Phosphor composition and LED device
By adding neodymium-containing inorganic compounds and/or neodymium-containing organic compounds as additives to phosphors, the problem of color mixing caused by excessive full width at half maximum (FWHM) of phosphors was solved, resulting in phosphor compositions with narrow FWHM and high color purity, thus improving luminescence performance.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- FOSHAN NATIONSTAR OPTOELECTRONICS CO LTD
- Filing Date
- 2024-12-04
- Publication Date
- 2026-06-11
AI Technical Summary
The phosphors currently used in backlighting have excessively large half-widths, resulting in mixed colors and reduced color purity and color gamut.
Neodymium-containing inorganic compounds and/or neodymium-containing organic compounds are used as phosphor additives to absorb the emission band of the phosphor through specific absorption peaks, forming a phosphor composition with narrow half-width, stable crystal structure, and superior luminescence performance.
A phosphor composition with narrow half-peak width was achieved, which improved color purity and color gamut, and enhanced luminescence performance.
Smart Images
Figure CN2024136766_11062026_PF_FP_ABST
Abstract
Description
A phosphor composition and an LED device Technical Field
[0001] This application belongs to the field of LED light-emitting technology and relates to a phosphor composition and an LED device. Background Technology
[0002] A light-emitting diode (LED) is a semiconductor device that converts electrical energy into light energy. Using LEDs as a backlight can improve image quality. In addition, LEDs have significant advantages in terms of luminous efficacy, response speed, and light decay.
[0003] If the main emission peak of the phosphor used in the backlight field has an excessively large half-width, it means that the phosphor has a wide emission spectrum. This can lead to unnecessary color mixing, resulting in a reduction in color purity and color gamut of the backlight device.
[0004] Therefore, there is a need for a phosphor composition with narrow half-width, stable crystal structure, and superior luminescence performance. Summary of the Invention
[0005] The following is an overview of the subject matter described in detail herein. This overview is not intended to limit the scope of the claims.
[0006] The purpose of this application is to provide a phosphor composition and an LED device, wherein the phosphor additive can improve the external quantum efficiency of the phosphor composition, resulting in a phosphor composition with narrow half-width, stable crystal structure and superior luminescence performance.
[0007] To achieve this objective, the present application adopts the following technical solution:
[0008] In a first aspect, this application provides a phosphor composition comprising phosphor and phosphor additives.
[0009] The phosphor additives include neodymium-containing inorganic compounds and / or neodymium-containing organic compounds.
[0010] The neodymium-containing inorganic compound includes Nd a A x B y O zAnd / or NdM, where a>0, x≥0, y≥0, z>0 and 3×a+n1×x+n2×y=2z, n1 is the valence state of A ion, and n2 is the valence state of B ion; A includes at least one of H, N, S, F, Cl, Br, I, Na, K, Al, Mg, Li, Ca, Sr, Ba, Al, Si, B, Ga, In, Ge or Sn; B includes at least one of H, N, S, F, Cl, Br, I, Na, K, Al, Mg, Li, Ca, Sr, Ba, Al, Si, B, Ga, In, Ge or Sn; M includes at least one of N, S, Cl, F, Br or I.
[0011] The neodymium-containing organic compound includes at least one of neodymium acetate, neodymium acetylacetonate, MOF-Nd, binary neodymium complexes, or ternary neodymium complexes.
[0012] The phosphor composition provided in this application, through the use of specific phosphor additives, can utilize the specific absorption peaks of the phosphor additives to absorb the emission bands in the phosphor, thereby obtaining a phosphor composition with narrow half-width, stable crystal structure, and superior luminescence performance.
[0013] In one embodiment, the phosphor additive is at least one of neodymium acetate, neodymium fluoride, or neodymium oxide.
[0014] In one embodiment, the average particle size of the phosphor additive is 0.1 μm or more and 10 μm or less, and more preferably 0.1 μm or more and 5 μm or less.
[0015] In one embodiment, the phosphor includes any one of fluorescent green, fluorescent yellow, or fluorescent red.
[0016] In one embodiment, the phosphor composition comprises, by weight percentage, 5 wt% to 90 wt% phosphor additives, and more optionally, the phosphor composition comprises 20 wt% to 50 wt% phosphor additives.
[0017] In one embodiment, the phosphor is β-SiAlON green phosphor.
[0018] The median particle size of the β-SiAlON green powder is 10 μm to 40 μm, and more preferably, the median particle size of the β-SiAlON green powder is 15 μm to 30 μm.
[0019] The aspect ratio of the β-SiAlON green powder is from 1:1 to 20:1, and more preferably, the aspect ratio of the β-SiAlON green powder is from 2:1 to 15:1.
[0020] In one embodiment, the emission spectrum of the phosphor composition has a peak wavelength λ of 520 nm to 550 nm.
[0021] The emission spectrum of the phosphor composition has a full width at half maximum (FWHM) of 30 nm to 60 nm for the main peak.
[0022] In one embodiment, the emission spectrum of the phosphor composition satisfies the following condition: the intensity at λ1 is greater than the intensity at λ2, where λ1 is λ-Δλ, λ2 is λ+Δλ, and Δλ is less than 30 nm.
[0023] In one embodiment, the emission spectrum of the phosphor composition includes a first characteristic peak and a second characteristic peak on both sides of the main peak.
[0024] The peak wavelength of the first characteristic peak is 500 nm to 530 nm, and can be further selected as 510 nm to 525 nm.
[0025] The peak wavelength of the second characteristic peak is 590 nm to 630 nm, and can be further selected as 600 nm to 620 nm.
[0026] In one embodiment, the peak intensity at the peak wavelength of the main peak is I1; the peak intensity at the peak wavelength of the first characteristic peak is I2; and the peak intensity at the peak wavelength of the second characteristic peak is I3.
[0027] The value of I2 is less than 80% of I1, and may further be less than 65%.
[0028] The value of I3 is less than 30% of I1, and may be further selected as less than 20%.
[0029] In one embodiment, the absorption spectrum of the phosphor composition includes a first absorption peak, a second absorption peak, and a third absorption peak.
[0030] The peak wavelength of the first absorption peak is from 500 nm to 522 nm.
[0031] The peak wavelength of the second absorption peak is from 521 nm to 540 nm.
[0032] The peak wavelength of the third absorption peak is between 570 nm and 600 nm.
[0033] In one embodiment, the peak intensity at the peak wavelength of the first absorption peak is I. a The peak intensity at the peak wavelength of the second absorption peak is I. b The peak intensity at the peak wavelength of the third absorption peak is I. c .
[0034] The I a The value of I is c More than 40%, and further options include more than 45%.
[0035] The I b The value of I is c More than 50%, and further options include more than 60%.
[0036] In one embodiment, the absorption spectrum of the phosphor composition further includes a fourth absorption peak.
[0037] The peak wavelength of the fourth absorption peak is between 620 nm and 700 nm.
[0038] In one embodiment, the peak intensity at the peak wavelength of the first absorption peak is I. a The peak intensity at the peak wavelength of the second absorption peak is I. b The peak intensity at the peak wavelength of the third absorption peak is I. c The peak intensity at the peak wavelength of the fourth absorption peak is I. d .
[0039] The I a The value of I is c More than 40%, and further options include more than 45%.
[0040] The I b The value of I is c More than 50%, and further options include more than 60%.
[0041] The I d The value of I is c More than 5%, and further options include more than 10%.
[0042] In a second aspect, this application provides an LED device comprising the phosphor composition described in the first aspect.
[0043] Compared with the prior art, this application has the following advantages:
[0044] The phosphor composition provided in this application, through the use of specific phosphor additives, can utilize the specific absorption peaks of the phosphor additives to absorb the emission bands in the phosphor, thereby obtaining a phosphor composition with narrow half-width, stable crystal structure, and superior luminescence performance.
[0045] After reading and understanding the accompanying diagrams and detailed descriptions, the other aspects can be understood. Attached Figure Description
[0046] The accompanying drawings are used to provide a further understanding of the technical solutions in this paper and form part of the specification. They are used together with the embodiments of this application to explain the technical solutions in this paper and do not constitute a limitation on the technical solutions in this paper.
[0047] Figure 1 shows the emission spectra of the phosphor composition in Example 1 and the phosphor in Comparative Example 1.
[0048] Figure 2 shows the absorption spectrum of the phosphor composition in Example 1.
[0049] Figure 3 shows the absorption spectrum of the phosphor in Comparative Example 1.
[0050] Figure 4 shows the emission spectrum of the light-emitting device in Application Example 1.
[0051] Figure 5 shows the color gamut of the light-emitting device in Application Example 1.
[0052] Figure 6 shows the emission spectrum of the light-emitting device in Comparative Application Example 1.
[0053] Figure 7 shows the emission spectra of the light-emitting devices in Application Examples 1-2 and 1-3.
[0054] Figure 8 shows the color zone diagram of the light-emitting device in Application Example 1-1.
[0055] Figure 9 shows the emission spectrum of the light-emitting device in Application Example 7 and Comparative Application Example 2.
[0056] Figures 10, 11 and 12 are schematic diagrams of the structure of the light-emitting device provided in this application.
[0057] Wherein: 101, substrate; 102, encapsulating adhesive; 103, phosphor composition; 104, light-emitting element. Detailed Implementation
[0058] The technical solution of this application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely to help understand this application and should not be regarded as specific limitations on this application.
[0059] In the specific embodiments of this application, the method for measuring the emission spectrum is as follows: after preparing the sample to be tested, it is placed on the sample stage of the fluorescence spectrometer, and the emission wavelength range λ is measured. min To λ max The internal spectra of the sample to be tested are acquired. λ min The excitation wavelength is 15 nm larger than that of the sample to be tested, λ max That is below 800nm.
[0060] In the specific embodiments of this application, the method for measuring the absorption spectrum is as follows: the measurement is performed using an ultraviolet-visible spectrophotometer. First, the tungsten lamp and deuterium lamp are preheated. The wavelength range is set to 200 nm to 800 nm, the scanning speed is 600 pm / min, the data sampling interval is 2 nm, and the slit width is 2 nm. The barium sulfate standard white plate is used for scanning. After correction, the sample to be tested is collected to obtain the reflectance R of the sample to be tested. Based on the correspondence between reflectance and absorptivity, the absorption spectrum of the sample to be tested in the range of 200 nm to 800 nm is calculated.
[0061] In the specific embodiments of this application, the median particle size is determined using a particle size analyzer.
[0062] In a specific embodiment of this application, the aspect ratio of β-SiAlON green powder is determined using a particle size analyzer.
[0063] In the specific embodiments of this application, a quantum efficiency tester is used to measure the emission spectrum, absorption spectrum, color temperature and chromaticity of the phosphor composition, the color gamut is calculated using color coordinates, and the luminous flux is measured using an integrating sphere.
[0064] One embodiment of this application provides a phosphor composition comprising phosphor and phosphor additives, wherein the phosphor additives comprise neodymium-containing inorganic compounds and / or neodymium-containing organic compounds.
[0065] The neodymium-containing inorganic compound includes Nd a A x B y O z And / or NdM, where a>0, x≥0, y≥0, z>0 and 3×a+n1×x+n2×y=2z, n1 is the valence state of A ion, and n2 is the valence state of B ion; A includes at least one of H, N, S, F, Cl, Br, I, Na, K, Al, Mg, Li, Ca, Sr, Ba, Al, Si, B, Ga, In, Ge or Sn; B includes at least one of H, N, S, F, Cl, Br, I, Na, K, Al, Mg, Li, Ca, Sr, Ba, Al, Si, B, Ga, In, Ge or Sn; M includes at least one of N, S, Cl, F, Br or I.
[0066] The neodymium-containing organic compounds include at least one of neodymium acetate, neodymium acetylacetonate, neodymium-based metal-organic frameworks (MOF-Nd), binary neodymium complexes, or ternary neodymium complexes.
[0067] In one embodiment, the binary neodymium complex includes at least one of NdCl2(Ph3P)2, Nd(NO3)3, Nd(ClO4)3, Nd(BF4)3, or Nd(SO4)2(H2O)4. Typical but non-limiting combinations include combinations of NdCl2(Ph3P)2 and Nd(NO3)3, combinations of Nd(NO3)3, Nd(ClO4)3 and Nd(BF4)3, combinations of Nd(BF4)3 and Nd(SO4)2(H2O)4, or combinations of NdCl2(Ph3P)2, Nd(NO3)3, Nd(ClO4)3, Nd(BF4)3 and Nd(SO4)2(H2O)4.
[0068] In one embodiment, the ternary neodymium complex comprises Nd(phen)2(GA)3·H2O.
[0069] In one embodiment, the phosphor additive is at least one of neodymium acetate, neodymium fluoride, or neodymium oxide. Typical but non-limiting combinations include combinations of neodymium acetate and neodymium fluoride, combinations of neodymium fluoride and neodymium oxide, combinations of neodymium acetate and neodymium oxide, or combinations of neodymium acetate, neodymium fluoride, and neodymium oxide.
[0070] A suitable average particle size for phosphor additives facilitates sufficient contact between the additive and the phosphor, thereby improving the phosphor's luminescence efficiency and promoting uniform emission upon excitation, thus enhancing the phosphor's performance stability. However, excessively small phosphor additive particle sizes can cause a shift in emission wavelength, affecting the purity of the phosphor's emitted color.
[0071] In one embodiment, the average particle size of the phosphor additive is 0.1 μm or more and 10 μm or less, for example, it can be 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 8 μm or 10 μm, and may be further selected as 0.1 μm or more and 5 μm or less.
[0072] In one embodiment, the phosphor includes any one of fluorescent green, fluorescent yellow, or fluorescent red.
[0073] In one embodiment, the fluorescent yellow powder includes yttrium aluminum garnet (YAG), gallium-doped yttrium aluminum garnet (Ga-YAG), lutetium aluminum garnet (LuAG), or La3Si6N. 11 (La3Si6N 11 :Ce 3+ At least one of the following, typical but non-limiting combinations include combinations of YAG and Ga-YAG, combinations of YAG and LuAG, and combinations of YAG and La3Si6N. 11 :Ce 3+Combinations of YAG, LuAG and La3Si6N 11 :Ce 3+ Combinations of YAG, Ga-YAG, LuAG and La3Si6N 11 :Ce 3+ The combination of .
[0074] In one embodiment, the fluorescent red powder includes nitride red powder 1113((SrCa)AlSiN3:Eu 2+ ), Nitride Red Powder 258 (Sr2Si5N8:Eu) 2+ ) or (Ca,Sr)S:Eu 2+ At least one of the following, typical but non-limiting combinations include combinations of nitride red powder 1113 and nitride red powder 258, and nitride red powder 1113 and (Ca,Sr)S:Eu 2+ The combination of nitride red powder 258 and (Ca,Sr)S:Eu 2+ Combinations, or, nitride red powder 1113, nitride red powder 258 and (Ca,Sr)S:Eu 2+ The combination of .
[0075] In one embodiment, the fluorescent green powder comprises β-SiAlON green powder and / or SrGa2S4:Eu 2+ .
[0076] Appropriate phosphor additives can improve the luminescence intensity of phosphor compositions, but excessive phosphor additives can affect color accuracy and saturation, and also pose a risk of reducing luminescence intensity.
[0077] In one embodiment, the phosphor composition comprises, by weight percentage, 5 wt% to 90 wt% of phosphor additives, such as 5 wt%, 10 wt%, 20 wt%, 40 wt%, 50 wt%, 60 wt%, 80 wt%, or 90 wt%.
[0078] In one embodiment, the phosphor is β-SiAlON green phosphor.
[0079] The median particle size of the β-SiAlON green powder is 10 μm to 40 μm, for example, it can be 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm or 40 μm, and can be further selected as 15 μm to 30 μm.
[0080] The aspect ratio of the β-SiAlON green powder is 1:1 to 20:1, for example, it can be 1:1, 2:1, 5:1, 10:1, 15:1 or 20:1, and can be further selected as 2:1 to 15:1.
[0081] In this application, the aspect ratio of β-SiAlON green powder refers to the ratio of the average length L to the average width W of the β-SiAlON green powder. The length L refers to the dimension of the β-SiAlON green powder along its longest axis, and the width W refers to the dimension of the β-SiAlON green powder along its shortest axis perpendicular to the length L.
[0082] In one embodiment, the peak wavelength λ of the main peak in the emission spectrum of the phosphor composition is 520 nm to 550 nm, for example, it can be 520 nm, 530 nm, 540 nm or 550 nm.
[0083] The emission spectrum of the phosphor composition has a full width at half maximum (FWHM) of 30 nm to 60 nm, for example, 30 nm, 40 nm, 50 nm or 60 nm.
[0084] In one embodiment, the emission spectrum of the phosphor composition satisfies the following condition: the intensity at λ1 is greater than the intensity at λ2, where λ1 is λ-Δλ, λ2 is λ+Δλ, and Δλ is less than 30 nm, such as 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, or 30 nm.
[0085] In one embodiment, the emission spectrum of the phosphor composition includes a first characteristic peak and a second characteristic peak on both sides of the main peak.
[0086] The peak wavelength of the first characteristic peak is 500nm to 530nm, for example, it can be 500nm, 505nm, 510nm, 515nm, 520nm, 525nm or 530nm, and can be further selected as 510nm to 525nm.
[0087] The peak wavelength of the second characteristic peak is 590nm to 630nm, for example, it can be 590nm, 595nm, 600nm, 610nm, 615nm, 620nm, 625nm or 630nm, and can be further selected as 600nm to 620nm.
[0088] In one embodiment, the peak intensity at the peak wavelength of the main peak is I1; the peak intensity at the peak wavelength of the first characteristic peak is I2; and the peak intensity at the peak wavelength of the second characteristic peak is I3.
[0089] The value of I2 is less than 80% of I1, for example, it can be 50%, 55%, 60%, 65%, 70%, 75% or 80%, and can be further selected as less than 65%.
[0090] The value of I3 is less than 30% of I1, for example, it can be 5%, 10%, 15%, 20%, 25% or 30%, and can be further selected as less than 20%.
[0091] In this application, the peak intensity at the peak wavelength of the main peak, the peak intensity at the peak wavelength of the first characteristic peak, and the peak intensity at the peak wavelength of the second characteristic peak are the peak intensities of the emission spectrum after normalization. Optionally, the normalization method includes: normalizing based on the peak height of the highest green peak, and the ratio of the intensity of the remaining peaks to the intensity of the highest peak is the normalized value of the remaining peaks.
[0092] In one embodiment, the absorption spectrum of the phosphor composition includes a first absorption peak, a second absorption peak, and a third absorption peak with successively increasing peak wavelengths.
[0093] The peak wavelength of the first absorption peak is 500nm to 522nm, for example, it can be 520nm, 505nm, 510nm, 515nm, 520nm or 522nm, etc.
[0094] The peak wavelength of the second absorption peak is 521nm to 540nm, for example, it can be 521nm, 522nm, 525nm, 528nm, 530nm, 535nm or 540nm, etc.
[0095] The peak wavelength of the third absorption peak is 570nm to 600nm, for example, it can be 570nm, 575nm, 580nm, 585nm, 590nm, 595nm or 600nm, etc.
[0096] In one embodiment, the peak intensity at the peak wavelength of the first absorption peak is I. a The peak intensity at the peak wavelength of the second absorption peak is I. b The peak intensity at the peak wavelength of the third absorption peak is I. c .
[0097] The I a The value of I is c It can be 40% or more, for example, 40%, 45%, 48%, 50%, 55%, 60% or 65%, and can be further selected as 45% or more.
[0098] The I b The value of I is c It can be 50% or more, for example, 50%, 55%, 60%, 65% or 70%, and can be further selected as 60% or more.
[0099] In one embodiment, the absorption spectrum of the phosphor composition further includes a fourth absorption peak.
[0100] The peak wavelength of the fourth absorption peak is 620nm to 700nm, for example, it can be 620nm, 630nm, 640nm, 650nm, 660nm, 680nm or 700nm, etc.
[0101] In one embodiment, the peak intensity at the peak wavelength of the first absorption peak is I. a The peak intensity at the peak wavelength of the second absorption peak is I. b The peak intensity at the peak wavelength of the third absorption peak is I. c The peak intensity at the peak wavelength of the fourth absorption peak is I. d .
[0102] In this application, the peak intensity at the peak wavelength of the first absorption peak, the peak intensity at the peak wavelength of the second absorption peak, and the peak intensity at the peak wavelength of the third absorption peak are the peak intensities of the absorption spectrum after normalization. The normalization method includes: normalizing based on the peak height of the third absorption peak, and the ratio of the intensity of the remaining peaks to the intensity of the highest peak is the normalized value of the remaining peaks.
[0103] The I a The value of I is c It can be 40% or more, for example, 40%, 45%, 48%, 50%, 55%, 60% or 65%, and can be further selected as 45% or more.
[0104] The I b The value of I is c It can be 50% or more, for example, 50%, 55%, 60%, 65% or 70%, and can be further selected as 60% or more.
[0105] The I d The value of I is c It can be 5% or more, for example, 5%, 10%, 15%, 20%, 25% or 30%, and can be further selected as 10% or more.
[0106] The phosphor composition that meets the requirements of this application has an absorption efficiency of 60% or more and an internal quantum efficiency of 70% or more; as an optional embodiment of this application, the phosphor composition can achieve an absorption efficiency of 90% and an internal quantum efficiency of 85%.
[0107] External quantum efficiency (EQE) refers to the ratio of the number of fluorescent photons emitted by the phosphor composition to the number of incident photons of the excitation light. It reflects the luminous efficiency of the phosphor composition in practical applications, and its value is the product of the absorption efficiency and the internal quantum efficiency. In this application, the EQE of the phosphor composition is 42% or higher, and in some embodiments, the EQE can reach 76%.
[0108] In one embodiment, the preparation method of the phosphor composition includes either a physical mixing method or a sol-gel method.
[0109] In one embodiment, the physical mixing method includes the following steps: mixing a formulated amount of phosphor additive and phosphor in an organic solvent to obtain a slurry; heat-treating to remove the organic solvent from the obtained slurry to obtain a solid mixture; and grinding the obtained solid mixture to obtain a phosphor composition.
[0110] In one embodiment, the organic solvent used in the physical mixing method includes anhydrous ethanol and / or acetone.
[0111] In one embodiment, the mixing method in the physical mixing method includes mechanical grinding and / or ball milling.
[0112] This application does not specify the specific mixing parameters in the physical mixing method, as long as the phosphor additive in the formulation is uniformly mixed with the phosphor.
[0113] In one embodiment, the heat treatment temperature in the physical mixing method is 80°C to 150°C, for example, it can be 80°C, 90°C, 100°C, 120°C, 140°C or 150°C.
[0114] In one embodiment, the sol-gel method includes: hydrolyzing the phosphor additive into neodymium hydroxide colloid; converting the resulting neodymium hydroxide colloid into a sol; then mixing the phosphor with the sol to form a gel; and drying and calcining the gel to obtain a phosphor composition.
[0115] In one embodiment, the drying temperature in the sol-gel method is 80°C to 150°C, for example, it can be 80°C, 90°C, 100°C, 120°C, 140°C or 150°C.
[0116] In one embodiment, the calcination temperature in the sol-gel method is above 300°C, for example, it can be 300°C, 320°C, 350°C, 380°C or 400°C, etc.; In this application, through calcination, the neodymium hydroxide obtained by hydrolyzing the phosphor additive is finally converted into nano-neodymium oxide and attached to the surface of the phosphor, thereby achieving modification of the phosphor.
[0117] One embodiment of this application provides an LED device comprising the phosphor composition of any embodiment.
[0118] One embodiment of this application provides a light-emitting device, which includes a light-emitting element and a wavelength conversion unit; the light-emitting element is used to emit primary light; the wavelength conversion unit is used to absorb the primary light emitted by the light-emitting element and emit secondary light with a longer wavelength; the wavelength conversion unit includes a phosphor composition as described in any embodiment and a red phosphor.
[0119] In this application, the light-emitting device can be a TOP type light-emitting device, a CHIP type light-emitting device, or a CSP type light-emitting device.
[0120] Figure 10 shows a schematic diagram of the structure of the TOP type light-emitting device, which includes a substrate 101 and a cup-shaped support. The cup-shaped support forms a receiving cavity, and the light-emitting element 104 is disposed in the receiving cavity. The encapsulating adhesive 102 containing phosphor composition 103 covers the light-emitting element and fills the receiving cavity.
[0121] Figure 11 shows a schematic diagram of the structure of the CHIP-type light-emitting device, which includes a substrate 101 and a light-emitting element 104 placed on the substrate 101; an encapsulating adhesive 102 containing a phosphor composition 103 covers the light-emitting element 104.
[0122] Figure 12 shows a schematic diagram of the CSP type light-emitting device, which directly uses an encapsulating adhesive 102 containing a phosphor composition 103 to cover the light-emitting element 104.
[0123] In one embodiment, the light-emitting element is a blue light-emitting element, and the main wavelength of the blue light emitted is 440nm to 465nm, for example, it can be 440nm, 445nm, 450nm, 455nm, 460nm or 465nm, etc.
[0124] In one embodiment, the peak wavelength of the blue light-emitting element is 5nm to 6nm smaller than the main wavelength, specifically 434nm to 460nm, such as 434nm, 435nm, 440nm, 445nm, 450nm, 455nm, or 460nm.
[0125] In one embodiment, the red phosphor comprises a fluoride phosphor (K2SiF6:Mn). 4+ KSF) and / or nitride phosphors ((SrCa)AlSiN3:Eu 2+ ).
[0126] In one embodiment, the red phosphor is a fluoride phosphor, and the mass ratio of the phosphor composition to the fluoride phosphor is 1:2 to 1:6, for example, it can be 1:2, 1:3, 1:4, 1:5 or 1:6, and more preferably 1:3 to 1:5.
[0127] In one embodiment, the red phosphor is a nitride phosphor, and the mass ratio of the phosphor composition to the nitride phosphor is 1:0.02 to 1:0.17, for example, it can be 1:0.05, 1:0.06, 1:0.08, 1:0.1, 1:0.12 or 1:0.15, etc., and is further selected as 1:0.09 to 1:0.13.
[0128] One embodiment of this application provides a method for fabricating a light-emitting device, the method comprising sequentially performing adhesive preparation and adhesive dispensing.
[0129] The formulation process involves mixing the formulated amount of phosphor composition, red luminescent phosphor, and encapsulating adhesive to form a uniform fluorescent adhesive.
[0130] In one embodiment, the mass ratio of the encapsulating adhesive to the phosphor composition is 10:1 to 10:9, for example, it can be 10:1, 10:3, 10:5, 10:6, 10:8 or 10:9.
[0131] The dispensing process includes: dispensing fluorescent adhesive onto the light-emitting element, and after curing, obtaining the light-emitting device.
[0132] One embodiment of this application provides a light-emitting device, the emission spectrum of which includes a main emission peak, and a first emission peak and a first emission valley respectively distributed on both sides of the main emission peak.
[0133] The peak wavelength of the main emission peak is 520nm to 550nm, for example, it can be 520nm, 530nm, 540nm or 550nm.
[0134] The full width at half maximum (FWHM) of the main emission peak is 30nm to 60nm, for example, it can be 30nm, 35nm, 40nm, 45nm, 50nm, 55nm or 60nm, and can be further selected as 35nm to 50nm.
[0135] The peak wavelength of the first emission peak is 500nm to 530nm, for example, it can be 500nm, 505nm, 510nm, 515nm, 520nm, 525nm or 530nm, and can be further selected as 510nm to 525nm.
[0136] The valley wavelength of the first emission valley is 550nm to 610nm, for example, it can be 550nm, 560nm, 580nm, 600nm or 610nm, and can be further selected as 560nm to 600nm.
[0137] In one embodiment, the peak intensity at the peak wavelength of the main emission peak is I. a The peak intensity at the peak wavelength of the first emission peak is I. b The peak-valley intensity of the first emission valley at wavelengths of 580 to 585 nm is I. c .
[0138] In this application, the peak intensity at the peak wavelength of the main emission peak, the peak intensity at the peak wavelength of the first emission peak, and the peak-valley intensity of the first emission valley at wavelengths of 580 to 585 nm are the peak intensities of the emission spectrum after normalization. Optionally, the normalization method includes: normalizing based on the peak height of the main emission peak, and the ratio of the intensity of the remaining peaks to the intensity at the peak wavelength of the main emission peak is the normalized value of the remaining peaks.
[0139] The I b The value of I is a It can be below 80%, for example, it can be 50%, 55%, 60%, 65%, 70%, 75% or 80%, and can be further selected as below 65%.
[0140] The I c The value of I is a It can be less than 40%, for example, it can be 20%, 25%, 30%, 35% or 40%, and can be further selected as less than 35%.
[0141] In one embodiment, the peak wavelength of the main emission peak is λ. a The emission spectrum of the light-emitting device satisfies: λ b The intensity at that point is greater than λ c The intensity at λ, where λ b For λ a -△λ a , λ c For λ a +△λ a , △λ a It is below 30nm.
[0142] For example, in a light-emitting device, the wavelength conversion section includes a green phosphor composition and a red nitride phosphor, and its emission spectrum has a red main emission peak in the wavelength range of 600 nm to 700 nm; the peak intensity at the peak wavelength of the red main emission peak is I. xNormalization is performed based on the peak height of the main emission peak within the green light wavelength range, I x The value range is 0.5-2.
[0143] In some embodiments, the wavelength conversion section of the light-emitting device includes a phosphor composition and fluoride red phosphor; the phosphor composition includes phosphor additives and phosphor; the phosphor includes fluorescent green phosphor or fluorescent yellow phosphor.
[0144] In one embodiment, the emission spectrum of the light-emitting device has a red main emission peak, a first red emission peak, and a second red emission peak in the wavelength range of 600 nm to 700 nm.
[0145] The first red light emission peak is located on the short-wave side of the main red light emission peak.
[0146] The second red light emission peak is located on the long-wavelength side of the main red light emission peak.
[0147] The peak intensity at the peak wavelength of the red light main emission peak is I. x The I x Greater than the I a .
[0148] In one embodiment, the peak wavelength of the red light main emission peak is 620 nm to 640 nm, and the full width at half maximum (FWHM) is 4 nm to 10 nm.
[0149] The peak wavelength of the first red light emission peak is 600nm to 620nm, for example, it can be 600nm, 605nm, 610nm, 615nm or 620nm, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0150] The peak wavelength of the second red light emission peak is 640nm to 670nm, for example, it can be 640nm, 645nm, 650nm, 655nm, 660nm, 665nm or 670nm, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0151] In one embodiment, the peak intensity at the peak wavelength of the red light main emission peak is I. x The peak intensity at the peak wavelength of the first red light emission peak is I. y The peak intensity at the peak wavelength of the second red light emission peak is I. z Then the I x Greater than the I y And the I y Greater than the I z .
[0152] In one implementation, normalization is performed based on the peak height of the main emission peak within the green light wavelength range, I x The value range is 0.8-4, for example, it can be 0.8, 1, 1.5, 2, 2.5, 3, 3.5 or 4, but is not limited to the listed values. Other unlisted values within the range are also applicable, preferably 2-4; I y The value range is 1-2, for example, it can be 1, 1.2, 1.5, 1.6, 1.8 or 2, but it is not limited to the listed values. Other unlisted values within the range also apply; I z The value range is 0.2-1, for example, it can be 0.2, 0.4, 0.5, 0.6, 0.8 or 1, but it is not limited to the listed values. Other unlisted values within the range are also applicable.
[0153] One embodiment of this application provides a light-emitting device with a color temperature of 6000K or higher, such as 6000K, 6500K, 7000K, 7500K, 8000K, 8500K, or 9000K, and more preferably 8000K or higher. K stands for Kelvin.
[0154] The target color area of the light-emitting device satisfies the following condition: the area enclosed by the first color point, the second color point, the third color point and the fourth color point in the color area diagram can be a regular shape or an irregular shape.
[0155] The coordinates of the first color point are (0.301, 0.313), which can be further selected as (0.298, 0.306), and further selected as (0.293, 0.298); the coordinates of the second color point are (0.259, 0.240), which can be further selected as (0.284, 0.283), and further selected as (0.288, 0.290); the coordinates of the third color point are (0.316, 0.293), which can be further selected as (0.305, 0.295), and further selected as (0.300, 0.288); the coordinates of the fourth color point are (0.274, 0.220), which can be further selected as (0.291, 0.273), and further selected as (0.295, 0.280).
[0156] The color coordinates of the light-emitting device at different color temperature center points satisfy: Δx is less than 0.1 and Δy is less than 0.1; further optionally, Δx is less than 0.05 and Δy is less than 0.05; further optionally, Δx is less than 0.02 and Δy is less than 0.02.
[0157] In one embodiment, the NTSC color gamut of the light-emitting device is 80% or more, for example, it can be 80%, 82%, 84%, 85%, 90%, 92% or 94%, and more preferably 84% or more.
[0158] In one embodiment, the DCI-P3 color gamut of the light-emitting device is above 90%, for example, it can be 90%, 91%, 92%, 93%, 94%, 95% or 96%, etc.
[0159] Example 1
[0160] This embodiment provides a phosphor composition, comprising phosphor and phosphor additives.
[0161] The phosphor is β-SiAlON green phosphor with a median particle size of 20 μm and an aspect ratio of 10:1.
[0162] The phosphor additive is neodymium acetate with an average particle size of 0.5 μm; the total mass percentage of phosphor and phosphor additive is 100%, of which the mass percentage of phosphor additive is 20%.
[0163] The preparation method of the phosphor composition provided in this embodiment includes: ball milling and uniformly mixing the phosphor additive and phosphor in anhydrous ethanol to obtain a mixture slurry; heat-treating the obtained mixture slurry at a temperature of 100°C to remove the anhydrous ethanol to obtain a solid mixture; and grinding the obtained solid mixture to obtain the phosphor composition.
[0164] The emission spectrum of the phosphor composition in this embodiment is shown in Figure 1, and the absorption spectrum is shown in Figure 2.
[0165] Comparative Example 1
[0166] This comparative example provides a phosphor, which is the β-SiAlON green phosphor from Example 1.
[0167] The emission spectrum of the phosphor in this comparative example is shown in Figure 1, and the absorption spectrum is shown in Figure 3.
[0168] The relevant parameters of the phosphor and phosphor additives in the phosphor compositions provided in Examples 1 to 6 and the phosphor provided in Comparative Example 1 are shown in Table 1.
[0169] Table 1
[0170] The emission spectrum data of the phosphor compositions provided in Examples 1 to 6, and the phosphor provided in Comparative Example 1, are shown in Table 2.
[0171] Table 2
[0172] The absorption spectrum data of the phosphor compositions provided in Examples 1 to 6, and the phosphor provided in Comparative Example 1, are shown in Table 3.
[0173] Table 3
[0174] Example 7
[0175] This embodiment provides a phosphor composition, comprising phosphor and phosphor additives.
[0176] The fluorescent powder is YAG fluorescent yellow powder.
[0177] The phosphor additive is neodymium acetate with an average particle size of 0.5 μm; the total mass percentage of phosphor and phosphor additive is 100%, of which the mass percentage of phosphor additive is 20%.
[0178] The preparation method of the phosphor composition provided in this embodiment includes: ball milling and uniformly mixing the phosphor additive and phosphor in anhydrous ethanol to obtain a mixture slurry; heat-treating the obtained mixture slurry at a temperature of 100°C to remove the anhydrous ethanol to obtain a solid mixture; and grinding the obtained solid mixture to obtain the phosphor composition.
[0179] Application Example 1-1
[0180] This application example provides a TOP type light-emitting device, which includes a light-emitting element and a wavelength conversion unit; the light-emitting element is used to emit primary light; the wavelength conversion unit is used to absorb the primary light emitted by the light-emitting element and emit secondary light with a longer wavelength; the wavelength conversion unit includes the phosphor composition in Example 1 and a red phosphor.
[0181] The light-emitting element in this application example is a blue light-emitting element with a dominant wavelength of 450nm and a peak wavelength of 445nm.
[0182] In this application example, the red phosphor is a fluoride phosphor KSF, and the mass ratio of the phosphor composition to the fluoride phosphor is 1:3.
[0183] The method for preparing the light-emitting device provided in this application example includes the following steps: providing a blue light-emitting element; uniformly mixing the formulated amount of phosphor composition, KSF, and encapsulating adhesive to obtain a phosphor adhesive; dispensing the phosphor adhesive onto the blue light-emitting element using a fluorescent agent, and then heating and curing to obtain the light-emitting device. The mass ratio of the encapsulating adhesive to the phosphor composition is 10.5:1.
[0184] The emission spectrum of the light-emitting device obtained in this application example is shown in Figure 4, the color gamut diagram is shown in Figure 5, and the color region diagram is shown in Figure 8.
[0185] Comparative Application Example 1
[0186] Except for replacing the phosphor composition with the phosphor in Comparative Example 1 by the same mass, the treatment in this comparative application example is the same as in Application Example 1-1.
[0187] The emission spectrum of the light-emitting device obtained in this comparative application example is shown in Figure 6.
[0188] Comparative Application Example 2
[0189] This comparative application example is identical to application example 1-1 except that the phosphor composition is replaced by the same mass as the phosphor in example 7.
[0190] The emission spectrum of the light-emitting device provided in this comparative application example is shown in Figure 9.
[0191] In Application Examples 1-2 to 1-3, except for the composition and amount of the red-based luminescent phosphor as shown in Table 4, everything else is the same as in Application Example 1-1. The emission spectra of the luminescent devices provided in Application Examples 1-2 and 1-3 are shown in Figure 7.
[0192] Table 4
[0193] Application Example 2
[0194] This application example provides a light-emitting device, which is the same as application example 1-1 except that the phosphor composition is the phosphor composition provided in example 2.
[0195] Application Example 3
[0196] This application example provides a light-emitting device, which is the same as application example 1-1 except that the phosphor composition is the phosphor composition provided in example 3.
[0197] Application Example 4
[0198] This application example provides a light-emitting device, which is the same as application example 1-1 except that the phosphor composition is the phosphor composition provided in example 4.
[0199] Application Example 5
[0200] This application example provides a light-emitting device, which is the same as application example 1-1 except that the phosphor composition is the phosphor composition provided in example 5.
[0201] Application Example 6
[0202] This application example provides a light-emitting device, which is the same as application example 1-1 except that the phosphor composition is the phosphor composition provided in example 6.
[0203] Application Example 7
[0204] This application example provides a light-emitting device, which is the same as application example 1-1 except that the phosphor composition is the phosphor composition provided in example 7.
[0205] The emission spectrum of the light-emitting device provided in this application example is shown in Figure 9.
[0206] The color coordinates, NTSC color gamut, and DCI-P3 color gamut data of the light-emitting devices provided in Application Examples 2 to 7, as well as Comparative Application Examples 1 and 2, are shown in Table 5.
[0207] Table 5
[0208] The emission spectrum data of the light-emitting devices in Application Examples 1-1 to 1-3, Application Examples 2 to 7, and Comparative Application Examples 1 and 2 are shown in Table 6.
[0209] Table 6
[0210] In summary, the phosphor composition provided in this application, through the use of specific phosphor additives, can utilize the specific absorption peaks of the phosphor additives to absorb the emission bands in the phosphor, thereby obtaining a phosphor composition with narrow half-width, stable crystal structure, and superior luminescence performance.
[0211] The above description is only a specific embodiment of this application, but the protection scope of this application is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in this application fall within the protection and disclosure scope of this application.
Claims
A fluorescent powder composition comprising fluorescent powder and fluorescent powder additives; The fluorescent powder additive includes neodymium-containing inorganic compounds and / or neodymium-containing organic compounds; The neodymium-containing inorganic compound includes Nd a A x B y O z And / or NdM, where a>0, x≥0, y≥0, z>0 and 3×a+n1×x+n2×y=2z, n1 is the valence state of A ion, and n2 is the valence state of B ion; A includes at least one of H, N, S, F, Cl, Br, I, Na, K, Al, Mg, Li, Ca, Sr, Ba, Al, Si, B, Ga, In, Ge or Sn; B includes at least one of H, N, S, F, Cl, Br, I, Na, K, Al, Mg, Li, Ca, Sr, Ba, Al, Si, B, Ga, In, Ge or Sn; M includes at least one of N, S, Cl, F, Br or I; The neodymium-containing organic compound includes at least one of neodymium acetate, neodymium acetylacetonate, MOF-Nd, binary neodymium complexes, or ternary neodymium complexes. According to claim 1, the phosphor composition, wherein, The fluorescent powder additive is at least one of neodymium acetate, neodymium fluoride, or neodymium oxide. According to claim 1, the phosphor composition, wherein, The average particle size of the fluorescent additive is greater than 0.1 μm and less than 10 μm. According to claim 1, the phosphor composition, wherein, The average particle size of the fluorescent additive is greater than 0.1 μm and less than 5 μm. According to claim 1, the phosphor composition, wherein, The phosphor includes any one of fluorescent green, fluorescent yellow, or fluorescent red. According to claim 1, the phosphor composition, wherein, The phosphor composition comprises 5 wt% to 90 wt% phosphor additives by weight percentage. According to claim 1, the phosphor composition, wherein, The phosphor composition comprises 20 wt% to 50 wt% phosphor additives by weight percentage. According to claim 5, the phosphor composition, wherein, The phosphor is β-SiAlON green phosphor; The median particle size of the β-SiAlON green powder is 10 μm to 40 μm; The aspect ratio of the β-SiAlON green powder is from 1:1 to 20:
1. According to claim 5, the phosphor composition, wherein, The median particle size of the β-SiAlON green powder is 15 μm to 30 μm; The aspect ratio of the β-SiAlON green powder is 2:1 to 15:
1. According to claim 1, the phosphor composition, wherein, In the emission spectrum of the phosphor composition, the peak wavelength λ of the main peak is 520 nm to 550 nm; The emission spectrum of the phosphor composition has a full width at half maximum (FWHM) of 30 nm to 60 nm for the main peak. According to claim 1, the phosphor composition, wherein, The emission spectrum of the phosphor composition satisfies the following condition: the intensity at λ1 is greater than the intensity at λ2, where λ1 is λ-Δλ, λ2 is λ+Δλ, and Δλ is below 30 nm. According to claim 1, the phosphor composition, wherein, The emission spectrum of the phosphor composition includes a first characteristic peak and a second characteristic peak on both sides of the main peak; The peak wavelength of the first characteristic peak is 500 nm to 530 nm; The peak wavelength of the second characteristic peak is between 590 nm and 630 nm. According to claim 12, the phosphor composition, wherein, The peak wavelength of the first characteristic peak is 510 nm to 525 nm; The peak wavelength of the second characteristic peak is 600 nm to 620 nm. According to claim 12, the phosphor composition, wherein, The peak intensity at the peak wavelength of the main peak is I1; the peak intensity at the peak wavelength of the first characteristic peak is I2; and the peak intensity at the peak wavelength of the second characteristic peak is I3. The value of I2 is less than 80% of the value of I1; The value of I3 is less than 30% of that of I1. According to claim 12, the phosphor composition, wherein, The peak intensity at the peak wavelength of the main peak is I1; the peak intensity at the peak wavelength of the first characteristic peak is I2; and the peak intensity at the peak wavelength of the second characteristic peak is I3. The value of I2 is less than 65% of the value of I1; The value of I3 is less than 20% of that of I1. According to claim 5, the phosphor composition, wherein, The absorption spectrum of the phosphor composition includes a first absorption peak, a second absorption peak, and a third absorption peak; The peak wavelength of the first absorption peak is from 500 nm to 522 nm; The peak wavelength of the second absorption peak is from 521 nm to 540 nm; The peak wavelength of the third absorption peak is between 570 nm and 600 nm. According to claim 16, the phosphor composition, wherein, The peak intensity at the peak wavelength of the first absorption peak is I a The peak intensity at the peak wavelength of the second absorption peak is I. b The peak intensity at the peak wavelength of the third absorption peak is I. c ; The I a The value of I is c More than 40%; The I b The value of I is c More than 50%. The phosphor composition according to claim 16 or 17, wherein, The absorption spectrum of the phosphor composition also includes a fourth absorption peak; The peak wavelength of the fourth absorption peak is between 620 nm and 700 nm. According to claim 18, the phosphor composition, wherein, The peak intensity at the peak wavelength of the first absorption peak is I a The peak intensity at the peak wavelength of the second absorption peak is I. b The peak intensity at the peak wavelength of the third absorption peak is I. c The peak intensity at the peak wavelength of the fourth absorption peak is I. d ; The I a The value of I is c More than 40%; The I b The value of I is c More than 50%; The I d The value of I is c More than 5%. An LED device comprising the phosphor composition according to any one of claims 1 to 19.