CN107674676B

CN107674676B - Sc-based carbonitride fluorescent powder and device containing same

Info

Publication number: CN107674676B
Application number: CN201710632649.9A
Authority: CN
Inventors: 庄卫东; 刘荣辉; 燕春培; 刘元红; 徐会兵; 杜甫; 陈磊; 马小乐
Original assignee: Grirem Advanced Materials Co Ltd
Current assignee: Grirem Advanced Materials Co Ltd
Priority date: 2016-08-01
Filing date: 2017-07-28
Publication date: 2021-05-04
Anticipated expiration: 2037-07-28
Also published as: CN107674676A

Abstract

The invention relates to Sc-based carbonitride fluorescent powder. The phosphor comprises an inorganic compound consisting of M¹、Sc、M²N, C and a luminescence center Ce, the chemical formula of which is M¹ _aSc_bM² _cN_dC_e: xCe, wherein M¹One or more selected from rare earth metal elements Y, La, Gd and Lu, M²One or more elements selected from Si, Al, Ga and B; a is more than 0 and less than 2, b is more than 0 and less than 2, c is more than 3 and less than or equal to 5, and d is more than or equal to 5<7, e is more than or equal to 0 and less than or equal to 2, and x is more than 0 and less than or equal to 0.2. The invention also relates to a device containing the fluorescent powder and a preparation method of the fluorescent powder. The fluorescent powder has the advantages of high efficiency, uniformity, no impurity phase and the like, and the preparation method is simple and easy to industrialize, and is particularly suitable for ultraviolet-violet excited white light LEDs.

Description

Sc-based carbonitride fluorescent powder and device containing same

Technical Field

The invention relates to Sc-based carbonitride fluorescent powder and a device containing the same, belonging to the technical field of luminescent materials.

Background

Compared with the traditional light emitting device, the Light Emitting Diode (LED) is used as a novel efficient light source, has the advantages of low voltage, high lighting effect, low energy consumption, long service life, no pollution and the like, has the characteristics of small volume, quick response, less heat generation, high reliability and the like, and becomes a strategic emerging industry of the key development of China in the 21 st century. In particular, the development of white light sources (suitable for general lighting) is important for greatly reducing the amount of power used for lighting.

At present, the main approach for realizing white light LED is to use blue light (440-470 nm) LED chip to excite fluorescent powder to compound white light. There are two common combinations: firstly, combining a blue LED chip and yellow fluorescent powder; the second is the combination of a blue LED chip and red and green fluorescent powder. The garnet-structured yellow fluorescent powder (YAG) matched blue LED chip is widely applied due to the advantages of high efficiency, simple manufacture and the like, but due to poor spectrum continuity and lack of red light, the color rendering index of a white LED device is low, the color temperature is high, and the requirement of high-quality illumination is difficult to meet. Therefore, the high-color-rendering-index white light is obtained by adding red powder or adopting a blue light chip to excite red and green fluorescent powder.

In recent years, with the increasing living standard and the continuous progress of semiconductor lighting technology, people have an increasing awareness of health and quality life, and the demand for lighting has gradually shifted from simple environmental protection and energy conservation to the pursuit of health and comfort. The traditional white LED formed by combining a blue LED chip and other color phosphors has the defects of unbalanced light-emitting wavelength, partial loss of cyan light and the like, and particularly has the problems of high peak intensity of blue light, easy arousing the physiological and psychological aspects of people and the like, so that the health requirement of people is difficult to meet. Therefore, researchers have proposed white LEDs using red (R), green (G), and blue (B) phosphors in combination on a violet LED chip, and compared with a blue LED chip, this method has higher efficiency of converting violet light into white light, balanced spectral distribution, and relatively better color rendering index, but this method has raised higher requirements on the chemical and thermal stability of the phosphor, and the like, and there is a need to develop new blue, green, and red phosphors suitable for high-density energy excitation, full-spectrum high-quality illumination, and violet or near-ultraviolet excitation.

Carbonitride has received much attention from researchers of luminescent materials because of its advantages such as stable physicochemical properties and mild synthesis conditions.

RE₂Si₄N₆C (RE = Y, Lu, Gd, La, etc.) is represented by MRESi₄N₇(M = Ca, Sr, Ba; RE = Yb, Y) (1147 for short) and is derived from trivalent RE³⁺Substituted divalent M²⁺To compensate for charge balance, [ N (N) in 1147₃)₄]Quilt [ C (N)₃)₄]Substitution to obtain RE₂Si₄N₆C. RE doped with different rare earth ions₂Si₄N₆C (RE = Y, Lu, Gd) has a good luminescence property (patent documents 1 to 3). At RE₂Si₄N₆In C, RE has two kinds of coordination, five coordination and six coordination, respectively (non-patent document 1). In general, ions with larger radii preferentially replace the hexacoordinated ions, while ions with smaller radii preferentially replace the pentacoordinated ions, and we assume that this class of materials has the general formula A_1-xB_1+xXN₆C, A represents a hexacoordinated ion, preferentially occupied by a large radius ion; b represents a penta-coordinated ion, preferentially substituted by a small radius ion; x is a four coordinate system, mainly occupied by Si, Al, B, Ge, Ga, etc., forming tetrahedrons with the surrounding N or O.

According to the above empirical rule, experimental research has been carried out to find that the small radius ions Sc can enter into the five-coordinate lattice and other large radius ions (Y, Ln) enter into the six-coordinate lattice, but in the experimental process, it has been found that when the small radius ions Sc and the large radius ions (Y, Ln) exist simultaneously, coordination variation is caused, so that the large radius ions are twelve-coordinate and the small radius ions Sc are six-coordinate. However, a novel Sc-containing carbon nitride matrix is formed, and at present, reports that solid-solution rare earth ions such as Ce are taken as luminescent materials are not found. In addition, on the basis of the series of fluorescent powder, twelve coordination ions are replaced by divalent metal ions (Ca, Sr, Ba, Zn and the like), and the proportion of N, C is adjusted, so that the aim of coordinating the light color performance is fulfilled.

Based on the research, the invention aims to provide the blue-green fluorescent powder which has good chemical and thermal stability and is suitable for near ultraviolet-purple excitation.

Non-patent document 1: duan C, Zhang Z, R sler S, et al Preparation, Characterisation, and Photopharmaceuticals Properties of Tb³⁺, Ce³⁺, and Ce³⁺/Tb³⁺-Activated RE₂Si₄N₆C (RE = Lu, Y, and Gd) Phosphors[J]. Chemistry of Materials, 2011, 23(7):1851-1861.

Patent document 1: CN 1922285A

Patent document 2: US 8007683B 2

Patent document 3: CN 102585822A

Disclosure of Invention

The invention aims to provide a fluorescent powder which can be effectively excited by near ultraviolet-violet light to emit blue-green light.

Another object of the present invention is to provide a simple and easy-to-operate method for preparing the phosphor.

In order to achieve the above purpose, the present invention adopts the following scheme:

the invention provides a Sc-based carbonitride fluorescent powder, which comprises an inorganic compound consisting of M¹、Sc、M²N, C and a luminescence center Ce, the chemical formula of which is M¹ _aSc_bM² _cN_dC_e: xCe, wherein M¹One or more selected from rare earth metal elements Y, La, Gd and Lu, M²One or more elements selected from Si, Al, Ga and B; a is more than 0 and less than 2, b is more than 0 and less than 2, c is more than 3 and less than or equal to 5, and d is more than or equal to 5<7，0≤e≤2，0＜x≤0.2。

Further preferably, M¹Selected from Y, or at least one M¹Is selected from Y; m²Selected from Si, or at least one M²Selected from Si.

More preferably, a is more than 0 and less than or equal to 1.749, b is more than or equal to 0.25 and less than or equal to 1.9, c is more than or equal to 3.5 and less than or equal to 4.5, d is more than or equal to 5.5 and less than or equal to 6.5, and e is more than or equal to 0.5 and less than or equal to 1.5.

More preferably, a is more than 0 and less than or equal to 1.5, b is more than or equal to 0.25 and less than or equal to 1.9, c is more than or equal to 3.5 and less than or equal to 4.5, d is more than or equal to 5.5 and less than or equal to 6.5, and e is more than or equal to 0.5 and less than or equal to 1.0.

Still more preferably, (a + x) b: c: d: e =1:1:4:6: 1.

Still more preferably, b = 1.

The excitation peak wavelength of the Sc-based carbonitride fluorescent powder is between 360 and 440nm, and the emission peak wavelength is between 450 and 500nm, so that the Sc-based carbonitride fluorescent powder is suitable for ultraviolet or near-ultraviolet LED chips.

In another aspect, the present invention further provides a method for preparing the Sc-based carbonitride phosphor powder, comprising the following steps:

(1) mixing materials: will M¹、M²Weighing simple substances or compounds corresponding to the Sc and a carbon source according to a stoichiometric ratio, grinding and mixing uniformly;

(2) placing the mixture obtained in the step (1) in a crucible, and sintering at a high temperature under a protective atmosphere to naturally cool at room temperature;

(3) and (3) carrying out post-treatment on the product obtained by sintering in the step (2) to obtain the product.

In the step (1), the raw material M¹Compounds corresponding to Sc include nitrides, oxides, carbonates, nitrates, and the like; m²The corresponding compounds include nitrides, carbides or oxides.

In the step (1), the carbon source comprises graphite, activated carbon, amorphous carbon, sucrose, urea and the like;

in the step (2), the crucible is made of corundum, boron nitride, tantalum, tungsten, molybdenum and the like;

in the step (2), the protective atmosphere can be Ar or N₂、Ar/H₂Or N₂/H₂Etc.;

in the step (2), the high-temperature sintering can be carried out once or for multiple times, the sintering temperature is 1500-1900 ℃, and the sintering time is 2-20 h;

in the step (3), the post-treatment comprises the processes of crushing, grinding, grading, screening and washing and the like.

In yet another aspect, the present invention further provides a light emitting device comprising a light source and a phosphor, wherein the phosphor comprises at least one Sc-based carbonitride phosphor selected from the group consisting of the foregoing.

Compared with the prior art, the invention has the following beneficial technical effects:

(1) the fluorescent powder has a wider excitation peak, is particularly suitable for excitation of purple and near ultraviolet, and has better applicability.

(2) The emission wavelength of the fluorescent powder disclosed by the invention covers 450-550nm, so that the blue-green part missing in the conventional LED illumination can be effectively made up.

(3) The fluorescent powder of the invention belongs to carbonitride and has better physical and chemical stability.

Drawings

FIG. 1 shows the composition (Y) of example 1_0.98,Ce_0.02)ScSi₄N₆And C, crystal structure spectrum of the fluorescent powder.

FIG. 2 shows the composition (Y) in example 1_0.98,Ce_0.02)ScSi₄N₆Excitation spectrum of phosphor of C.

FIG. 3 shows the composition (Y) in example 1_0.98,Ce_0.02)ScSi₄N₆Emission spectrum of phosphor of C.

FIG. 4 shows the composition (Y) in example 2_0.98,Ce_0.02)ScSi₄N₆And the appearance of the SEM of the fluorescent powder of C.

FIG. 5 is a graph showing an emission spectrum of a white LED device of example 14.

Fig. 6 is a physical diagram of a white LED device according to example 14.

Detailed Description

In order to better understand the phosphor and the preparation method thereof of the present invention, the following embodiments are combined (and attached figures) to further explain the present invention. The following description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited by these embodiments, and is defined by the claims.

Comparative example

YScSi according to the chemical formula of the phosphor₄N₆C, weighing 2.0687g of Sc₂O₃、3.387g Y₂O₃、3.1564g Si₃N₄0.8918g C. After fully and uniformly mixing and grinding, placing the mixture in a tungsten crucible in N₂Roasting in the atmosphere, wherein the sintering temperature is 1750 ℃, the roasting time is 10 hours, and naturally cooling along with the room temperature. Crushing, grading, washing, drying and screening the roasted product to obtain YScSi₄N₆C, a substrate. The test of the luminous property is carried out, and the light is not seen in the range of ultraviolet to blue light.

Example 1

According to the chemical formula (Y) of the phosphor_0.98,Ce_0.02)ScSi₄N₆C, weighing 2.0687g of Sc₂O₃、3.3194g Y₂O₃、3.1564g Si₃N₄、0.8918g C、0.1033g CeO₂. After fully and uniformly mixing and grinding, placing the mixture in a tungsten crucible in N₂Roasting in the atmosphere, wherein the sintering temperature is 1750 ℃, the roasting time is 10 hours, and naturally cooling along with the room temperature. Crushing, grading, washing, drying and screening the roasted product to obtain the composition (Y)_0.98,Ce_0.02)ScSi₄N₆And C, fluorescent powder. Phase analysis and SrYSi₄N₇The crystal structure of (fig. 1) is similar. The excitation spectrum (490 nm monitoring) and the emission spectrum (400 nm excitation) are shown in fig. 2 and fig. 3, and it can be seen that the excitation wavelength range covers 260-450 nm, the emission wavelength covers 410-575 nm, and the peak wavelength is 474 nm.

Example 2

According to formula (Y)_0.98,Ce_0.02)ScSi₄N₆The stoichiometric proportion of C, YN (purity 99.9%), ScN (purity 99.9%), Si are accurately weighed₃N₄(purity 99.9%), SiC (purity 99.9%), and CeN (purity 99.99%) raw materials, and mixed to form a mixed raw material. And fully mixing and grinding the mixed raw materials in a glove box for 30min to obtain a mixture. Heating the mixture to 1900 ℃ at the heating rate of 10 ℃/min, then preserving the temperature for 10h at 1900 ℃, and naturally cooling to obtain a roasted product. After taking out the roasted product, crushing, washing, sieving and drying were carried out to obtain (Y) of example 2_0.98,Ce_0.02)ScSi₄N₆And C, fluorescent powder. SEM topography for example 2 is shown in FIG. 4

Example 3

According to formula (Y)_0.94,Ce_0.06)ScSi₄N₆The stoichiometric proportion of C, YN (purity 99.9%), ScN (purity 99.9%), Si are accurately weighed₃N₄(purity 99.9%), SiC (purity 99.9%), and CeN (purity 99.99%) raw materials, and mixed to form a mixed raw material. And fully mixing and grinding the mixed raw materials in a glove box for 30min to obtain a mixture. Heating the mixture to 1900 ℃ at the heating rate of 10 ℃/min, then preserving the temperature for 10h at 1900 ℃, and naturally cooling to obtain a roasted product. After taking out the calcined product, crushing, washing, sieving and drying were carried out to obtain (Y) of example 3_0.94,Ce_0.06)ScSi₄N₆And C, fluorescent powder.

Example 4

According to formula (Y)_0.85,Ce_0.15)ScSi₄N₆The stoichiometric proportion of C, YN (purity 99.9%), ScN (purity 99.9%), Si are accurately weighed₃N₄(purity 99.9%), SiC (purity 99.9%), and CeN (purity 99.99%) raw materials, and mixed to form a mixed raw material. And fully mixing and grinding the mixed raw materials in a glove box for 30min to obtain a mixture. Heating the mixture to 1900 ℃ at the heating rate of 10 ℃/min, then preserving the temperature for 10h at 1900 ℃, and naturally cooling to obtain a roasted product. After taking out the calcined product, crushing, washing, sieving and drying were carried out to obtain (Y) of example 4_0.85,Ce_0.15)ScSi₄N₆And C, fluorescent powder.

Example 5

According to formula (Y)_0.8,Ce_0.2)ScSi₄N₆The stoichiometric proportion of C, YN (purity 99.9%), ScN (purity 99.9%), Si are accurately weighed₃N₄(purity 99.9%), SiC (purity 99.9%), and CeN (purity 99.99%) raw materials, and mixed to form a mixed raw material. And fully mixing and grinding the mixed raw materials in a glove box for 30min to obtain a mixture. Heating the mixture to 1900 deg.C at a heating rate of 10 deg.C/min, maintaining the temperature at 1900 deg.C for 10 hr, and naturally cooling to obtain the final productAnd (4) roasting the product. After taking out the calcined product, crushing, washing, sieving and drying were carried out to obtain (Y) of example 5_0.8,Ce_0.2)ScSi₄N₆And C, fluorescent powder.

Example 6

According to formula (Y)_0.02,Ce_0.08)Sc_1.9Si₄N₆The stoichiometric proportion of C, YN (purity 99.9%), ScN (purity 99.9%), Si are accurately weighed₃N₄(purity 99.9%), SiC (purity 99.9%), and CeN (purity 99.99%) raw materials, and mixed to form a mixed raw material. And fully mixing and grinding the mixed raw materials in a glove box for 30min to obtain a mixture. Heating the mixture to 1900 ℃ at the heating rate of 10 ℃/min, then preserving the temperature for 10h at 1900 ℃, and naturally cooling to obtain a roasted product. After taking out the calcined product, crushing, washing, sieving and drying were carried out to obtain (Y) of example 6_0.02,Ce_0.08)Sc_1.9Si₄N₆And C, fluorescent powder.

Example 7

According to formula (Y)_1.749,Ce_0.001)Sc_0.25Si₄N₆The stoichiometric proportion of C, YN (purity 99.9%), ScN (purity 99.9%), Si are accurately weighed₃N₄(purity 99.9%), SiC (purity 99.9%), and CeN (purity 99.99%) raw materials, and mixed to form a mixed raw material. And fully mixing and grinding the mixed raw materials in a glove box for 30min to obtain a mixture. Heating the mixture to 1900 ℃ at the heating rate of 10 ℃/min, then preserving the temperature for 10h at 1900 ℃, and naturally cooling to obtain a roasted product. After taking out the calcined product, crushing, washing, sieving and drying were carried out to obtain (Y) of example 7_1.749,Ce_0.001)Sc_0.25Si₄N₆And C, fluorescent powder.

Example 8

According to formula (Y)_1.9,Ce_0.0.05)Sc_0.0.05Si₄N₆The stoichiometric proportion of C, YN (purity 99.9%), ScN (purity 99.9%), Si are accurately weighed₃N₄(purity 99.9%), SiC (purity 99.9%), and CeN (purity 99.99%) raw materials, and mixed to form a mixed raw material. Mixing the raw materials inFully mixing and grinding for 30min in a glove box to obtain a mixture. Heating the mixture to 1900 ℃ at the heating rate of 10 ℃/min, then preserving the temperature for 10h at 1900 ℃, and naturally cooling to obtain a roasted product. After taking out the calcined product, crushing, washing, sieving and drying were carried out to obtain (Y) of example 8_1.9,Ce_0.0.05)Sc_0.0.05Si₄N₆And C, fluorescent powder.

Example 9

According to the chemical formula (Lu)_0.94,Ce_0.06)ScSi₄N₆The stoichiometric proportion of C, LuN (purity 99.9%), ScN (purity 99.9%), Si are accurately weighed₃N₄(purity 99.9%), SiC (purity 99.9%), and CeN (purity 99.99%) raw materials, and mixed to form a mixed raw material. And fully mixing and grinding the mixed raw materials in a glove box for 30min to obtain a mixture. Heating the mixture to 1900 ℃ at the heating rate of 10 ℃/min, then preserving the temperature for 10h at 1900 ℃, and naturally cooling to obtain a roasted product. The calcined product was taken out, crushed, washed, sieved and dried to obtain (Lu) of example 9_0.94,Ce_0.06)ScSi₄N₆And C, fluorescent powder.

Example 10

According to the formula (La)_0.94,Ce_0.06)ScSi₄N₆The stoichiometric proportion of C, LaN (purity 99.9%), ScN (purity 99.9%), Si are accurately weighed₃N₄(purity 99.9%), SiC (purity 99.9%), and CeN (purity 99.99%) raw materials, and mixed to form a mixed raw material. And fully mixing and grinding the mixed raw materials in a glove box for 30min to obtain a mixture. Heating the mixture to 1900 ℃ at the heating rate of 10 ℃/min, then preserving the temperature for 10h at 1900 ℃, and naturally cooling to obtain a roasted product. The calcined product was taken out, crushed, washed, sieved and dried to obtain (La) of example 10_0.94,Ce_0.06)ScSi₄N₆And C, fluorescent powder.

Example 11

According to the formula (Gd)_0.94,Ce_0.06)ScSi₄N₆The stoichiometric proportion of C, GdN (purity 99.9%), ScN (purity 99.9%), Si are accurately weighed₃N₄(purity 99.9%), SiC (purity 99.9%), and CeN (purity 99.99%) raw materials, and mixed to form a mixed raw material. And fully mixing and grinding the mixed raw materials in a glove box for 30min to obtain a mixture. Heating the mixture to 1900 ℃ at the heating rate of 10 ℃/min, then preserving the temperature for 10h at 1900 ℃, and naturally cooling to obtain a roasted product. The calcined product was taken out, crushed, washed, sieved and dried to obtain (Gd) of example 11_0.94,Ce_0.06)ScSi₄N₆And C, fluorescent powder.

Example 12

According to formula (Y)_0.94,Ce_0.06)ScSi_3.5Al_0.5N_6.5C_0.5Accurately weighing YN (purity 99.9%), ScN (purity 99.9%), and Si according to the stoichiometric proportion₃N₄(purity 99.9%), SiC (purity 99.9%), AlN (purity 99.9%), and CeN (purity 99.99%) raw materials, and mixed to form a mixed raw material. And fully mixing and grinding the mixed raw materials in a glove box for 30min to obtain a mixture. Heating the mixture to 1900 ℃ at the heating rate of 10 ℃/min, then preserving the temperature for 10h at 1900 ℃, and naturally cooling to obtain a roasted product. After taking out the calcined product, crushing, washing, sieving and drying were carried out to obtain (Y) of example 12_0.94,Ce_0.06)ScSi_3.5Al_0.5N_6.5C_0.5And (3) fluorescent powder.

Example 13

According to formula (Y)_0.94,Ce_0.06)ScSi_3.5Al_0.5N_6.5C_0.5Accurately weighing YN (purity 99.9%), ScN (purity 99.9%), and Si according to the stoichiometric proportion₃N₄(purity 99.9%), SiC (purity 99.9%), AlN (purity 99.9%), and CeN (purity 99.99%) raw materials, and mixed to form a mixed raw material. And fully mixing and grinding the mixed raw materials in a glove box for 30min to obtain a mixture. Heating the mixture to 1900 ℃ at the heating rate of 10 ℃/min, then preserving the temperature for 10h at 1900 ℃, and naturally cooling to obtain a roasted product. After taking out the calcined product, crushing, washing, sieving and drying were carried out to obtain (Y) of example 13_0.94,Ce_0.06)ScSi_3.9Al_0.1N_6.9C_0.1FluorescenceAnd (3) pulverizing.

Example 14

(Y) obtained in example 4 above_0.94,Ce_0.06)ScSi₄N₆C and green fluorophor beta-Sialon Eu²⁺Red phosphor CaAlSiN₃:Eu²⁺The mass ratio of the three phosphors is 20:10:10, the three phosphors are mixed and added into silica gel to form a sticky matter, the sticky matter is coated on a 405nm near ultraviolet LED chip to obtain a white light LED device, a remote SIS-3_1.0m steel photometric integrating sphere _ R98 is used, the driving current is 60mA, and the white light LED device is obtained through detection, wherein the color rendering index is 94.7, and the color temperature is 4159K. Fig. 5 is a spectrum diagram of light emitted from the white LED device, and fig. 6 is a physical diagram.

The emission peak wavelength results of the phosphors of the above examples are shown in table 1. The color rendering index was measured using HAAS 2000.

TABLE 1 composition of each raw material in comparative example and example

	M¹	M²	a	b	c	d	e	x	Emission peak wavelength
										Example 1	Y	Si	0.98	1	4	6	1	0.02	474
Example 2	Y	Si	0.98	1	4	6	1	0.02	474
										Example 3	Y	Si	0.94	1	4	6	1	0.06	476
Example 4	Y	Si	0.85	1	4	6	1	0.15	483
										Example 5	Y	Si	0.8	1	4	6	1	0.2	485
Example 6	Y	Si	0.02	1.9	4	6	1	0.08	459
										Example 7	Y	Si	1.749	0.25	4	6	1	0.001	499
Example 8	Y	Si	1.9	0.05	4	6	1	0.05	520
										Example 9	Lu	Si	0.94	1	4	6	1	0.06	478
Example 10	La	Si	0.94	1	4	6	1	0.06	450
										Example 11	Gd	Si	0.94	1	4	6	1	0.06	481
Example 12	Y	Si_3.5Al_0.5	0.94	1	-	6.5	0.5	0.06	482
										Example 13	Y	Si_3.9Al_0.1	0.94	1	-	6.9	0.1	0.06	473

It is noted that a, b, c, d, e, and x represent the stoichiometric ratios of the different elements in the specific molecular formulas of the samples of the examples, respectively.

As can be seen from the above experimental data, if M¹When the Y is taken as a standard and is gradually replaced by La/Lu, the emission spectrum generates blue shift; the emission spectrum is gradually red-shifted when gradually substituted by Gd. When M is²When Si in the lattice site is gradually substituted by Al, the emission spectrum is gradually red-shifted.

In addition, the X-ray scanning results of the phosphors of examples 1-13 above all showed the same color as SrYSi₄N₇Similar diffraction peaks are subjected to structural refinement by a Rietveld method, and the results show that the similar diffraction peaks all have the same structure as SrYSi₄N₇The same crystal structure.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A Sc-based carbonitride phosphor characterized in that the phosphor comprises an inorganic compound consisting of M¹、Sc、M²N, C and a luminescence center Ce, the chemical formula of which is M¹ _aSc_bM² _cN_dC_e: xCe, wherein M¹One or more of rare earth metal elements Y, La, Gd and Lu, M²Is Si; a is more than 0 and less than or equal to 1.749, b is more than or equal to 0.25 and less than or equal to 1.9, c =4, d is more than or equal to 6 and less than or equal to 6.5, e is more than or equal to 0.5 and less than or equal to 1, and x is more than 0 and less than or equal to 0.2;

the inorganic compound has a chemical structure similar to SrYSi₄N₇Similar crystal structures, belong to the hexagonal structure.

2. The Sc-based carbonitride phosphor of claim 1 characterized in that M is¹Is Y, or at least one M¹Is Y.

3. A Sc-based carbonitride phosphor according to claim 1 characterized in that (a + x) b: c: d: e =1:1:4:6: 1.

4. The Sc-based carbonitride fluorescent powder as set forth in claim 1, wherein the excitation peak wavelength of the fluorescent powder is between 360-440nm, and the emission peak wavelength is between 450-500nm, suitable for ultraviolet LED chips.

5. A method of making a Sc-based carbonitride phosphor powder according to any one of claims 1 to 4 characterized by the steps of:

(1) will M¹、M²Weighing simple substance or compound corresponding to Sc, carbon source, nitrogen source and cerium source according to stoichiometric ratio, grinding and mixing uniformly;

(2) placing the mixture obtained in the step (1) in a crucible, sintering at high temperature under a protective atmosphere, and then naturally cooling at room temperature;

6. A light emitting device comprising a light source and a phosphor, wherein the phosphor comprises at least one Sc-based carbonitride phosphor as set forth in any one of claims 1-4.