CN110627024A - Aluminum-doped silicon nitride material, aluminum-doped silicon nitride-based orange-red fluorescent material and preparation method thereof - Google Patents
Aluminum-doped silicon nitride material, aluminum-doped silicon nitride-based orange-red fluorescent material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an aluminum-doped silicon nitride material, an aluminum-doped silicon nitride-based orange-red fluorescent material and a preparation method thereof, wherein the preparation method of the aluminum-doped silicon nitride material comprises the following steps: mixing silicon powder and aluminum powder, placing the mixture in a nitrogen atmosphere, and reacting for 2-48 hours at 1300-2000 ℃ to obtain an aluminum-doped silicon nitride material; the molar ratio of the silicon powder to the aluminum powder is 2000: 1-20: 1.
Description
Technical Field
The invention relates to an aluminum-doped silicon nitride and aluminum-doped silicon nitride-based orange-red fluorescent material and a preparation method thereof, belonging to the technical field of photoelectric materials.
Background
Silicon nitride has many excellent physical properties: high temperature resistance, radiation resistance, strong thermal shock resistance, high hardness and the like, so the material is widely applied to the mechanical industry and the electronic industry. For example, silicon nitride is a common material for high temperature bearings, turbine blades, and high speed cutting tools. In addition, silicon nitride thin films are widely used in the field of microelectronics as impurity diffusion masking films, surface passivation films, and insulating dielectrics.
Chinese patent application 1 (chinese application No. 200910054967.7) discloses an aluminum-doped silicon nitride material with a band gap width reduced from 5.3eV to 2.64eV, which is prepared by a CVD method. This shows that it is feasible to adjust the band structure of silicon nitride by doping with aluminum. However, the patent does not discuss the relationship between the aluminum content and the band gap of aluminum-doped silicon nitride, and the CVD method has a low production yield. Since the doped rare earth element europium content in the patent is very low, the obtained aluminum-doped silicon nitride-based fluorescent material doped with the rare earth element europium has a narrow light-emitting range, and the aluminum-doped silicon nitride-based fluorescent material doped with the rare earth element europium and a blue light chip are not compounded into a white light LED.
Chinese patent application 2 (Chinese publication No. CN102093887A) discloses a silicon nitride orange-red light luminescent material for a low color temperature white light LED and a preparation method thereof, wherein the raw materials are silicon nitride, aluminum nitride, europium oxide and the like, and the morphology of the obtained composite material is micron-particle. Although the application of the white light LED is suggested, the emission peak coverage is narrow, and the orange red light intensity is weak, so that the obtained white light LED has low luminous intensity and high color temperature, and cannot meet the practical application.
Disclosure of Invention
In view of the above problems, the present invention provides an aluminum-doped silicon nitride and aluminum-doped silicon nitride-based orange-red fluorescent material and a preparation method thereof.
In a first aspect, the invention provides a preparation method of an aluminum-doped silicon nitride material, which comprises the steps of mixing silicon powder and aluminum powder, placing the mixture in a nitrogen atmosphere, and reacting at 1300-2000 ℃ for 2-48 hours to obtain the aluminum-doped silicon nitride material; the molar ratio of the silicon powder to the aluminum powder is 2000: 1-20: 1.
During the whole reaction process, white silicon nitride is generated by silicon vapor and nitrogen, and meanwhile, aluminum atoms enter the positions of gaps and silicon atoms in the silicon nitride due to thermal movement, so that interstitial aluminum and substitutional aluminum are formed. The aluminum atoms entering the silicon nitride lattice preferentially orient the growth of the silicon nitride and, ultimately, form a silicon nitride micron band along the preferential growth direction.
Preferably, the flow rate of the nitrogen atmosphere is 50 to 1000ml/min, and the pressure is maintained between 0.8 to 4 atm.
Preferably, the mixing is ball milling mixing in an inert atmosphere; the rotation speed of ball milling mixing is 100-400 r/min, and the time is 2-4 hours.
In a second aspect, the invention provides a preparation method of an aluminum-doped silicon nitride-based orange-red fluorescent material, which comprises the steps of mixing silicon powder, aluminum powder and europium oxide, placing the mixture in a nitrogen atmosphere, and reacting at 1300-2000 ℃ for 2-48 hours to obtain the aluminum-doped silicon nitride-based orange-red fluorescent material; the molar ratio of the silicon powder to the aluminum powder is 2000: 1-20: 1, and the molar ratio of the silicon element in the silicon powder to the europium element in the europium oxide is 1000: 1-30: 1.
During the whole reaction process, while the silicon vapor and the nitrogen gas generate white silicon nitride, aluminum atoms enter the silicon nitride crystal lattice in an interstitial and substitutional mode. The addition of aluminum not only ensures the growth of silicon nitride to generate preferred orientation, but also is beneficial to filling rare earth element europium in silicon nitride lattices. When the rare earth element europium enters a silicon nitride crystal lattice, the color of a silicon nitride micro-strip is gradually changed from white to yellow, and the micro-strip is changed from yellow to orange along with the increase of the content of the rare earth element europium.
Preferably, the flow rate of the nitrogen atmosphere is 50 to 1000ml/min, and the pressure is maintained between 0.8 to 4 atm.
Preferably, the mixing is ball milling mixing in an inert atmosphere; the rotation speed of ball milling mixing is 100-400 r/min, and the time is 2-4 hours.
In a third aspect, the invention provides an aluminum-doped silicon nitride material prepared by the preparation method, wherein the aluminum-doped silicon nitride material is Al-doped alpha-Si3N4Micron belt, Al element 0.05-5.75 atomic%.
Preferably, the optical band gap of the aluminum-doped silicon nitride material is 2.30-2.95 eV; the Al-doped alpha-Si3N4The size of the micron band is 10 to 200 μm × 0.5 to 5 μm × 0.01 to 0.5 μm.
In a fourth aspect, the invention provides an aluminum-doped silicon nitride-based orange-red fluorescent material prepared according to the preparation method, wherein the atomic percent of Al element in the aluminum-doped silicon nitride-based orange-red fluorescent material is 0.05% -5.75%, and the atomic percent of Eu element is 0.01% -3.50%.
Preferably, the aluminum-doped silicon nitride-based orange-red fluorescent material exhibits broadband luminescence of 500-800 nm under the excitation of blue light with the wavelength of 420-460 nm.
In a fifth aspect, the invention provides a method for adjusting an optical band gap of an aluminum-doped silicon nitride material, wherein silicon powder and aluminum powder are selected as raw material powder and mixed in a nitrogen atmosphere for reaction to prepare the aluminum-doped silicon nitride material, and the optical band gap of the aluminum-doped silicon nitride material is controllable between 2.30 eV and 2.95eV by controlling the molar ratio of the silicon powder to the aluminum powder to be 2000: 1-20: 1.
According to theoretical calculation results, the reason that the aluminum doping can reduce the silicon nitride band gap is that the interstitial aluminum can introduce impurity energy levels into the silicon nitride band gap, so that the silicon nitride band gap is reduced.
In a sixth aspect, the invention provides a preparation method of a white light LED, which is characterized in that the aluminum-doped silicon nitride-based orange-red fluorescent material and a binder are mixed and then coated on the surface of a blue light chip and dried to obtain the white light LED; the mass ratio of the aluminum-doped silicon nitride-based orange-red fluorescent material to the binder is 0.3: 1-0.1: 1.
Preferably, the binder is epoxy resin and polyurethane.
Has the advantages that:
(1) compared with pure silicon nitride, the band gap of the aluminum-doped silicon nitride material obtained by the invention is greatly reduced, and the regulation and control of the size of the band gap can be realized by changing the content of aluminum;
(2) the aluminum-doped silicon nitride-based orange-red fluorescent material doped with the rare earth element europium presents an orange-red broadband emission peak of 500-800 nm under the excitation of blue light. This shows that the fluorescent material is a novel orange-red fluorescent material for white light LED which can be excited by blue light. The method can accurately control the content of the doped aluminum and the rare earth element, and realize the accurate control of the band gap of the aluminum-doped silicon nitride material;
(3) the aluminum-doped silicon nitride-based orange-red fluorescent material prepared by the direct nitridation method has a wide emission peak coverage range (500-800 nm) and a red shift of the peak position, can meet the requirements of practical application, and can widen the application of silicon nitride to the field of solid-state lighting.
Drawings
Fig. 1 is an X-ray diffraction pattern of an aluminum-doped α -phase silicon nitride and an aluminum-doped α -phase silicon nitride-based orange-red fluorescent material doped with rare-earth element europium, and it can be seen from the pattern that aluminum doped into a silicon nitride lattice changes the number of atoms, the kinds of atoms, and the arrangement of the atoms in the silicon nitride lattice, so that the silicon nitride is preferentially oriented, and finally, the diffraction peak intensity of a sample is greatly changed compared with a standard card;
FIG. 2 is an SEM image of aluminum-doped alpha-phase silicon nitride obtained with a molar ratio of silicon powder to aluminum powder of 1000:1(a), 200:1(b), 100:1(c), and 50:1(d), and it can be seen that the increase in aluminum content promotes the increase in the size of the micron band because aluminum atoms play a role as a catalyst during the growth of the silicon nitride micron band. The higher the content of the aluminum element is, the more remarkable the tendency of the silicon nitride micro-strip to grow along a certain direction is;
FIG. 3 is an HRTEM image of Al-doped alpha-phase silicon nitride obtained at a molar ratio of 50:1 of Si powder to Al powder and Al-doped alpha-phase silicon nitride obtained at a molar ratio of 200:1 of Si powder to Al powder (a, b, c) and (d, e, f), wherein the inset in b is SAED and the inset in e is SAED, and it can be seen that different amounts of Al can cause preferential growth of silicon nitride micro-bands in different directions, and the difference in microstructure is an inherent cause of the difference in the band gap of Al-doped silicon nitride formed by different Si/Al molar ratios;
FIG. 4 is a graph of the UV-VIS absorption spectra of aluminum-doped alpha-phase silicon nitride of varying amounts and (. alpha.h v)2-h v dependence, from which it can be seen that the band gap of aluminum-doped silicon nitride formed by different silicon to aluminum molar ratios increases with increasing aluminum content;
fig. 5 is an excitation spectrum (a) of the al-doped α -phase silicon nitride-based fluorescent material and an emission spectrum (b) of a white LED formed by encapsulating a blue light chip and the al-doped silicon nitride-based orange-red fluorescent material prepared in example 5, and it can be seen from the figure that under excitation of blue light of 450nm, a broadband emission peak of the fluorescent material covers 500 to 800 nm;
fig. 6 is a CIE coordinate of the white LED formed by packaging the aluminum-doped silicon nitride-based orange-red fluorescent material with different content and the blue light chip, and it can be known from the CIE coordinate that the color temperature of the white LED gradually increases as the content of the fluorescent material gradually decreases.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, the main phase of the aluminum-doped silicon nitride-based orange-red fluorescent material is alpha-phase silicon nitride, and has a microstrip structure. Wherein, the atomic percentage of the aluminum element in the material is 0.05 to 5.75 percent, and the atomic percentage of the europium element in the material is 0.01 to 3.50 percent. Wherein, the aluminum-doped silicon nitride-based orange-red fluorescent material presents an orange-red broadband emission peak under the excitation of blue light.
In the present disclosure, the main phase of the aluminum-doped silicon nitride material is α -phase silicon nitride, the atomic percentage of aluminum element in the material is 0.05% to 5.75%, and the structure is an Al-doped α -phase silicon nitride micro-strip. The size of the micro-strip can be 10 to 200 μm × 0.5 to 5 μm × 0.01 to 0.5 μm. Wherein the optical band gap of the aluminum-doped silicon nitride material can be 2.30-2.95 eV.
In the embodiment of the invention, the aluminum-doped silicon nitride material or the aluminum-doped silicon nitride-based orange-red fluorescent material is prepared by adopting a direct nitridation mode. The following exemplary method for preparing aluminum-doped silicon nitride material is described.
And weighing silicon powder and Al powder and uniformly mixing the raw materials to obtain mixed powder. The molar ratio of the silicon powder to the aluminum powder can be 2000: 1-20: 1. The mixing can be ball milling mixing in inert atmosphere; the rotation speed of ball milling mixing is 100-400 r/min, and the time is 2-4 hours.
And reacting in a reaction furnace continuously filled with nitrogen, and obtaining a final product after the reaction is finished. The flow rate of nitrogen is 50-1000 ml/min, and the pressure is maintained at 1 atm. The reaction temperature can be 1300-2000 ℃, and the reaction time can be 2-48 h.
The following exemplarily illustrates a method for preparing the aluminum-doped silicon nitride-based orange-red fluorescent material.
And weighing silicon powder, Al powder and europium oxide, and uniformly mixing the raw materials to obtain mixed powder. The molar ratio of the silicon powder to the aluminum powder can be 2000: 1-20: 1. The molar ratio of the silicon element to the europium element can be 1000: 1-30: 1. The mixing can be ball milling mixing in inert atmosphere; the rotation speed of ball milling mixing is 100-400 r/min, and the time is 2-4 hours.
And reacting in a reaction furnace continuously filled with nitrogen, and obtaining a final product after the reaction is finished. After addition of europium oxide, the reaction gives an orange-red product. The flow rate of nitrogen is 50-1000 ml/min, and the pressure is maintained at 1 atm. The reaction temperature can be 1300-2000 ℃, and the reaction time can be 2-48 h.
In one embodiment of the invention, the optical band gap is regulated and controlled by the addition of Al, and the optical band gap (2.30-2.95 eV) of the aluminum-doped silicon nitride material is changed along with the change of the aluminum content (0.05 at% -5.75 at%).
In an embodiment of the present invention, an aluminum-doped silicon nitride-based fluorescent material doped with rare-earth element europium (i.e., an aluminum-doped silicon nitride-based orange-red fluorescent material) and a blue light chip are combined to form a white LED. Specifically, the aluminum-doped silicon nitride-based orange-red fluorescent material and the binder are mixed and then coated on the surface of a blue light chip and dried to obtain the white light LED. The mass ratio of the aluminum-doped silicon nitride-based orange-red fluorescent material to the binder can be (0.3-0.1): 1. the binder may be epoxy resin, polyurethane, etc. The drying temperature can be 60-80 ℃, and the drying time can be 12-24 hours. Preferably, the thickness of the coating obtained on the surface of the blue light chip is not more than 1 mm.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Respectively weighing 4g of silicon powder and 0.0038g of aluminum powder, ball-milling and uniformly mixing under an inert atmosphere, placing in a graphite tube, reacting at 1300 ℃ for 12h, and taking out a product. Continuously introducing nitrogen in the whole reaction process, wherein the nitrogen flow rate is 100 ml/min;
the product is characterized by an X-ray diffractometer, and the aluminum-doped silicon nitride of the invention all presents alpha-Si3N4And (4) phase(s). The product is characterized by an energy spectrometer, the element components of the aluminum-doped silicon nitride are Si, N and Al, and the atomic percent of aluminum in the product is 0.1%. The product is characterized by an ultraviolet visible absorption spectrometer, and the band gap of the aluminum-doped silicon nitride is 2.58 eV.
Example 2
Respectively weighing 4g of silicon powder and 0.0192g of aluminum powder, ball-milling and uniformly mixing under inert atmosphere, placing the mixture in a graphite tube, reacting for 8 hours at 1550 ℃, and taking out the product. Nitrogen was continuously introduced throughout the reaction at a flow rate of 200 ml/min. The product is characterized by an X-ray diffractometer, and the aluminum-doped silicon nitride of the invention all presents alpha-Si3N4And (4) phase(s). The product is characterized by a scanning electron microscope and a transmission electron microscope, and the aluminum-doped silicon nitride is a micron band with the length of 11 mu m, the width of 460nm and the thickness of 33nm and grows by stacking a (012) crystal face. The product is characterized by an energy spectrometer, the element components of the aluminum-doped silicon nitride are Si, N and Al, and the atomic percent of aluminum in the product is 0.49%. The product is characterized by an ultraviolet visible absorption spectrometer, and the band gap of the aluminum-doped silicon nitride is 2.67 eV.
Example 3
Respectively weighing 4g of silicon powder and 0.0384g of aluminum powder, ball-milling and uniformly mixing under an inert atmosphere, placing in a graphite tube, reacting at 1600 ℃ for 6 hours, and taking out a product. Nitrogen was continuously introduced throughout the reaction. The nitrogen flow rate is 400 ml/min;
the product is characterized by an X-ray diffractometer, and the aluminum-doped silicon nitride of the invention all presents alpha-Si3N4And (4) phase(s). The product is characterized by an energy spectrometer, the element components of the aluminum-doped silicon nitride are Si, N and Al, and the atomic percent of aluminum in the product is 0.97%. The product is characterized by an ultraviolet visible absorption spectrometer, and the band gap of the aluminum-doped silicon nitride is 2.74 eV.
Example 4
Respectively weighing 4g of silicon powder and 0.0769g of aluminum powder, ball-milling and uniformly mixing under inert atmosphere, placing in a graphite tube, reacting at 1700 ℃ for 2h, and taking out the product. Nitrogen was continuously introduced throughout the reaction. The nitrogen flow rate was 600 ml/min.
The product is characterized by an X-ray diffractometer, and the aluminum-doped silicon nitride of the invention all presents alpha-Si3N4And (4) phase(s). The product is characterized by a scanning electron microscope and a transmission electron microscope, the aluminum-doped silicon nitride is a micron band with the length of 78 mu m, the width of 2 mu m and the thickness of 340nm, and the (011) crystal face is subjected to stacking growth. The product is characterized by an energy spectrometer, the element components of the aluminum-doped silicon nitride are Si, N and Al, and the atomic percent of aluminum in the product is 1.70%. The product is characterized by an ultraviolet visible absorption spectrometer, and the band gap of the aluminum-doped silicon nitride is 2.85 eV.
Example 5
Respectively weighing 4g of silicon powder, 0.0125g of europium oxide and 0.0038g of aluminum powder, ball-milling and uniformly mixing under an inert atmosphere, placing in a graphite tube, reacting at 1300 ℃ for 12h, and taking out an orange product. Nitrogen was continuously introduced throughout the reaction. The nitrogen flow rate is 100 ml/min;
the product is characterized by an X-ray diffractometer, and the aluminum-doped silicon nitride of the invention all presents alpha-Si3N4And (4) phase(s). The product is characterized by an energy spectrometer, and the inventionThe aluminum-doped silicon nitride-based orange-red fluorescent material comprises the element components of Si, N, Eu and Al, wherein the atomic percent of aluminum in the product is 0.1%, and the atomic percent of europium in the material is 0.01%. The product is characterized by a fluorescence spectrometer, and under the excitation of blue light of 450nm, the product presents an orange-red broadband emission peak with the peak position of 570 nm. The emission peak at 570nm was monitored, and an excitation peak with a peak position of 481nm was obtained.
Example 6
Respectively weighing 4g of silicon powder, 0.0627g of europium oxide and 0.0192g of aluminum powder, ball-milling and uniformly mixing under the nitrogen atmosphere, placing the mixture into a graphite tube, reacting at 1550 ℃ for 8 hours, and taking out an orange product. Nitrogen was continuously introduced throughout the reaction. The nitrogen flow rate is 200 ml/min;
the product is characterized by an X-ray diffractometer, and the aluminum-doped silicon nitride of the invention all presents alpha-Si3N4And (4) phase(s). The product is characterized by an energy spectrometer, the element components of the aluminum-doped silicon nitride-based orange-red fluorescent material are Si, N, Eu and Al, the atomic percent of aluminum in the product is 0.49%, and the atomic percent of europium in the material is 0.06%. The product is characterized by a fluorescence spectrometer, and under the excitation of blue light of 450nm, the product presents an orange-red broadband emission peak with the peak position of 570 nm. The emission peak at 570nm was monitored, and an excitation peak with a peak position at 464nm was obtained.
Example 7
Respectively weighing 4g of silicon powder, 0.1253g of europium oxide and 0.0384g of aluminum powder, ball-milling and uniformly mixing under the nitrogen atmosphere, placing the mixture into a graphite tube, reacting at 1600 ℃ for 6 hours, and taking out an orange product. Nitrogen was continuously introduced throughout the reaction. The nitrogen flow rate is 400 ml/min;
the product is characterized by an X-ray diffractometer, and the aluminum-doped silicon nitride of the invention all presents alpha-Si3N4And (4) phase(s). The product is characterized by an energy spectrometer, the element components of the aluminum-doped silicon nitride-based orange-red fluorescent material are Si, N, Eu and Al, the atomic percent of the aluminum in the product is 0.97%, and the atomic percent of the europium in the material is 0.11%. The product was characterized by fluorescence spectroscopy at 450nm blue lightUnder excitation, the product shows an orange-red broadband emission peak with the peak position at 570 nm. The emission peak at 570nm was monitored, and an excitation peak with a peak position at 452nm was obtained.
Example 8
Respectively weighing 4g of silicon powder, 0.4389g of europium oxide and 0.0769g of aluminum powder, ball-milling and uniformly mixing under the nitrogen atmosphere, placing the mixture into a graphite tube, reacting at 1700 ℃ for 2 hours, and taking out an orange product. Nitrogen was continuously introduced throughout the reaction. The nitrogen flow rate is 1000 ml/min;
the product is characterized by an X-ray diffractometer, and the aluminum-doped silicon nitride of the invention all presents alpha-Si3N4And (4) phase(s). The product is characterized by an energy spectrometer, the element components of the aluminum-doped silicon nitride-based orange-red fluorescent material are Si, N, Eu and Al, the atomic percent of the aluminum in the product is 1.70%, and the atomic percent of the europium in the material is 0.42%. The product is characterized by a fluorescence spectrometer, and under the excitation of blue light of 450nm, the product presents an orange-red broadband emission peak with the peak position of 570 nm. The emission peak at 570nm was monitored, and an excitation peak with a peak position at 435nm was obtained.
Example 9
Weighing three parts (0.2g, 0.15g and 0.12g) of the aluminum-doped silicon nitride-based orange-red fluorescent material obtained in example 5 as a raw material, taking epoxy resin (1g) as a binder, mixing, respectively coating the mixture on the surfaces of different blue light chips, and drying to obtain the white light LED. The thickness of the fluorescent coating on the obtained white light LED is 0.5-1 mm. The drying temperature is 60 ℃ and the drying time can be 12 hours.
And (3) placing the three obtained white light LED samples in a dry environment, and performing white light test by using an ultraviolet-visible-near infrared spectrum analysis system and an integrating sphere to obtain white lights with the color temperatures of 3381K, 5602K and 6523K respectively, which are shown as (a), (b) and (c) in fig. 6.
Claims (10)
1. A preparation method of an aluminum-doped silicon nitride material is characterized in that silicon powder and aluminum powder are mixed and then placed in a nitrogen atmosphere to react for 2-48 hours at 1300-2000 ℃ to obtain the aluminum-doped silicon nitride material; the molar ratio of the silicon powder to the aluminum powder is 2000: 1-20: 1.
2. A preparation method of an aluminum-doped silicon nitride-based orange-red fluorescent material is characterized in that silicon powder, aluminum powder and europium oxide are mixed and then placed in a nitrogen atmosphere to react for 2-48 hours at 1300-2000 ℃ to obtain the aluminum-doped silicon nitride-based orange-red fluorescent material; the molar ratio of the silicon powder to the aluminum powder is 2000: 1-20: 1, and the molar ratio of the silicon element in the silicon powder to the europium element in the europium oxide is 1000: 1-30: 1.
3. The method according to claim 1 or 2, wherein the flow rate of the nitrogen atmosphere is 50 to 1000ml/min, and the pressure is maintained between 0.8 to 4 atm.
4. The production method according to claim 1 or 2, wherein the mixing is ball-milling mixing in an inert atmosphere; the rotation speed of ball milling mixing is 100-400 r/min, and the time is 2-4 hours.
5. The aluminum-doped silicon nitride material prepared by the preparation method according to claim 1, wherein the aluminum-doped silicon nitride material is Al-doped alpha-Si3N4Micron belt, Al element 0.05-5.75 atomic%.
6. The aluminum-doped silicon nitride material as claimed in claim 5, wherein the optical band gap of the aluminum-doped silicon nitride material is 2.30-2.95 eV; the Al-doped alpha-Si3N4The size of the micron band is 10 to 200 μm × 0.5 to 5 μm × 0.01 to 0.5 μm.
7. The aluminum-doped silicon nitride-based orange-red fluorescent material prepared by the preparation method according to claim 2, wherein the atomic percent of Al element in the aluminum-doped silicon nitride-based orange-red fluorescent material is 0.05-5.75%, and the atomic percent of Eu element in the aluminum-doped silicon nitride-based orange-red fluorescent material is 0.01-3.50%.
8. The aluminum-doped silicon nitride-based orange-red fluorescent material as claimed in claim 7, wherein the aluminum-doped silicon nitride-based orange-red fluorescent material exhibits broadband luminescence of 500-800 nm under the excitation of blue light with a wavelength of 420-460 nm.
9. A method for adjusting an optical band gap of an aluminum-doped silicon nitride material is characterized in that silicon powder and aluminum powder are selected as raw material powder and mixed, then the mixture is placed in a nitrogen atmosphere to react to prepare the aluminum-doped silicon nitride material, and the optical band gap of the aluminum-doped silicon nitride material is controllable between 2.30 eV and 2.95eV by controlling the molar ratio of the silicon powder to the aluminum powder to be 2000: 1-20: 1.
10. A preparation method of a white light LED is characterized in that the aluminum-doped silicon nitride-based orange-red fluorescent material of claim 7 or 8 is mixed with an adhesive, coated on the surface of a blue light chip and dried to obtain the white light LED; the mass ratio of the aluminum-doped silicon nitride-based orange-red fluorescent material to the binder is 0.3: 1-0.1: 1.
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