Fluoride fluorescent powder and light-emitting device

Abstract

The invention discloses fluoride fluorescent powder and a light-emitting device, the fluoride fluorescent powder comprises an inorganic compound, the composition formula of the inorganic compound is AaEeMmFy: xMn, and the inorganic compound has the same crystal structure as Cs2LiAlF6 and has a # imgabs0 # space group; the element A comprises Cs, the element E comprises Li, and the element M comprises Al; 1.8 < = a < = 2.2, 0.8 < = e < = 1.2, 0.8 < = m < = 1.05, 5.9 < = f < = 6.1, 0lt; and x is less than or equal to 0.2. Through the inorganic compound with richer components and higher controllability, the spatial configuration of the material can flexibly regulate and control the coordination field environment of luminescence center ions, and the luminescence property of the material is improved by optimizing a local coordination structure.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and in particular to a fluoride phosphor and a luminescent device. Background Art

[0002] Semiconductor solid-state light sources offer advantages such as energy conservation, environmental protection, high luminous efficiency, and long life, and are widely used in the display field. In display technology, white light-emitting diodes (LEDs) and white laser diodes (LDs) backlights are core components that determine the color reproduction of screen displays. To achieve more vivid and realistic displays, white LED / LD backlights that can display a wider color gamut are required.

[0003] The combination of blue LED / LD chips and narrow-band green and red phosphors has become the mainstream method for achieving white LED / LD backlighting in commercial displays. The longer the emission wavelength of the phosphor, the narrower the half-peak width, and the wider the color gamut. To meet the demand for ultra-high color gamut display backlights, it is necessary to develop narrow-band long-wavelength green and red phosphors. 4+ Activated fluoride has the advantages of low synthesis cost, low phonon energy, high efficiency, narrow spectrum emission (half-maximum width <12nm), and emission range within the sensitive range of the human eye (<650nm). It is a red phosphor that can meet the color gamut required for ultra-high-definition displays at low cost. 4+ Designing the fluoride matrix to further redshift its wavelength is of great significance to promoting the development of ultra-high color gamut display.

[0004] In addition, the Cs3AlF6:Mn 4+ The CIE x coordinates of fluoride fluorescent pink are all around 0.69 and the luminous efficiency is low, which makes it difficult to meet the requirements of ultra-high color gamut LED / LD backlight sources. Summary of the Invention

[0005] The purpose of the embodiments of the present invention is to provide a fluoride phosphor and a light-emitting device. By using inorganic compounds with richer components and higher controllability, its spatial configuration can flexibly regulate the coordination field environment of the luminescent center ion, and by optimizing the local coordination structure, the luminescence performance of the material is improved.

[0006] In order to solve the above technical problems, the first aspect of the embodiment of the present invention provides a fluoride phosphor, comprising an inorganic compound, the inorganic compound composition formula is A a E e M m F y :xMn, has the same crystal structure as Cs2LiAlF6, with Space group; the A element includes Cs, the E element includes Li, and the M element includes Al; and 1.8≤a≤2.2, 0.8≤e≤1.2, 0.8≤m≤1.05, 5.9≤f≤6.1, 0 <x≤0.2。

[0007] Furthermore, the A element also includes: K, Rb or NH4 + , K, Rb and NH4 in the A element + The molar ratio of one of the elements A is i; and / or

[0008] The E element further comprises Na, and the molar ratio of Na in the E element to the E element is j; and / or

[0009] The M element further comprises Ga, In or Sc, and the molar ratio of one of Ga, In and Sc in the M element to the M element is k.

[0010] Furthermore, 0 <i≤20%,j=0,k=0。

[0011] Furthermore, the A element includes Cs and Rb, and 1%≤i≤15%.

[0012] Furthermore, i=0,0 <j≤25%,k=0。

[0013] Furthermore, the E element includes Li and Na, and 1%≤j≤15%.

[0014] Furthermore, i=0, j=0, 0 <k≤25%。

[0015] Furthermore, the M element includes Al and In, and 1%≤k≤10%.

[0016] Furthermore, 0<i≤20%, 0<j≤25%, k=0, i+j≤30%.

[0017] Furthermore, 1%≤i≤15%, 1%≤j≤15%, and 0.8≤i / j≤1.2.

[0018] Correspondingly, a second aspect of an embodiment of the present invention provides a light-emitting device, comprising a semiconductor chip emitting ultraviolet light, violet light, or blue light and a phosphor coated on the semiconductor chip, wherein the phosphor is the above-mentioned fluoride phosphor.

[0019] The above technical solutions of the embodiments of the present invention have the following beneficial technical effects:

[0020] 1. By using inorganic compounds with richer components and higher controllability, the spatial configuration can flexibly control the coordination field environment of the luminescent center ion, thereby improving the luminescence performance of the material by optimizing the local coordination structure;

[0021] 2. Fluoride red phosphor can be excited by a variety of light sources / bands, especially blue light, and has a high luminous intensity. The fluorescent pink coordinate x>0.70, which can meet the needs of ultra-high color gamut display backlight sources. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 1 is the XRD pattern of the phosphors in the comparative example and Examples 1-3 provided in the embodiments of the present invention;

[0023] Figure 2 This is an excitation-emission spectrum diagram of the phosphor in Example 1 provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0024] To make the objectives, technical solutions, and advantages of the present invention more clearly understood, the present invention will be further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings. It should be understood that these descriptions are merely exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, descriptions of well-known structures and technologies are omitted to avoid unnecessary confusion of the concepts of the present invention.

[0025] Please refer to Figure 1 The first aspect of the embodiment of the present invention provides a fluoride phosphor, characterized in that it contains an inorganic compound, the inorganic compound composition formula is A a E e M m F y :xMn, has the same crystal structure as Cs2LiAlF6, with Space group; A elements include Cs, E elements include Li, M elements include Al; and 1.8≤a≤2.2, 0.8≤e≤1.2, 0.8≤m≤1.05, 5.9≤f≤6.1, 0 <x≤0.2。

[0026] The inorganic compound comprises element A, element E, element M, element F and element Mn, and has the composition formula: a E e M m F y :xMn 4+ , where x is the doping ion Mn 4+ The molar percentage of element M. The phosphor has the same trigonal structure as Cs2LiAlF6, and the space group is Compared with other systems, the above structure has richer component diversity and higher controllability; its unique spatial configuration can flexibly regulate the coordination field environment of luminescent center ions, and by optimizing the local coordination structure, the luminescence performance of the material can be improved.

[0027] Elements E and M form [EF6] and [MF6] octahedra respectively, and are alternately connected through shared F atoms, presenting a three-dimensional chain structure. Element A is located at the center of the polyhedron formed by 12 adjacent F elements, forming a tetrakaidecahedron [AF 12 , constituting the same phase structure as Cs2LiAlF6. Due to energy splitting, Mn4+ ions can only exist stably in tetrahedral or octahedral environments, and the lattice site of A cannot be occupied by Mn 4+ substituted. In addition, the six-coordinated ionic radius of element E differs greatly from that of element M, and the valence state is relatively low. Therefore, Mn 4+ ions preferentially occupy the lattice sites of M, and [MF6] can provide a suitable lattice environment for the luminescence of Mn 4+ in the six-coordinated crystal length.

[0028] Specifically, the ionic radii of and in element A are similar, and the ionic radii of Li + (0.76) and Na + (1.02) in element E are similar. As important components in the Cs2LiAlF6-type crystal structure, A and E can be used to adjust the luminescence performance by element substitution as needed. The properties of elements Ga, In, Sc, and Al in element M are similar, and the six-coordinated ionic radius and is close to Part of Al can be replaced by appropriate amounts of In, Ga, or Sc as needed to adjust the unit cell parameters and crystal field characteristics, and further realize the regulation of luminescence characteristics.

[0029] Furthermore, the value ranges of each element in the composition formula of the inorganic compound can be: 0 < x ≤ 0.2, 1.8 ≤ a ≤ 2.2, 0.8 ≤ e ≤ 1.2, 0.8 ≤ m ≤ 1.05, 5.9 ≤ f ≤ 6.1. Under this composition, the main phase can form the same structure as Cs2LiAlF6 mentioned above.

[0030] In a specific embodiment of the embodiment of the present invention, element A further includes: K, Rb, or NH4 + , K, Rb, and NH4 in element A +One of them has a molar ratio of element A of i; and / or, element E further includes Na, and the molar ratio of Na in element E is j; and / or, element M further includes Ga, In or Sc, and the molar ratio of one of Ga, In and Sc in element M is k.

[0031] Optionally, in a specific embodiment of the embodiments of the present invention, 0 < i ≤ 20%, j = 0, k = 0. Only when the A site is mainly Cs can a purer Cs2LiAlF6 phase structure be obtained, which is more conducive to the luminescence of Mn; on the other hand, the A site can also be appropriately doped with K + , NH4 + , Rb + , as a long-range regulation strategy, adjacent cation substitution can precisely regulate the photoluminescence performance of materials by changing the local coordination environment or electronic structure, and obtain better luminescence intensity.

[0032] Furthermore, in another specific embodiment of the embodiments of the present invention, element A includes Cs and Rb, and 1% ≤ i ≤ 15%. Cs + has a relatively large ionic radius and occupies the hole position in the lattice, resulting in certain distortion and stress in the lattice. The ionic radius of is slightly smaller than + When Cs + is substituted by a small amount of Rb 4+ ions, the lattice distortion decreases, making the lattice more ordered, which can reduce non-radiative transitions, such as phonon scattering or defect-related energy loss, thereby enhancing the luminescence efficiency of Mn 4+ . In addition, after substitution, the local lattice shrinks and the crystal field strength increases, resulting in an increase in the oscillator strength of the luminescence transition of Mn 2 E → 4 A2), and the luminescence intensity is enhanced. In addition, it can also optimize the coordination environment of Mn 4+ , making the arrangement of fluoride ions (F - ) around it more symmetrical or stable. This coordination environment can effectively reduce the non-radiative recombination probability of Mn 4+ , thereby enhancing the luminescence intensity. Therefore, when the doping ratio of Rb + is 1% ≤ i ≤ 15%, it has stronger luminescence intensity.

[0033] Optionally, in another specific embodiment of the embodiments of the present invention, i = 0, 0 < j ≤ 25%, k = 0. Li + has a 1s 2 electronic configuration and has a stronger polarization effect than other alkali metal ions. The high polarization ability can enhance the interaction with the anion F -Bonding strength, reduce lattice vibration (phonon energy), thereby reducing the probability of non-radiative transition, which is more conducive to the luminescence of Mn; on the other hand, Na can also be doped appropriately + , adjust the crystal microstructure to obtain better luminescence intensity.

[0034] Furthermore, in another specific embodiment of the embodiment of the present invention, the E element includes Li and Na, and 1% ≤ j ≤ 15%. The high charge density of Li + will also lead to stronger F - →Mn 4+ charge transfer, enhance covalency, but excessive covalency will weaken the luminescence transition dipole moment of Mn 4+ . Introducing Na with lower polarization ability at the Li element lattice site + can balance covalency and ionicity, thereby maintaining a high radiative transition probability, which is beneficial to the 4+ higher luminescence efficiency of Mn. In addition, when Mn 4+ replaces the M lattice site, due to the strong rigidity of the matrix lattice, it is easy to introduce greater lattice distortion, resulting in the generation of more non-radiative recombination centers (such as defects, dislocations), reducing the luminescence efficiency. Introducing larger Na + ions at the Li element lattice site can buffer lattice distortion and reduce non-radiative recombination, thereby enhancing the luminescence intensity. Therefore, when the doping ratio of Na + is 1% ≤ j ≤ 15%, it has stronger luminescence intensity.

[0035] [[ID=2,6]]Optionally, in another specific embodiment of the embodiment of the present invention, i = 0, j = 0, 0 < k ≤ 25%. Only when the E site is mainly Al can a purer Cs2LiAlF6 phase structure be obtained, which is more conducive to the luminescence of Mn; on the other hand, in the six-coordination case, compared with and The effective ionic radius of is slightly larger than Mn 4+ is more likely to replace Ga 3+ , In 3+ , Sc 3+ positions. Under the same experimental conditions, the doping amount of Mn 4+ in the matrix is higher, thereby realizing the enhancement regulation of the luminescence intensity.

[0036] Furthermore, in another specific embodiment of the embodiment of the present invention, the M element includes Al and In, and 1% ≤ k ≤ 10%. Since the six-coordination ionic radius of the Al element is very close to that of Mn 4+ , and it belongs to non-equivalent substitution. When Mn 4+ replaces Al 3 + ]>, + a Cs may be generatedor Li + Vacancies to compensate for trivalent M and Mn 4+ The imbalance of valence between ions causes the matrix lattice to shrink, which is not conducive to the Mn 4+ In addition, Mn 4+ Al in a highly symmetrical 3+ Site, inversion center exists, the dd transition of [MnF6] octahedron is parity forbidden, and the luminous intensity is low. Using a larger radius replace The space occupied by the M site may be larger. This larger cavity is conducive to the 4+ The eccentric displacement of the ion eliminates the inversion center, reduces the symmetry of the [MnF6] octahedron, and the forbidden transition becomes partially allowed, effectively improving the luminescence intensity. + The doping ratio of 1%≤k≤10% has stronger luminescence intensity.

[0037] Optionally, in another specific implementation of the embodiment of the present invention, 0<i≤20%, 0<j≤25%, k=0, i+j≤30%. 4+ The charge of the M site in the matrix crystal is unbalanced. When a Mn 4+ When an M ion replaces an M ion, 4+ An ion vacancy defect, either A or E, will simultaneously appear nearby to compensate for the charge imbalance. Simultaneously substituting appropriate ions at both A and E effectively minimizes crystal distortion and enhances structural stability, resulting in better luminescence performance. On the other hand, excessive ion substitution can also increase lattice distortion and lead to structural instability. Therefore, within these conditions, smaller lattice defects and a more stable structure are achieved, ensuring that the phosphor has a similar crystal structure to Cs2LiAlF6.

[0038] Optionally, in another specific implementation of the embodiment of the present invention, 1%≤i≤15%, 1%≤j≤15%, the lattice distortion is smaller, the structure is more stable, and the luminous intensity is higher.

[0039] Preferably, the ratio of i to j is 0.8≤i / j≤1.2. + Vacancy or Cs + Interlayer gap can flexibly balance Mn 4+The charge imbalance introduced by replacing the M site can adjust the degree of lattice distortion of the crystal structure by changing the molar ratio of A / E, thereby regulating the ligand field strength of the [MnF6] octahedron. When the ratio of i (A-site doping amount) to j (E-site doping amount) is 0.8≤i / j≤1.2, it can not only suppress the phase transition or defect accumulation caused by excessive distortion, thereby maintaining the stability of the crystal structure; but also enhance the parity forbidden relaxation of dd electron transitions through moderate octahedral compression, thereby significantly improving the Mn 4+ of 2 E→ 4 Therefore, within the above ratio range, the synergistic effect of lattice distortion and charge compensation enables the material to maintain structural dynamic equilibrium during the excitation-emission cycle, avoiding the generation of non-radiative recombination channels.

[0040] Optionally, when A is Cs, E is Li, and M is Al, it also has excellent luminous efficiency, and the luminous intensity is increased by more than 18% compared with the Mn-activated Cs3AlF6 structure phosphor in the prior art.

[0041] The preparation process of the above phosphor is as follows:

[0042] In step S100 , the oxides, phosphates, carbonates, nitrates, fluorides and fluoromanganate of raw materials A, E and M are weighed respectively according to the stoichiometric ratio of the molecular formula.

[0043] Step S200, uniformly mix the above raw materials in HF aqueous solution, transfer it to a polytetrafluoroethylene-lined high-pressure reactor, and heat it at a temperature of 180-230°C for 3-8 hours; after naturally cooling to room temperature, collect the powder precipitate by centrifugation to obtain a yellow solid sample.

[0044] Step S300 , washing the yellow solid sample with glacial acetic acid and anhydrous ethanol in sequence, and drying to obtain phosphor powder.

[0045] The preparation process and test results of the phosphor are described in detail below through several examples and comparative examples.

[0046] Comparative Example 1

[0047] The red phosphor described in this comparative example contains a compound having the formula Cs3Al 0.95 F 6.05 :0.05Mn 4+ .

[0048] Weigh AlF3 (7.98g) and Cs2MnF6 (2.17g) and dissolve them in 200mL 41wt% HF solution; CsF (45.57g) is dissolved in 50mL deionized water and poured into the above solution; after vigorous stirring for 30 minutes, the mixed solution is transferred to a polytetrafluoroethylene-lined autoclave and heated at 180°C for 3 hours; after cooling naturally to room temperature, the powder precipitate is collected by centrifugation to obtain a yellow solid sample; the sample is washed with deionized water and anhydrous ethanol in turn, and dried to obtain the phosphor. The phosphor is a cubic crystal with a space group of The luminescence intensity under 460nm blue light excitation was set to 100.

[0049] Example 1

[0050] The red phosphor described in this embodiment contains a compound with the formula Cs2LiAl 0.95 F 6.05 :0.05Mn 4+ .

[0051] AlF3 (7.98 g) and Cs2MnF6 (2.17 g) were weighed and dissolved in 200 mL of 41 wt% HF solution; CsF (30.38 g) and LiF (2.59 g) were uniformly mixed in 50 mL of deionized water, and the above solution was poured into the mixture; after vigorous stirring for 30 minutes, the mixed solution was transferred to a polytetrafluoroethylene-lined autoclave and heated at 200°C for 6 hours; after cooling naturally to room temperature, the powder precipitate was collected by centrifugation to obtain a yellow solid sample; the sample was washed with glacial acetic acid and anhydrous ethanol in sequence and dried to obtain the phosphor. The phosphor obtained in Example 1 was tested using X-ray spectroscopy (Co target), and its XRD diffraction pattern was consistent with PDF#00-026-0385, showing a trigonal Cs2LiAlF6 crystal structure, as shown in FIG. Figure 1 The material was analyzed by fluorescence spectrometer. It was found that the material had a narrow spectrum of red light under 460nm blue light excitation, and its peak wavelength was 633nm (as shown in FIG. Figure 2 as shown), with a relative strength of 118.

[0052] Example 2

[0053] The red phosphor described in this embodiment contains a compound with the formula Cs 1.95 Li 1.06 Al 0.9 F 5.91 :0.05Mn 4+ .

[0054] AlF3 (7.56 g) and Cs2MnF6 (2.17 g) were weighed and dissolved in 200 mL of 41 wt% HF solution; CsF (29.62 g) and LiF (2.75 g) were uniformly mixed in 50 mL of deionized water and poured into the above solution; after vigorous stirring for 30 minutes, the mixed solution was transferred to a polytetrafluoroethylene-lined autoclave and heated at 210°C for 6 hours; after cooling naturally to room temperature, the powder precipitate was collected by centrifugation to obtain a yellow solid sample; the sample was washed with glacial acetic acid and anhydrous ethanol in turn, and dried to obtain the phosphor. The phosphor obtained in Example 2 was analyzed by X-ray diffraction to obtain its X-ray diffraction pattern, as shown in FIG. Figure 1 The fluorescent powder obtained in Example 2 was analyzed using a fluorescence spectrometer. The spectrum of the material under 460nm blue light excitation was consistent with that of Example 1, and the relative luminous intensity was 110.

[0055] Example 3

[0056] The red phosphor described in this embodiment contains a compound with the formula Cs 1.9 Rb 0.1 LiAl 0.95 F 6.05 :0.05Mn 4+ .

[0057] AlF3 (7.98 g) and Cs2MnF6 (2.17 g) were weighed and dissolved in 200 mL of 41 wt% HF solution; CsF (28.86 g), Rb2CO3 (2.31 g) and LiF (2.59 g) were uniformly mixed in 50 mL of deionized water and poured into the above solution; after vigorous stirring for 30 minutes, the mixed solution was transferred to a polytetrafluoroethylene-lined autoclave and heated at 200°C for 5.5 hours; after cooling naturally to room temperature, the powder precipitate was collected by centrifugation to obtain a yellow solid sample; the sample was washed with glacial acetic acid and anhydrous ethanol in turn, and dried to obtain the phosphor. The phosphor obtained in Example 3 was analyzed by X-ray diffraction to obtain its X-ray diffraction pattern, as shown in FIG. Figure 1 The fluorescent powder obtained in Example 3 was analyzed using a fluorescence spectrometer. The material had a spectrum consistent with that of Example 1 under 460nm blue light excitation, and a relative luminous intensity of 152.

[0058] The preparation and characterization methods for the phosphors of Examples 4-31 are similar to those of Examples 1-3. Based on the target compound composition in each example, the appropriate amount of raw materials was selected for dissolution, and appropriate heating conditions and post-processing were employed to produce the phosphors shown in Table 1. The relative luminous intensities of the compositions of Comparative Example 1 and Examples 1-31 are shown in Table 1.

[0059] Table 1 Composition elements and luminescence properties of each embodiment

[0060]

[0061]

[0062] The data in Table 1 demonstrates that Examples 1-31 all possess the phosphor compositions of the present invention. Taking the luminous intensity of the comparative example as 100%, the phosphors provided by the present invention exhibit significantly higher luminous intensity when excited by a blue light chip. Their peak emission wavelength is 633 nm, and their CIE x color coordinates are greater than 0.7, meeting the application requirements of ultra-high color gamut display backlight sources.

[0063] According to Examples 1-13, it can be seen that the luminescence intensity can be effectively enhanced without changing the original Cs2LiAlF6 matrix phase structure by replacing a small amount of elements at the A, E, and M sites respectively. In addition, when the elements replacing the A, E, and M sites are Rb, Na, and In, respectively, the luminescence intensity is higher.

[0064] As can be seen from Examples 14-25, the phosphors obtained by simultaneously doping a small amount of elements at two sites exhibit higher overall relative emission intensity than the phosphors obtained by simultaneously doping elements at three sites in Examples 26-28. This is because appropriate element substitution can effectively reduce crystal distortion and enhance structural stability, resulting in better luminescence performance. However, excessive ion substitution can also increase lattice distortion, leading to structural instability and thus affecting luminescence intensity.

[0065] According to Examples 14-20, it can be seen that when the doping ratio of Rb to Na satisfies 0.8≤i / j≤1.2, the luminescence intensity reaches its peak. This is because at this ratio, the phase transition or defect accumulation caused by excessive distortion can be suppressed, maintaining the stability of the crystal structure; and the parity forbidden relaxation of dd electron transitions can be enhanced through moderate octahedral compression, thereby increasing the Mn 4+ of 2 E→ 4 The A2 transition red light emission efficiency is improved, thereby obtaining a better luminous intensity.

[0066] In addition, it should be noted that when the diffraction angles (28.21°, 33.43° and 38.83°) corresponding to the three strongest peaks in the XRD spectrum of other phosphors are the same as those of the present invention, the corresponding diffraction angle positions and relative intensities of other peaks change slightly, or the XRD diffraction peak positions of other phosphors show an overall left or right shift due to the expansion or contraction of the unit cell, they are all regarded as having the same crystal structure type as the phosphor described in the present invention.

[0067] Correspondingly, a second aspect of the embodiments of the present invention provides a light-emitting device, including a semiconductor chip emitting ultraviolet light, violet light or blue light and a phosphor coated on the semiconductor chip, and the phosphor is the above-mentioned fluoride phosphor.

[0068] The embodiments of the present invention aim to protect a fluoride phosphor and a light-emitting device. The fluoride phosphor includes an inorganic compound, and the compositional formula of the inorganic compound is A a E e M m F y :xMn, having the same crystal structure as Cs2LiAlF6, having space group; element A includes Cs, element E includes Li, element M includes Al; and 1.8 ≤ a ≤ 2.2, 0.8 ≤ e ≤ 1.2, 0.8 ≤ m ≤ 1.05, 5.9 ≤ f ≤ 6.1, 0 < x ≤ 0.2. The above technical solutions have the following effects:

[0069] 1. Through an inorganic compound with richer components and higher controllability, the spatial configuration thereof can flexibly regulate the coordination field environment of the luminescent center ions, and by optimizing the local coordination structure, the luminescence performance of the material is improved;

[0070] 2. The fluoride red phosphor can be excited by a variety of light sources / wavelength bands, especially blue light, and has a high luminescence intensity. The chromaticity coordinates of the phosphor x > 0.70, which can meet the requirements of the backlight source for ultra-high color gamut display.

[0071] It should be understood that the above specific embodiments of the present invention are only used for exemplary illustration or explanation of the principle of the present invention, and do not constitute a limitation to the present invention. Therefore, any modifications, equivalent replacements, improvements, etc. made without departing from the spirit and scope of the present invention shall be included within the protection scope of the present invention. In addition, the appended claims of the present invention aim to cover all changes and modification examples falling within the scope and boundary of the appended claims, or equivalent forms of such scope and boundary.

Claims

1. A fluoride phosphor, characterized in that: Contains an inorganic compound, the inorganic compound composition formula is A a E e M m F y :xMn, has the same crystal structure as Cs2LiAlF6, with space group; The A element includes Cs, the E element includes Li, and the M element includes Al; And 1.8≤a≤2.2, 0.8≤e≤1.2, 0.8≤m≤1.05, 5.9≤f≤6.1, 0 <x≤0.2。 2. The fluoride phosphor according to claim 1, characterized in that: The A element also includes: K, Rb or NH4 + , K, Rb and NH4 in the A element + The molar ratio of one of the elements A is i; and / or The E element further comprises Na, and the molar ratio of Na in the E element to the E element is j; and / or The M element further comprises Ga, In or Sc, and the molar ratio of one of Ga, In and Sc in the M element to the M element is k.

3. The fluoride phosphor according to claim 2, characterized in that: 0 <i≤20%,j=0,k=0。 4. The fluoride phosphor according to claim 3, characterized in that: The A element includes Cs and Rb, and 1%≤i≤15%.

5. The fluoride phosphor according to claim 2, characterized in that: i=0,0 <j≤25%,k=0。 6. The fluoride phosphor according to claim 5, characterized in that: The E element includes Li and Na, and 1%≤j≤15%.

7. The fluoride phosphor according to claim 2, characterized in that: i=0,j=0,0 <k≤25%。 8. The fluoride phosphor according to claim 7, characterized in that: The M element includes Al and In, and 1%≤k≤10%.

9. The fluoride phosphor according to claim 2, characterized in that: 0<i≤20%, 0<j≤25%, k=0, i+j≤30%.

10. The fluoride phosphor according to claim 9, characterized in that: 1%≤i≤15%, 1%≤j≤15%, 0.8≤i / j≤1.

2.

11. A light emitting device, characterized in that: A semiconductor chip emitting ultraviolet light, violet light or blue light and phosphor coated on the semiconductor chip, wherein the phosphor is the fluoride phosphor according to any one of claims 1 to 10.

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