CN114759131B - Light emitting device and lighting apparatus - Google Patents
Light emitting device and lighting apparatus Download PDFInfo
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- CN114759131B CN114759131B CN202210393938.9A CN202210393938A CN114759131B CN 114759131 B CN114759131 B CN 114759131B CN 202210393938 A CN202210393938 A CN 202210393938A CN 114759131 B CN114759131 B CN 114759131B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
- H01L33/504—Elements with two or more wavelength conversion materials
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77347—Silicon Nitrides or Silicon Oxynitrides
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7737—Phosphates
- C09K11/7738—Phosphates with alkaline earth metals
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- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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Abstract
The application discloses a light-emitting device and a lighting device, and belongs to the technical field of luminescent materials. The light emitting device includes a fluorescent layer and an excitation chip; the fluorescent layer comprises blue fluorescent powder, green fluorescent powder, yellow fluorescent powder, red fluorescent powder and near infrared fluorescent powder; wherein the blue fluorescent powder contains a blue fluorescent material a; the blue fluorescent material a is selected from any one of substances shown in a formula I-1. The similarity between the spectrum emitted by the solar spectrum light-emitting device in the visible light range (380-780 nm) and the solar spectrum is above 98%, and the aim of being consistent with the solar spectrum is basically achieved.
Description
Technical Field
The present application relates to the field of luminescent materials, and in particular, to a light emitting device and a lighting apparatus.
Background
With the improvement of the requirements of people on the quality of light, the future illumination development tends to be artificial illumination, and the artificial illumination refers to the creation of an illumination art simulating natural sunlight for improving the functions of a human body, and can improve the functions, comfort, health and happiness of the human body.
In the existing LED illumination, the similarity between the simulated sunlight spectrum and the real sunlight has a certain difference, the fitting degree of the wave band of 430-687nm can reach more than 98%, but the whole visible light range of 380-780nm can only reach more than 90%, and the requirements of people on high-quality simulated natural sunlight cannot be met.
Disclosure of Invention
The application provides a light-emitting device, which utilizes a specific blue fluorescent material a and is matched with green fluorescent powder, yellow fluorescent powder, red fluorescent powder and near infrared fluorescent powder for use, so that the similarity between the spectrum emitted by the solar spectrum light-emitting device in the visible light range (380-780 nm) and the solar spectrum is over 98 percent, and the aim of being consistent with the solar spectrum is basically fulfilled.
A light emitting device comprising a fluorescent layer and an excitation chip; the fluorescent layer comprises blue fluorescent powder, green fluorescent powder, yellow fluorescent powder, red fluorescent powder and near infrared fluorescent powder;
wherein the blue fluorescent powder contains a blue fluorescent material a;
the blue fluorescent material a is selected from any one of substances shown in a formula I-1;
(M 3-a-x ，A a )Mg(Si 2-b ，D b )O 8-a E a ：xEu 2+ i-1
In formula I, M comprises an element Sr;
a is at least one selected from alkali metal elements;
d, selecting at least one element in IVA group;
e is selected from at least one of halogen;
a is more than or equal to 0.001 and less than or equal to 0.3;
b is more than or equal to 0 and less than or equal to 0.3;
x is more than or equal to 0.001 and less than or equal to 0.4.
Alternatively, in formula I-1, M is an Sr element; or M also comprises at least one of Ca element and Ba element.
Optionally, in the formula I-1, A is at least one of Na element and K element; and/or the number of the groups of groups,
d is at least one selected from Ge element and Sn element; and/or the number of the groups of groups,
e is at least one selected from Cl element and F element.
Alternatively, the substance of formula I-1 belongs to space group P21/a.
Optionally, the peak of the emission spectrum of the substance represented by formula I-1 corresponds to a wavelength in the range of 460nm to 470 nm.
Optionally, the blue fluorescent powder also contains a blue fluorescent material b and a blue fluorescent material c;
the wavelength corresponding to the peak value of the emission spectrum of the blue fluorescent material b is in the range of 410nm to 430 nm;
the peak value of the emission spectrum of the blue fluorescent material c corresponds to a wavelength in the range of 480nm to 500 nm.
Optionally, the blue fluorescent material b is selected from any one of substances shown as a formula I-2;
(Ca 1-x-y ，Sr y ) 2 P 2 O 7 ：xEu 2+ i-2
In the formula I-2, the values of x and y are respectively 0.001-0.2 and 0-0.5;
the blue fluorescent material c is selected from any one of substances shown in a formula I-3;
(Q 1 ) 5-x (PO 4 ) 3 Cl：xEu 2+ i-3
In formula I-3, Q 1 At least one selected from Sr, ba, ca and Mg, and the value range of x is more than or equal to 0.001 and less than or equal to 0.5.
Optionally, the wavelength corresponding to the peak value of the emission spectrum of the green fluorescent powder is in the range of 510 nm-540 nm;
the wavelength corresponding to the peak value of the emission spectrum of the yellow fluorescent powder is in the range of 540 nm-570 nm;
the wavelength corresponding to the peak value of the emission spectrum of the red fluorescent powder is in the range of 600 nm-780 nm;
the wavelength corresponding to the peak value of the emission spectrum of the near infrared fluorescent powder is in the range of 780 nm-850 nm.
In the application, the red fluorescent powder in the prior art has lower luminous intensity in the range of about 730-780 nm, so the near infrared fluorescent powder is selected to supplement the luminous intensity in the deep red range. Although the wavelength corresponding to the peak of the emission spectrum of the near infrared phosphor is in the range of 780nm to 850nm, the emission spectrum has a half-width, so that the emission intensity in the range of 730 to 780nm can be supplemented.
Optionally, the green fluorescent powder is selected from any one of substances shown in a formula II,
(Q 2 ) 2-x SiO 4 ：xEu 2+ II type
In formula II, Q 2 At least one selected from Ba, sr and Ca, wherein the value range of x is more than or equal to 0.001 and less than or equal to 0.2; and/or the number of the groups of groups,
the yellow fluorescent powder is selected from any one of substances shown in a formula III,
(Q 3 ) 3-x (R) 5 O 12 ：xCe 3+ III
In formula III, Q 3 At least one of Y, lu or Gd, R is at least one of Al and Ga, and the value range of x is more than or equal to 0.001 and less than or equal to 0.2; and/or the number of the groups of groups,
the red fluorescent powder is selected from any one of substances shown in a formula IV,
(Q 4 ) 1-x AlSiN 3 ：xEu 2+ IV
In formula IV, Q 4 At least one selected from Sr and Ca, wherein the value range of x is more than or equal to 0.001 and less than or equal to 0.1; and/or the number of the groups of groups,
the near infrared fluorescent powder is selected from any one of substances shown in a formula V;
(Q 5 ) 2-x O 3 ：xCr 3+ v (V)
In V, Q 5 At least one selected from Ga and Sc, wherein the value range of x is more than or equal to 0.001 and less than or equal to 0.2.
Optionally, the mass ratio of the blue fluorescent powder to the green fluorescent powder to the yellow fluorescent powder to the red fluorescent powder to the near infrared fluorescent powder is: 45-60: 3 to 5: 5-10: 5-10: 15-20.
Optionally, the mass ratio of the blue fluorescent material a, the blue fluorescent material b, the blue fluorescent material c, the green fluorescent powder, the yellow fluorescent powder, the red fluorescent powder and the near infrared fluorescent powder is as follows: 10 to 15: 20-25: 10-20: 3 to 5: 5-10: 5-10: 15-20.
Optionally, the fluorescent layer further comprises an organic colloid; the mass ratio of the total amount of the fluorescent powder to the organic colloid is 0.5-2: 1.
optionally, the peak of the excitation spectrum of the excitation chip corresponds to a wavelength in a range from 380nm to 420 nm.
Optionally, the peak of the excitation spectrum of the excitation chip corresponds to a wavelength in the range of 380nm to 390 nm.
There is also provided according to a second aspect of the present application a lighting apparatus comprising a light emitting device as defined in any one of the preceding claims.
The technical scheme provided by the application has the beneficial effects that at least:
1) In the application, the specific blue fluorescent material a is used and is matched with the blue fluorescent materials b and c, the green fluorescent powder, the yellow fluorescent powder, the red fluorescent powder and the near infrared fluorescent powder, so that the similarity between the spectrum emitted by the solar spectrum light-emitting device in the visible light range (380-780 nm) and the solar spectrum is more than 98 percent, and the aim of being consistent with the solar spectrum is basically achieved.
2) In the application, the blue fluorescent powder adopts a specific blue fluorescent material a, and adopts a blue fluorescent material b and a blue fluorescent material c, and different types of blue fluorescent materials are used together, for example, the blue fluorescent material a emits light with a wavelength of 440-480nm, the material b covers 410-430nm, and the material c covers 480-500nm, and after the three materials are matched, the whole blue light spectrum is covered, and the similarity with solar spectrum is further improved.
3) The excitation light is in a purple light wave band, the effect of exciting green or red fluorescent powder is slightly poor, blue fluorescent powder a, b and c are excited by the purple light chip, and blue light emitted by the blue light chip can effectively excite other long-wave band fluorescent powder, so that the high efficiency of the whole light-emitting device is maintained.
4) The application effectively supplements the defects of deep red and near infrared spectrum of the existing high-color-rendering luminescent device by adding the near infrared fluorescent powder, improves the consistency with solar spectrum, and is beneficial to the visual health of human beings.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a light emitting device according to an embodiment of the present application;
FIG. 2 is a graph showing the comparison of the test spectrum of the sample in example 1 with the spectrum of sunlight A30 (3000K) provided in the examples of the present application;
FIG. 3 is a graph showing the comparison of the test spectrum of the sample in example 1 with the spectrum of sunlight D50 (5000K) provided in the examples of the present application;
FIG. 4 is a graph showing the comparison of the test spectrum of the sample in comparative example 3 with the spectrum of sunlight A30 according to the present application;
FIG. 5 is a graph showing the comparison of the test spectrum of the sample in comparative example 3 with the D50 spectrum of sunlight according to the present application;
FIG. 6 is a graph showing the comparison of the test spectra and D50 spectra of inventive example 1 and comparative example 1;
FIG. 7 is a graph showing the comparison of the test spectrum of the sample in example 5 of the present application with the spectrum of sunlight A30 (3000K);
FIG. 8 is a graph showing the comparison of the test spectrum of the sample in example 5 of the present application with the spectrum of sunlight D50 (5000K).
FIG. 9 is a graph showing the comparison of the test spectrum of the sample in example 6 of the present application with the spectrum of sunlight A30 (3000K);
FIG. 10 is a graph showing the comparison of the test spectrum of the sample in example 6 of the present application with the spectrum of sunlight D50 (5000K).
Detailed Description
A light emitting device includes a fluorescent layer and an excitation chip; the fluorescent layer comprises blue fluorescent powder, green fluorescent powder, yellow fluorescent powder, red fluorescent powder and near infrared fluorescent powder;
wherein the blue fluorescent powder contains a blue fluorescent material a, and the blue fluorescent material a is selected from any one of substances shown in a formula I-1;
(M 3-a-x ，A a )Mg(Si 2-b ，D b )O 8-a E a ：xEu 2+ i-1
In formula I, M comprises an element Sr;
a is at least one selected from alkali metal elements;
d, selecting at least one element in IVA group;
e is selected from at least one of halogen;
a is more than or equal to 0.001 and less than or equal to 0.3;
b is more than or equal to 0 and less than or equal to 0.3;
x is more than or equal to 0.001 and less than or equal to 0.4.
Specifically, in the blue fluorescent material a, on one hand, the coordination of the element A and the element E realizes charge balance; on the other hand, the combined substitution of E and A improves the symmetry of the crystal field around the Eu element, reduces the Stokes displacement of Eu, and obviously enhances the absorption of Eu to 380-420 nm long-wave purple light. The addition of the element D can improve the ageing resistance of the fluorescent powder.
Optionally, M is an Sr element; or M also comprises at least one of Ca element and Ba element.
Specifically, M may be an Sr element in one example, or M contains Sr and also contains at least one of Ca, ba in another example.
Optionally, a is at least one of Na element and K element; and/or the number of the groups of groups,
d is at least one selected from Ge element and Sn element; and/or the number of the groups of groups,
e is at least one selected from Cl element and F element.
Optionally, in the formula I, the value range of a is more than or equal to 0.02 and less than or equal to 0.2; and/or the number of the groups of groups,
b is more than or equal to 0 and less than or equal to 0.1; and/or the number of the groups of groups,
x is more than or equal to 0.01 and less than or equal to 0.2.
Optionally, the blue fluorescent material a belongs to the space group P21/a.
Optionally, the crystallinity of the blue fluorescent material a is 90% -99.9%.
The knot is provided withThe crystallinity can be obtained from the X-ray diffraction spectrum of the fluorescent powder, and the calculation formula is crystallinity X c ＝I c/ (I c +I a )
Wherein I is c Is the sum of the intensities of all diffraction peaks, I a Is the scattering intensity of the amorphous phase.
Alternatively, the median particle diameter of the blue fluorescent material a is 2 to 30 μm. The median particle diameter here is D50.
Optionally, the blue fluorescent material a is excited by ultraviolet light, and the wavelength corresponding to the peak value of the emission spectrum of the blue fluorescent material a is in the range of 460nm to 470 nm.
Optionally, the blue fluorescent powder further contains a blue fluorescent material b and a blue fluorescent material c, wherein the wavelength corresponding to the peak value of the emission spectrum of the blue fluorescent material b is in the range of 410nm to 430 nm; the peak value of the emission spectrum of the blue fluorescent material c corresponds to a wavelength in the range of 480nm to 500 nm. The blue fluorescent material b and the blue fluorescent material c further improve the similarity with the solar spectrum. The blue light emitted by the blue fluorescent powder a, b and c can effectively excite other long-wave-band fluorescent powder, and the high efficiency of the whole light-emitting device is maintained.
The blue fluorescent material b is selected from any one of substances shown as a formula I-2; (Ca) 1-x-y ，Sr y ) 2 P 2 O 7 ：xEu 2+ Formula I-2. In the formula I-2, preferably, the values of x and y are respectively equal to or more than 0.01 and equal to or less than 0.1, and equal to or more than 0 and equal to or less than 0.3. For example, blue fluorescent material b may be Ca 1.9 P 2 O 7 ：0.1Eu 2+ 、Ca 1.7 Sr 0.2 P 2 O 7 ：0.1Eu 2+ 。
The blue fluorescent material c is selected from any one of substances shown as a formula I-3; (Q) 1 ) 5-x (PO 4 ) 3 Cl：xEu 2+ Formula I-3. Preferably, in the formula I-3, x is in the range of 0.05.ltoreq.x.ltoreq.0.4. For example, the blue fluorescent material c may be Sr 4.8 (PO 4 ) 3 Cl：0.2Eu 2+ ，Sr 4.6 Ca 0.2 (PO 4 ) 3 Cl：0.2Eu 2+ 。
The green fluorescent powder is selected from any one of substances shown in a formula II, and (Q) 2 ) 2-x SiO 4 ：xEu 2+ Formula II. The preferable value range of x is 0.03-0.08. For example, the green phosphor may be Sr 0.5 Ba 1.45 SiO 4 :0.05Eu。
The yellow fluorescent powder is selected from any one of substances shown in a formula III, and (Q) 3 ) 3-x (R) 5 O 12 ：xCe 3+ Formula III. The preferable value range of x is 0.03-0.15. For example, the yellow phosphor may be Y 2.92 Al 5 O 12 ：0.08Ce 3+ 。
The red fluorescent powder is selected from any one of substances shown in a formula IV, and (Q) 4 ) 1-x AlSiN 3 ：xEu 2+ Formula IV. The preferable value range of x is 0.01-0.1. For example, the red phosphor may be Ca 0.98 AlSiN 3 ：0.02Eu 2+ ,Ca 0.08 Sr 0.9 AlSiN 3 ：0.02Eu 2+ 。
The near infrared fluorescent powder is selected from any one of substances shown in a formula V; (Q) 5 ) 2-x O 3 ：xCr 3+ Formula V. The preferable value range of x is 0.01-0.15. For example, the near infrared phosphor may be Ga 1.8 Sc 0.15 O 3 ：0.05Cr 3+ 。
Optionally, the mass ratio of the blue fluorescent powder to the green fluorescent powder to the yellow fluorescent powder to the red fluorescent powder to the near infrared fluorescent powder is 45-60: 3 to 5: 5-10: 5-10: 15-20. The application adopts the proportioning relation, and can realize the effects/actions of spectrum continuity and consistent with the spectrum of sunlight.
Preferably, the mass ratio of the blue fluorescent powder to the green fluorescent powder to the yellow fluorescent powder to the red fluorescent powder to the near infrared fluorescent powder is 30-45: 6-8: 8-15: 7-11: 20 to 25.
Optionally, the mass ratio of the blue fluorescent material a, the blue fluorescent material b, the blue fluorescent material c, the green fluorescent powder, the yellow fluorescent powder, the red fluorescent powder and the near infrared fluorescent powder is 10-15: 20-25: 10-20: 3 to 5: 5-10: 5-10: 15-20.
Preferably, the mass ratio of the blue fluorescent material a, the blue fluorescent material b, the blue fluorescent material c, the green fluorescent powder, the yellow fluorescent powder, the red fluorescent powder and the near infrared fluorescent powder is 35-50: 7-10: 6-13: 5-10: 15-20.
Optionally, the fluorescent layer further comprises an organic colloid.
Specifically, the organic colloid may be silica gel, or may also be silicone resin, epoxy resin, or the like.
Optionally, the mass ratio of the total amount of the fluorescent powder to the organic colloid is 0.5-2: 1. in this range, the light-emitting device has the advantages of high operability, high light color concentration of the light-emitting device and the like.
Optionally, the excitation chip in the application adopts a purple light excitation chip, and the purple light is light with a wavelength in a range of 380nm to 420nm corresponding to at least partial peak value in the spectrum.
Preferably, the violet light is light having a wavelength in the range of 380nm to 390nm corresponding to at least a portion of the peak in the spectrum. The excitation light of the wave band is selected to match with luminescent materials with different colors, so that the device can realize the effects of high light efficiency and good spectral continuity on the whole.
The light emitting device of the present application may specifically refer to the schematic diagram in fig. 1. In fig. 1, the light emitting device holder 3 is provided with a concave groove, and the cross section of the groove may be trapezoidal as shown in fig. 1, or may be any other suitable shape, for example, rectangular, square, or elliptical, etc., which is not strictly limited by the present application. The excitation chip 2 is placed on the inner bottom surface of the recess, and then the recess is filled with a mixture containing a fluorescent layer and an organic colloid.
When in use, the excitation chip 2 is fixed on the light-emitting device bracket 3, the chip emits light after being electrified and lightened, and fluorescent powder excited by light emitted by the chip forms required mixed light.
Preparation of blue fluorescent material a:
s100, mixing an M source, an A source, an Mg source, an Si source, an E source, an Eu source and a D source according to the stoichiometric ratio meeting the formula I to obtain a mixture;
s200, burning the mixture at 1150-1500 ℃ for 1-10 h in a reducing atmosphere to obtain the fluorescent powder material.
Alternatively, the M source comprises any one of M oxide, M carbonate.
For example, the M source may be SrCO 3 、BaCO 3 、CaCO 3 、CaO、SrO、BaO。
Alternatively, the a source comprises any one of an a oxide, an a carbonate, an a halide.
For example, the A source may be NaCl, KCl, naCO 3 、KCO 3 、K 2 O，Na 2 O, etc.
Alternatively, the E source comprises an A halide, NH 4 Any one of the salt halides.
For example, the E source may be NaCl, KCl, NH 4 Cl, and the like.
Optionally, the D source comprises D oxide.
For example, the D source may be GeO 2 ，SnO 2 Etc.
In the process of batching, the element A and the element E are equimolar.
The better batching mode is as follows: the A halide is used as the A source and the E source, and the M source and the D source are selected from non-halide forms.
Optionally, the heating process of the firing includes:
a first temperature rising stage: the temperature range is 25-800 ℃, and the heating rate is 8-20 ℃/min;
a second temperature rising stage: the temperature range is 800-1100 ℃, the heating rate is not more than 4 ℃/min and not more than 5 ℃/min;
and a third temperature rising stage: the temperature is higher than 1100 ℃ in a temperature interval, the heating rate is not lower than 1 ℃/min and not higher than 5 ℃/min.
Specifically, the heating process of the firing comprises the following steps:
a first temperature rising stage: the upper limit of the heating rate is selected from any value of 9 ℃/min, 10 ℃/min, 11 ℃/min, 12 ℃/min, 15 ℃/min and 20 ℃/min, and the lower limit of the heating rate is selected from any value of 8 ℃/min, 9 ℃/min, 10 ℃/min, 11 ℃/min, 12 ℃/min and 15 ℃/min in the temperature range of 25-800 ℃.
A second temperature rising stage: the upper limit of the temperature rising rate is selected from any value of 4.5 ℃/min and 5 ℃/min in the temperature range of 800-1100 ℃; the lower limit of the temperature rising rate is selected from any value of 4 ℃/min and 4.5 ℃/min.
And a third temperature rising stage: the upper limit of the temperature rising rate is selected from any value of 2 ℃/min, 3 ℃/min and 5 ℃/min in a temperature interval above 1100 ℃; the lower limit of the heating rate is selected from any one of 1 ℃/min, 2 ℃/min and 3 ℃/min.
Example 1
Preparation of blue fluorescent Material a used in example 1
41.34g SrCO is weighed 3 ，4.03g MgO，12.02g SiO 2 ，0.584NaCl，1.76g Eu 2 O 3 Mixing uniformly and then filling into a corundum crucible. Placing the mixture in a box-type electric furnace, introducing flowing mixed gas of nitrogen and hydrogen (hydrogen content is 75%) after sealing, and heating the electric furnace according to the temperature-raising program: the temperature rising rate of the first section at 25-800 ℃ is 8 ℃/min; a second temperature rising stage: 800-1100 deg.c, 5 deg.c/min. In the third stage, the temperature rising rate of the temperature range above 1100 ℃ is 5 ℃/min, and the temperature rises to 1350 ℃ and is kept for 5 hours. Naturally cooling to obtain a burning product; and grinding the firing product into powder, washing and drying to obtain the blue fluorescent powder for the light-emitting device. Molecular formula (Sr) 2.8 ，Na 0.1 )MgSi 2 O 7.9 Cl 0.1 ：0.1Eu 2+ The emission wavelength is 460nm.
Example 2
Preparation of blue fluorescent Material a used in example 2
36.17g SrCO is weighed 3 ，4.03g MgO，11.41g SiO 2 ，1.17NaCl，2.64g Eu 2 O 3 ,1.05gGeO 2 3.95g BaCO 3 Mixing uniformly and then filling into a corundum crucible. Placing the mixture in a box-type electric furnace, introducing flowing mixed gas of nitrogen and hydrogen (hydrogen content is 75%) after sealing, and heating the electric furnace according to the temperature-raising program: the temperature range of the first section is 25-800 DEG CHeating rate is 15 ℃/min; a second temperature rising stage: 800-1100 deg.c, 5 deg.c/min. In the third stage, the temperature rising rate of the temperature range above 1100 ℃ is 4 ℃/min, and the temperature rises to 1150 ℃ and is kept for 10 hours. Naturally cooling to obtain a burning product; and grinding the firing product into powder, washing and drying to obtain the blue fluorescent powder for the LED. Molecular formula (Sr) 2.45 Ba 0.2 Na 0.2 )MgSi 1.9 Ge 0.1 O 7.8 Cl 0.2 ：0.15Eu 2+ The emission wavelength is 465nm.
Example 3
Preparation of blue fluorescent Material a used in example 3
40.15g SrCO was weighed out 3 ，4.03g MgO，12.02g SiO 2 ，0.596KF，1.76g Eu 2 O 3 ，0.5g CaCO 3 0.987g BaCO 3 Mixing uniformly and then filling into a corundum crucible. Placing the mixture in a box-type electric furnace, introducing flowing mixed gas of nitrogen and hydrogen (hydrogen content is 75%) after sealing, and heating the electric furnace according to the temperature-raising program: the temperature rising rate of the first section 25-800 ℃ is 10 ℃/min; a second temperature rising stage: 800-1100 deg.c, 5 deg.c/min. In the third stage, the temperature rising rate of the temperature range above 1100 ℃ is 4 ℃/min, the temperature rises to 1370 ℃ and the temperature is kept for 4 hours. Naturally cooling to obtain a burning product; and grinding the firing product into powder, washing and drying to obtain the blue fluorescent powder for the LED. Molecular formula (Sr) 2.72 Ba 0.05 Ca 0.05 K 0.08 )MgSi 2 O 7.92 F 0.08 ：0.1Eu 2+ The emission wavelength is 462nm.
Example 4
Preparation of blue fluorescent Material a used in example 4
39.86g SrCO is weighed 3 ，4.03g MgO，12.02g SiO 2 ，0.373KCl，0.292NaF，0.88g Eu 2 O 3 And 1.97g BaCO 3 Mixing uniformly and then filling into a corundum crucible. Placing the mixture in a box-type electric furnace, introducing flowing mixed gas of nitrogen and hydrogen (hydrogen content is 75%) after sealing, and heating the electric furnace according to the temperature-raising program: the temperature rising rate of the first section at 25-800 ℃ is 11 ℃/min; a second temperature rising stage: 800 DEG CTemperature range is about 1100 ℃,5 ℃/min. In the third stage, the temperature rising rate of the temperature range above 1100 ℃ is 4 ℃/min, the temperature rises to 1390 ℃ and the temperature is kept for 4 hours. Naturally cooling to obtain a burning product; and grinding the firing product into powder, washing and drying to obtain the blue fluorescent powder for the LED. Molecular formula (Sr) 2.7 Ba 0.1 K 0.05 Na 0.05 )MgSi 2 O 7.9 F 0.05 Cl 0.05 ：0.1Eu 2+ The emission wavelength is 463nm.
Other fluorescent materials used in the examples of the present application are commercially available.
Example 1
1.5g of (Sr) 2.8 Na 0.1 )MgSi 2 O 7.9 Cl 0.1 ：0.1Eu 2+ (blue fluorescent Material a), 2.0g of Ca 1.7 P 2 O 7 :0.1Eu 2+ (blue fluorescent Material b), 1.5g of Sr 4.6 Ba 0.2 (PO 4 ) 3 Cl：0.2Eu 2+ (blue fluorescent material c), 0.5g of Sr 0.5 Ba 1.45 SiO 4 0.05Eu (green phosphor), 1.0g Y 2.92 Al 5 O 12 ：0.08Ce 3+ (yellow phosphor), 1.0g of Ca 0.08 Sr 0.9 AlSiN 3 ：0.02Eu 2+ (Red phosphor), 1.8g Ga 1.8 Sc 0.15 O 3 ：0.05Cr 3+ (near infrared phosphor) and 10g of silica gel were mixed to obtain a mixture.
The mixture is coated on an excitation chip, and the wavelength corresponding to the peak value of the excitation spectrum of the excitation chip in the embodiment is 385nm, so that the light-emitting device can be obtained.
Example 2
1.6g of (Sr) 2.45 Ba 0.2 Na 0.2 )MgSi 1.9 Ge 0.1 O 7.8 Cl 0.2 ：0.15Eu 2+ (blue fluorescent Material a), 2.2g of Ca 1.98 P 2 O 7 :0.02Eu 2+ (blue fluorescent material b), 1.4g of (Sr) 0.89 Ba 0.1 ) 5 (PO 4 ) 3 Cl：0.05Eu 2+ (blue fluorescence)Material c), 0.6g (Ba 0.6 ,Sr 0.36 ) 2 SiO 4 ：0.08Eu 2+ (Green phosphor), 1.1g of Y 2.95 Al 5 O 12 ：0.05Ce 3+ (yellow phosphor), 1.1g (Sr) 0.9 Ca 0.08 )AlSiN 3 ：0.02Eu 2+ (Red phosphor), 1.9g (Ga 0.885 ,Sc 0.1 ) 2 O 3 ：0.03Cr 3+ (near infrared phosphor) and 10.5g of silica gel were mixed to obtain a mixture.
The mixture is coated on an excitation chip, and the wavelength corresponding to the peak value of the excitation spectrum of the excitation chip in the embodiment is 385nm, so that the light-emitting device can be obtained.
Example 3
1.5g of (Sr) 2.72 Ba 0.05 Ca 0.05 K 0.08 )MgSi 2 O 7.92 F 0.08 ：0.1Eu 2+ (blue fluorescent Material a), 2.0g of Ca 1.95 P 2 O 7 :0.05Eu 2+ (blue fluorescent material b), 1.5g of (Sr) 0.65 Ba 0.3 ) 5 (PO 4 ) 3 Cl：0.15Eu 2+ (blue fluorescent material c), 0.5g (Ba) 0.7 ,Sr 0.27 ) 2 SiO 4 ：0.06Eu 2+ (Green phosphor), 1.0g of Y 2.92 Al 5 O 12 ：0.08Ce 3+ (yellow phosphor), 1.0g (Sr) 0.9 Ca 0.09 )AlSiN 3 ：0.01Eu 2+ (Red phosphor), 1.8g (Ga 0.89 ,Sc 0.1 ) 2 O 3 ：0.02Cr 3+ (near infrared phosphor) and 10g of silica gel were mixed to obtain a mixture.
The mixture is coated on an excitation chip, and the wavelength corresponding to the peak value of the excitation spectrum of the excitation chip in the embodiment is 390nm, so that the light-emitting device can be obtained.
Example 4
1.4g of (Sr) 2.7 Ba 0.1 K 0.05 Na 0.05 )MgSi 2 O 7.9 F 0.05 Cl 0.05 ：0.1Eu 2+ (blue fluorescent Material a)) 2.1g of Ca 1.99 P 2 O 7 :0.01Eu 2+ (blue fluorescent material b), 1.5g of (Sr) 0.5 Ba 0.45 ) 5 (PO 4 ) 3 Cl：0.25Eu 2+ (blue fluorescent material c), 0.6g (Ba) 0.8 ,Sr 0.17 ) 2 SiO 4 ：0.06Eu 2+ (Green phosphor), 1.1g of Y 2.9 Al 5 O 12 ：0.1Ce 3+ (yellow phosphor), 1.05g (Sr) 0.87 Ca 0.08 )AlSiN 3 ：0.05Eu 2+ (Red phosphor), 1.9g (Ga 0.79 ,Sc 0.2 ) 2 O 3 ：0.02Cr 3+ (near infrared phosphor) and 11g of silica gel were mixed to obtain a mixture.
The mixture is coated on an excitation chip, and the wavelength corresponding to the peak value of the excitation spectrum of the excitation chip in the embodiment is 390nm, so that the light-emitting device can be obtained.
Example 5
Similar to example 1, the difference is that: blue fluorescent material b and blue fluorescent material c are not added.
Example 6
The difference from example 1 is that the blue fluorescent material c is not added.
Examples spectral testing
The light emitting devices in examples 1 to 6 were subjected to spectral test. The luminescent device with the fluorescent powder scheme simulates the standard color temperature spectrum of sunlight: a30 (3000K), D50 (5000K).
1) The spectrum fitting degree calculating method is as follows:
the fitness coefficient e (GFC) is calculated as follows:
wherein:
S LED -the relative spectral power distribution of the LEDs under test;
S Target -relative spectral power distribution of standard light source, pair 5The energy at 60nm is normalized to 100.
Wherein the GFC has an analog wavelength in the range of 380-780nm.
2) Test method
The light source device in the above example was fabricated, and the photo-color parameters were measured with a photo-integrating sphere.
3) Test results
The test results show that the light-emitting devices in examples 1 to 4 have a degree of fitting with the spectrum of sunlight A30 of 99% or more in the range of 380nm to 780nm and a degree of fitting with the spectrum of D50 of 99% or more in the range of 380nm to 780nm.
As typified by example 1, fig. 2 is a graph showing a fitting curve of the test spectrum of the sample in example 1 to the spectrum of sunlight a30 (3000K), and it can be seen that the fitting degree of the test spectrum to the spectrum of a30 is 99.3% in the range of 380 to 780nm.
Fig. 3 is a graph showing the fit between the test spectrum of the sample in example 1 and the spectrum of sunlight D50 (5000K), and it can be seen that the fit between the test spectrum and the spectrum of sunlight D50 is 99.6% in the range of 380 to 780nm.
FIG. 7 is a graph showing the fit between the test spectrum of the sample in example 5 and the spectrum of sunlight A30 (3000K), and it can be seen that the fit between the test spectrum and the spectrum of sunlight A30 is 93.7% in the range of 380-780nm.
Fig. 8 is a graph showing the fit between the test spectrum of the sample in example 5 and the spectrum of sunlight D50 (5000K), and it can be seen that the fit between the test spectrum and the spectrum of sunlight D50 is 93.2% in the range of 380 to 780nm.
Fig. 9 is a graph showing the fit between the test spectrum of the sample in example 6 and the spectrum of sunlight a30 (3000K), and it can be seen that the fit between the test spectrum and the spectrum of sunlight a30 is 95.8% in the range of 380 to 780nm.
Fig. 10 is a graph showing the fit between the test spectrum of the sample in example 6 and the spectrum of sunlight D50 (5000K), and it can be seen that the fit between the test spectrum and the spectrum of sunlight D50 is 95.7% in the range of 380 to 780nm.
Comparative example 1
Unlike example 1, no (Sr) was used 2.8 Na 0.1 )MgSi 2 O 7.9 Cl 0.1 ：0.1Eu 2+ (blue)Color fluorescent material a), the remainder being the same.
Table 1 shows the luminous flux of example and comparative example 1 and the parameters related to the spectral fitness with sunlight D50 (5000K). FIG. 6 is a graph showing the comparison between the test spectrum and D50 spectrum of example 1 and comparative example 1 in the range of 380 to 780nm.
TABLE 1
As can be seen from table 1, the use of blue phosphor a can improve the fitting of the device to sunlight, and the fitting gradually improves with the manner of blue phosphor a+b and the manner of blue phosphor a+b+c.
Comparative example 2
The difference from example 1 is that blue phosphor is not used, the rest being the same.
Table 2 shows the brightness comparison data of example 1 and comparative example 2.
TABLE 2
As can be seen from table 2, blue light emitted through the blue phosphors a, b, c can effectively excite other long-band phosphors, maintaining high efficiency of the entire light emitting device.
Comparative example 3
The luminescent materials in the common sunlight-like luminescent devices in the market are prepared from the following fluorescent powder:
1) 10g of blue fluorescent powder Sr 5 (PO 4 ) 3 Cl:Eu 2+ ，430-480nm
2) 3g of yellow-green fluorescent powder: (Y, lu, gd) 3 (Al,Ga) 5 O 12 ：Ce 3+ 500-540nm
3) 1g of red fluorescent powder: (Sr, ca) AlSiN 3 ：Eu 2+ 600-680nm
4) 15g of silica gel.
The light emitting device manufactured in comparative example 3 was subjected to a spectrum test, and the test results are shown in fig. 4 and 5. Fig. 4 is a graph showing the fit between the test spectrum of the sample in comparative example 3 and the spectrum of sunlight a30, and it can be seen that the fit between the test spectrum and the spectrum of sunlight a30 is 91.3% in the range of 380 to 780nm. Fig. 5 is a graph showing the fit between the test spectrum of the sample in comparative example 3 and the D50 spectrum of sunlight, and it can be seen that the fit between the test spectrum and the D50 spectrum is 92.8% in the range of 380-780nm.
Therefore, the similarity with solar spectrum can be further improved by using three different blue fluorescent powders in a matched mode, and blue light emitted by the blue fluorescent powders a, b and c can effectively excite other long-wave-band fluorescent powders, so that the high efficiency of the whole light-emitting device is maintained.
The above-described embodiments are merely illustrative of the preferred embodiments of the present application and are not intended to limit the scope of the present application, and various modifications and improvements made by those skilled in the art to the technical solution of the present application should fall within the scope of protection defined by the claims of the present application without departing from the design spirit of the present application.
Claims (9)
1. A light emitting device comprising a fluorescent layer and an excitation chip;
the fluorescent layer comprises blue fluorescent powder, green fluorescent powder, yellow fluorescent powder, red fluorescent powder and near infrared fluorescent powder;
wherein the blue fluorescent powder contains a blue fluorescent material a;
the blue fluorescent material a is selected from any one of substances shown in a formula I-1;
（M 3-a-x ，A a ）Mg（Si 2-b ，D b ）O 8-a E a ：xEu 2+ i-1
In formula I, M comprises an element Sr;
a is at least one selected from alkali metal elements;
d, selecting at least one element in IVA group;
e is selected from at least one of halogen;
a is more than or equal to 0.001 and less than or equal to 0.3;
b is more than or equal to 0 and less than or equal to 0.3;
x is more than or equal to 0.001 and less than or equal to 0.4;
the peak value of the emission spectrum of the substance shown in the formula I-1 corresponds to the wavelength in the range of 460nm to 470 nm;
the blue fluorescent powder also contains a blue fluorescent material b and a blue fluorescent material c;
the wavelength corresponding to the peak value of the emission spectrum of the blue fluorescent material b is in the range of 410nm to 430 nm;
the wavelength corresponding to the peak value of the emission spectrum of the blue fluorescent material c is in the range of 480nm to 500 nm;
the wavelength corresponding to the peak value of the emission spectrum of the green fluorescent powder is in the range of 510 nm-540 nm;
the wavelength corresponding to the peak value of the emission spectrum of the yellow fluorescent powder is within the range of 540 nm-570 nm;
the wavelength corresponding to the peak value of the emission spectrum of the red fluorescent powder is within the range of 600 nm-780 nm;
the wavelength corresponding to the peak value of the emission spectrum of the near infrared fluorescent powder is in the range of 780 nm-850 nm;
the peak value of the excitation spectrum of the excitation chip corresponds to the wavelength in the range of 380nm to 420 nm.
2. The light-emitting device according to claim 1, wherein the light-emitting device satisfies at least one of the following conditions,
condition a:
in the formula I-1, M is Sr element; or M also comprises at least one of Ca element and Ba element;
condition b:
in the formula I-1, A is at least one of Na element and K element; and/or the number of the groups of groups,
d is at least one selected from Ge element and Sn element; and/or the number of the groups of groups,
e is at least one selected from Cl element and F element;
condition c:
the substance shown in the formula I-1 belongs to a space group P21/a.
3. The light-emitting device according to claim 1, wherein the blue fluorescent material b is selected from any one of substances having a formula i-2;
(Ca 1-x-y ，Sr y ) 2 P 2 O 7 ：xEu 2+ i-2
In the formula I-2, the values of x and y are respectively 0.001-0.1 and 0-1;
the blue fluorescent material c is selected from any one of substances shown in a formula I-3;
（Q 1 ) 5-x (PO 4 ) 3 Cl：xEu 2+ i-3
In formula I-3, Q 1 At least one selected from Sr, ba, ca and Mg, and the value range of x is more than or equal to 0.001 and less than or equal to 0.5.
4. The light-emitting device according to claim 1, wherein the green phosphor is selected from any one of substances having a formula II,
（Q 2 ) 2-x SiO 4 ：xEu 2+ II type
In formula II, Q 2 At least one selected from Ba, sr and Ca, wherein the value range of x is more than or equal to 0.001 and less than or equal to 0.2; and/or the number of the groups of groups,
the yellow fluorescent powder is selected from any one of substances shown in a formula III,
(Q 3 ) 3-x (R) 5 O 12 ：xCe 3+ III
In formula III, Q 3 At least one of Y, lu or Gd, R is at least one of Al and Ga, and the value range of x is more than or equal to 0.001 and less than or equal to 0.2; and/or the number of the groups of groups,
the red fluorescent powder is selected from any one of substances shown in a formula IV,
（Q 4 ) 1-x AlSiN 3 ：xEu 2+ IV
In formula IV, Q 4 At least one selected from Sr and Ca, wherein the value range of x is more than or equal to 0.001 and less than or equal to 0.1; and/or the number of the groups of groups,
the near infrared fluorescent powder is selected from any one of substances shown in a formula V;
(Q 5 ) 2-x O 3 ：xCr 3+ v (V)
In V, Q 5 At least one selected from Ga and Sc, wherein the value range of x is more than or equal to 0.001 and less than or equal to 0.2.
5. The light-emitting device according to claim 1, wherein the mass ratio of the blue phosphor, the green phosphor, the yellow phosphor, the red phosphor and the near infrared phosphor is:
45~60：3~5：5~10：5~10：15~20。
6. the light-emitting device according to claim 5, wherein the mass ratio of the blue fluorescent material a, the blue fluorescent material b, the blue fluorescent material c, the green fluorescent powder, the yellow fluorescent powder, the red fluorescent powder, and the near infrared fluorescent powder is:
10~15：20~25：10~20：3~5：5~10：5~10：15~20。
7. the light-emitting device of claim 1, wherein the fluorescent layer further comprises an organic colloid;
the mass ratio of the total amount of the fluorescent powder to the organic colloid is 0.5-2: 1.
8. the light-emitting device according to claim 1, wherein a peak of an excitation spectrum of the excitation chip corresponds to a wavelength in a range of 380nm to 390 nm.
9. A lighting device, characterized in that the lighting device comprises the light emitting device according to any one of claims 1 to 8.
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