited by near-ultraviolet light, and the emission wavelength does not meet the cyan band.

[0115] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A Ce 3+ The activated cyan phosphor of nitrogen oxides has the following general formula: A 1-x AlSi5N7O2:xCe 3+ ; in, A is any one or more of the elements Ba, Sr, or Ca; x = 0~0.3, not 0.

2. The Ce as described in claim 1 3+ Activated nitrogen oxide cyan phosphor, characterized in that, x=0.01~0.3。 3. Ce according to claim 1 or 2 3+ Activated nitrogen oxide cyan phosphor, characterized in that, The Ce 3+ The activated nitrogen oxide cyan phosphor is selected from any one of the following formulas: Ba 0.99 AlSi5N7O2:0.01Ce 3+ Ba 0.97 AlSi5N7O2:0.03Ce 3+ Ba 0.94 AlSi5N7O2:0.06Ce 3+ Ba 0.91 AlSi5N7O2:0.09Ce 3+ Ba 0.88 AlSi5N7O2:0.12Ce 3+ Ba 0.85 AlSi5N7O2:0.15Ce 3+ Ba 0.82 AlSi5N7O2:0.18Ce 3+ Ba 0.79 AlSi5N7O2:0.21Ce 3+ Ba 0.76 AlSi5N7O2:0.24Ce 3+ Ba 0.73 AlSi5N7O2:0.27Ce 3+ Ba 0.7 AlSi5N7O2:0.3Ce 3+ Ca 0.99 AlSi5N7O2:0.01Ce 3+ ;Sr 0.99 AlSi5N7O2:0.01Ce 3+ 。 4. A Ce as described in any one of claims 1 to 3 3+ A method for preparing activated cyan phosphor of nitrogen oxides, characterized in that, Includes the following steps: S1: Mix the cerium source, the metal source containing element A, the aluminum source, the silicon source, and the nitrogen source to obtain a raw material mixture; S2: Sinter the raw material mixture obtained in step S1 to obtain Ce 3+ Activated nitrogen oxide cyan phosphor.

5. The preparation method according to claim 4, characterized in that, The cerium source includes any one or a combination of at least two of cerium-containing oxides, carbonates, nitrides, oxalates, acetates, or nitrates; The metal source containing element A includes any one or a combination of at least two of the following: oxides, carbonates, nitrides, oxalates, acetates, or nitrates containing element A. The aluminum source includes any one or a combination of at least two of aluminum-containing oxides, carbonates, nitrides, oxalates, acetates, or nitrates. The silicon source includes any one or a combination of at least two of silicon-containing oxides, carbonates, nitrides, oxalates, acetates, or nitrates. The nitrogen source includes any one or a combination of at least two of nitrogen-containing oxides, carbonates, nitrides, oxalates, acetates, or nitrates.

6. The preparation method according to claim 4 or 5, characterized in that, The sintering temperature is 1000~1600℃, and the time is 2~10 h.

7. The preparation method according to any one of claims 4 to 6, characterized in that, The sintering is carried out in a reducing atmosphere; The reducing atmosphere is selected from any one or a combination of at least two of the following: a carbon monoxide reducing atmosphere, a gaseous atmosphere produced by the combustion of carbon particles or activated carbon in air, a mixed atmosphere of hydrogen and nitrogen, or a mixed atmosphere of hydrogen and argon.

8. The preparation method according to any one of claims 4 to 7, characterized in that, After mixing is completed in step S1, grinding is performed once; After sintering in step S2, cooling and secondary grinding are performed.

9. The preparation method according to any one of claims 4 to 8, characterized in that, The time for the first and second grinding is 5 to 120 minutes each.

10. A white LED device, characterized in that, By Ce 3+ Activated nitrogen oxide cyan phosphor, red commercial powder CaAlSiN3:Eu²⁺, and green commercial powder Lu3Al5O 12 :Ce 3+ Combined packaging is used to obtain; The Ce 3+ The activated cyan phosphor of oxynitride is Ce as described in any one of claims 1 to 3. 3+ Activated cyan nitride phosphor or Ce prepared by the method according to any one of claims 4 to 9 3+ Activated nitrogen oxide cyan phosphor.

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