CN115044374A - Red luminescent material, preparation method thereof and luminescent device - Google Patents
Red luminescent material, preparation method thereof and luminescent device Download PDFInfo
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Abstract
The application relates to the technical field of luminescent materials, and provides a red luminescent material with a chemical general formula A m D n E q M z ：xEu 3+ Wherein, A comprises at least one of La, Gd, Lu and Y elements, D comprises at least one of Al, Ga and In elements, E comprises at least one of Ca, Sr and Ba elements, and M comprises O element; m is more than or equal to 0.9 and less than or equal to 1.1, n is more than or equal to 0.9 and less than or equal to 1.1, q is more than or equal to 1.9 and less than or equal to 2.1, z is more than or equal to 4.8 and less than or equal to 5.2, and x is more than 0 and less than or equal to 0.2. The red luminescent material provided by the application uses rare earth ions Eu 3+ As an activator, A m D n E q M z Is a luminescent matrix, Eu is due to rare earth ion 3+ The emission spectrum of the red luminescent material is linear emission, and the gallate containing Gd and Sr has high luminescent efficiency, so that the red luminescent material has wide absorption range, high color purity and high-temperature lightLow attenuation efficiency, high luminous efficiency and good stability under the excitation of ultraviolet light.
Description
Technical Field
The application belongs to the technical field of luminescent materials, and particularly relates to a red luminescent material, a preparation method thereof and a luminescent device.
Background
Currently, blue LED (light emitting diode) chips are used to excite YAG: the yellow Ce (cerium) phosphor is a common way to produce white light emission, is simple to manufacture, has low cost, and can be applied to large-scale commercial application. However, the emission spectrum of the light emitting device is seriously lost in a red region, so that the color rendering index of white light is low, the color temperature is high, and human eyes are damaged after the light emitting device is used for a long time. In order to improve the defect, red fluorescent powder in a long wave direction is usually added on the basis to reduce the color temperature, improve the color rendering index and perfect the spectrum components of white light. In addition, the fluorescent powder adopting the near ultraviolet chip to excite the blue, green and red three colors can obtain the white light with high color rendering index and low color temperature, and the two modes need to add the red fluorescent powder material suitable for the chip excitation, so the red fluorescent powder material occupies a very important position in the field of white light LED illumination.
The existing red fluorescent powder mainly comprises nitride fluorescent powder with broadband emission and fluoride narrow-band red fluorescent powder, however, the nitride fluorescent powder is easy to mutually absorb with other fluorescent powder due to the characteristic of broadband emission, so that the luminous efficiency of the device is low; the fluoride narrow-band red fluorescent powder is easy to decompose and lose efficacy in rainwater or a humid environment due to poor water resistance, poor in chemical stability and high in price.
Therefore, how to develop a red light emitting material with high light emitting efficiency and good chemical stability is a problem to be solved urgently.
Disclosure of Invention
The present application aims to provide a red luminescent material, a preparation method thereof and a luminescent device, and aims to solve the problems of poor luminescent efficiency and chemical stability of the existing red luminescent material.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a red light emitting material, which has a chemical formula A m D n E q M z ：xEu 3+ Wherein A comprises at least one of La, Gd, Lu and Y elements, D comprises at least one of Al, Ga and In elements, E comprises at least one of Ca, Sr and Ba elements, and M comprises O element; m is more than or equal to 0.9 and less than or equal to 1.1, n is more than or equal to 0.9 and less than or equal to 1.1, q is more than or equal to 1.9 and less than or equal to 2.1, z is more than or equal to 4.8 and less than or equal to 5.2, and x is more than 0 and less than or equal to 0.2.
In a second aspect, the present application provides a method for preparing a red light emitting material, comprising the following steps:
the chemical formula of the red luminescent material provided by the application is A m D n E q M z ：xEu 3+ Weighing compound raw materials of each element according to the metering ratio, and mixing and grinding the compound raw materials to obtain a raw material mixture;
and sintering the raw material mixture, and crushing to obtain the red luminescent material.
In a third aspect, the present application provides a light-emitting device, comprising a light source and a luminescent material excited by the light source, wherein the luminescent material comprises the red luminescent material provided by the present application or the red luminescent material prepared by the preparation method of the red luminescent material provided by the present application.
Compared with the prior art, the method has the following beneficial effects:
the red luminescent material provided by the first aspect of the application comprises a compound with a chemical formula of A m D n E q M z ：xEu 3+ Inorganic compound of (1), which employs rare earth ion Eu 3+ As activators, A m D n E q M z As a luminescent matrix component, A m D n E q M z The luminescent substrate is rare earth ion Eu 3+ Providing crystal field environment to make rare earth ion Eu 3+ The outer 5d energy level electrons absorb energy under the action of an external electric field and jump to a high energy state in the 5d energy level group, and then the relaxation transition is carried out to a low energy level state, wherein partial energy is released in the form of photons to emit light. Due to rare earth ion Eu 3+ Exist of 5 D 0 - 7 F 2 Transition makes the emission spectrum of the gallium arsenide compound linear emission and contains Gd and Sr elements m D n E q M z ) Has high luminous efficiency, so that the red luminescent material adopts rare earth ion Eu 3+ Excitation A m D n E q M z Has the advantages of wide absorption range, high color purity, low light effect attenuation rate at high temperature, and the like. Therefore, the red luminescent material can emit bright red light under the excitation of ultraviolet light, and has high luminous efficiency and good chemical stability. In addition, the red luminescent material can be matched with blue fluorescent powder and green fluorescent powder for use, and can generate white light with high color rendering index, low color temperature and high luminous efficiency, so that the white light quality is improved, and the red luminescent material has a great application prospect in the field of white light LEDs.
The preparation method of the red luminescent material provided by the second aspect of the present application is to firstly follow the chemical general formula A of the red luminescent material m D n E q M z ：xEu 3+ The compound raw materials of each element are weighed according to the metering ratio, mixed and ground, then the obtained raw material mixture is sintered, and the red luminescent material with high luminous efficiency and good chemical stability can be obtained after crushing. The preparation process is simple, the raw materials are easy to obtain, no pollution is caused to the environment, and the preparation method is suitable for large-scale production.
The light-emitting device provided by the third aspect of the present application contains the red light-emitting material of the present application or the red light-emitting material prepared by the preparation method of the present application, so that the light-emitting device has high light-emitting efficiency, good chemical stability and good application prospect.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a process flow chart of a method for preparing a red luminescent material provided in an embodiment of the present application;
fig. 2 is an XRD spectrum of the red luminescent material provided in examples 1, 6, 14 and 18 of the present application;
fig. 3 shows emission spectra of the red luminescent materials provided in examples 1, 6, 14 and 18 of the present application under excitation at 380 nm.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
In a first aspect, embodiments of the present application provide a red luminescent material, where a chemical formula of the red luminescent material is a m D n E q M z ：xEu 3+ Wherein, A comprises at least one of La element, Gd element, Lu element and Y element, D comprises at least one of Al element, Ga element and In element, E comprises at least one of Ca element, Sr element and Ba element, and M comprises O element; m is more than or equal to 0.9 and less than or equal to 1.1, n is more than or equal to 0.9 and less than or equal to 1.1, q is more than or equal to 1.9 and less than or equal to 2.1, z is more than or equal to 4.8 and less than or equal to 5.2, and x is more than 0 and less than or equal to 0.2.
The red luminescent material provided by the embodiment of the application comprises a compound with a chemical general formula A m D n E q M z ：xEu 3+ The position of E is substituted by Eu, which adopts rare earth ion Eu 3+ As activators, A m D n E q M z As a luminescent matrix component, A m D n E q M z The luminescent substrate is rare earth ion Eu 3+ Providing crystal field environment to make rare earth ion Eu 3+ The outer 5d level electrons absorb energy under the action of an external electric field and jump to a high energy state in the 5d level group, then the relaxation transition is carried out to a low energy state, and partial energy is released in the form of photons to emit light. Due to rare earth ion Eu 3+ Exist of 5 D 0 - 7 F 2 Transition makes the emission spectrum of the gallium arsenide compound linear emission and contains Gd and Sr elements m D n E q M z ) Has high luminous efficiency, so that the red luminescent material adopts rare earth ion Eu 3+ Excitation A m D n E q M z Has the advantages of wide absorption range, high color purity, low light effect attenuation rate at high temperature, and the like. Therefore, the red luminescent material can emit bright red light under the excitation of ultraviolet light, and has high luminous efficiency and good chemical stability. In addition, the red luminescent material can be used in combination with blue fluorescent powder and green fluorescent powder, so that the white light quality is improved, and the red luminescent material has a wide application prospect in the field of white light LEDs.
In the examples, the red luminescent material has the general chemical formula A m D n E q M z ：xEu 3+ Wherein A comprises at least one of La (lanthanum), Gd (gadolinium), Lu (lutetium) and Y (yttrium), D comprises at least one of Al (aluminum), Ga (gallium) and In (indium), E comprises at least one of Ca (calcium), Sr (strontium) and Ba (barium), M comprises O (oxygen), and the value ranges of M, n, q, z and x are as follows: m is more than or equal to 0.9 and less than or equal to 1.1, n is more than or equal to 0.9 and less than or equal to 1.1, q is more than or equal to 1.9 and less than or equal to 2.1, z is more than or equal to 4.8 and less than or equal to 5.2, and x is more than 0 and less than or equal to 0.2. Preferably 0.95-1.05 m, 0.95-1.05 n, 1.9-2.0 q, 4.9-5 z.1，0.05≤x≤0.15。
In the examples, the red luminescent material has the general chemical formula A m D n E q M z ：xEu 3+ Wherein A is Gd element, D is Ga element, E is Sr element, M is O element, M is 1, n is 1, q is 1.9, z is 5, x is 0.1, and the red luminescent material is GdGaSr 1.9 O 5 ：0.1Eu 3+ Determination of GdGaSr 2 O 5 Eu in pure luminescent matrix 3+ The optimum concentration of ions and thus the emission intensity can be adjusted. If the activator Eu 3+ When the concentration is less than the optimal concentration, Eu is activated 3+ The quantity of ions (luminescence center ions) is insufficient, and the quantity of photons emitted by the ions is limited, so that the luminescence intensity of the ions is weak; if the activator Eu 3+ At a concentration higher than the optimum concentration, Eu 3+ The critical distance of ions in the crystal lattice is reduced, and the emitted energy is reduced due to mutual absorption, so that the luminous intensity is weakened; therefore, the red luminescent material is in the activator Eu 3+ At an optimum concentration of (1), and GdGaSr 1.9 O 5 As a pure luminescent substrate, the red luminescent material has good luminescent intensity and thermal stability, so that the luminescent intensity of the red luminescent material is optimal.
In the examples, the red luminescent material has the general chemical formula A m D n E q M z ：xEu 3+ Wherein A comprises Gd element, and A further comprises at least one of La element, Lu element and Y element; the atomic ratio of Gd element in a to the total amount of other elements in a is 1: (0.01-0.25). By doping La element, Lu element, Y element and the like with a certain proportion, which are in the same family or have similar ionic radius and same valence with Gd element, the components of the matrix material can be regulated and controlled, and rare earth ion Eu is used 3+ The luminescence is that the outer layer electrons carry out f-f transition in a sublevel, and the f-f transition is basically not influenced by the crystal field environment change caused by the regulation and control of matrix components, so that the position of the peak wavelength of an emission spectrum can be kept unchanged, and therefore, by doping elements with similar plasma radiuses and same valence states of La elements, Lu elements and Y elements, the raw material dosage of Gd elements can be reduced under the condition of ensuring that the change of the luminous efficiency is not large, and the preparation cost can be reduced. In thatIn a specific embodiment, a may include Gd element and La element, or Gd element and Lu element, or Gd element and Y element, a may further include Gd element, La element and Lu element, or Gd element, Lu element and Y element, or Gd element, La element and Y element, and a may further include Gd element, La element, Lu element and Y element.
In the examples, the red luminescent material has the general chemical formula A m D n E q M z ：xEu 3+ Wherein D comprises Ga element, and D further comprises at least one of Al element and In element; the atomic ratio of Ga element in D to the total amount of other elements in D is 1: (0.01-0.2). By doping Al element, In element and the like with a certain proportion, the same family as Ga element or similar ionic radius and the same valence state, the components of the matrix material can be regulated and controlled, and rare earth ion Eu is used 3+ The luminescence is that the outer layer electron carries out f-f transition In the energy level, and the luminescence is basically not influenced by the crystal field environment change caused by the regulation and control of the matrix components, so that the position of the peak wavelength of the emission spectrum can be kept unchanged, and therefore, the raw material dosage of high-cost Ga element can be reduced under the condition of ensuring that the luminous efficiency is not changed greatly by doping the elements with similar plasma radii and the same valence states of Al element and In element, and the preparation cost can be reduced. In a specific embodiment, D may include Ga element and Al element, D may further include Ga element and In element, and D may further include Ga element, Al element, and In element.
In the examples, the red luminescent material has the general chemical formula A m D n E q M z ：xEu 3+ In (b), E includes Sr element, and E further includes at least one of Ca element and Ba element. The atomic ratio of Sr element in E to the total amount of other elements in E is 1: (0.01-0.1). By doping Ca element and Ba element with a certain proportion, which have the same family or similar ionic radius and same valence as Sr element, the composition of matrix material can be regulated and controlled, and rare earth ion Eu 3+ The luminescence is that the outer electron carries out f-f transition in the sub-energy level, and the luminescence is basically not influenced by the crystal field environment change caused by the regulation and control of the matrix component, so that the position of the peak wavelength of the emission spectrum can be kept unchanged, and the doping is carried outThe elements with similar plasma radius and same valence state of the mixed Ca element and the Ba element can widen the research range of the red luminescent material under the condition of ensuring that the luminous efficiency is not changed greatly. In a specific embodiment, E may include Sr element and Ca element, E may further include Sr element and Ba element, and E may further include Sr element, Ca element, and Ba element.
In the examples, the red luminescent material has the general chemical formula A m D n E q M z ：xEu 3+ M further includes at least one of F element and N element. The atomic ratio of the O element in M to the total amount of the other elements in M is 1: (0.001-0.08). Under the condition of ensuring that the main structure of the red luminescent material substrate is not changed, a certain proportion of replaceable elements can be added, so that the solid solution red luminescent material with various components is formed. Alternative elements may refer to elements of the same group or adjacent surroundings in the periodic table of elements having similar ionic radii, electronegativities, valence states, and the like. Specifically, M may include an O element and an F element, M bits may further include an O element and an N element, and M bits may further include an O element, an F element, and an N element.
In an embodiment, the excitation wavelength of the red luminescent material is 320-400 nm, the peak wavelength of the emission spectrum is 585-590nm, and further the excitation wavelength of the red luminescent material is 380nm, and the peak wavelength of the emission spectrum is 588 nm. The red luminescent material of the embodiment has the advantages of good excitation efficiency, good luminescent stability and good luminous efficiency under the excitation of ultraviolet.
A second aspect of the embodiments of the present application provides a method for preparing a red light emitting material, including the following steps:
s10: the chemical formula of the red luminescent material provided by the application is A m D n E q M z ：xEu 3+ Weighing compound raw materials of each element according to the metering ratio, and mixing and grinding the compound raw materials to obtain a raw material mixture;
s20: and sintering the raw material mixture, and crushing to obtain the red luminescent material.
The preparation method of the red luminescent material provided by the embodiment of the application firstly adopts the red luminescent materialChemical general formula A m D n E q M z ：xEu 3+ The compound raw materials of each element are weighed according to the metering ratio, mixed and ground, then the obtained raw material mixture is sintered, and the red luminescent material with high luminous efficiency and good chemical stability can be obtained after crushing. The preparation process is simple, the raw materials are easy to obtain, no pollution is caused to the environment, and the preparation method is suitable for large-scale production.
In the above step S10, the compound raw material is mainly selected from oxides, nitrides, fluorides, carbonates, phosphates, etc. of the corresponding elements, and the raw material purity is not less than 99.9%.
In an embodiment, a method of preparing a feedstock mixture comprises: according to A m D n E q M z ：xEu 3+ Accurately weighing each element raw material, and grinding in a grinding mill for 15-25min to obtain a raw material mixture.
In the step S20, the sintering temperature is 1200-1350 ℃ and the sintering time is 7-9 h. For example: the sintering treatment temperature can be 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃ and the time can be 7h, 7.5h, 8h, 8.5h and 9 h.
In an embodiment, a method of sintering a raw material mixture includes: placing the raw material mixture into an alumina crucible, placing the alumina crucible into a high-temperature muffle furnace at 1200-1350 ℃ for sintering for 7-9h, cooling the alumina crucible to room temperature (25-27 ℃) along with the furnace to obtain a roasted product, and then crushing and grinding the roasted product to obtain the red luminescent material
In a third aspect, the present application provides a light-emitting device, comprising a light source and a luminescent material excited by the light source, wherein the luminescent material comprises the red luminescent material provided by the present application or the red luminescent material prepared by the preparation method of the red luminescent material provided by the present application.
The light-emitting device provided by the embodiment of the application contains the red light-emitting material or the red light-emitting material prepared by the preparation method of the application, so that the light-emitting device has high light-emitting efficiency, good chemical stability and good application prospect.
In an embodiment, the light-emitting device comprises a light-emitting materialThe material also comprises blue fluorescent powder and green fluorescent powder, and the blue fluorescent powder is BaMgAl 10 O 17 :Eu 2+ The green phosphor is (Ca, Sr) 2 SiO 4 :Eu 2+ 。
The following description will be given with reference to specific examples.
Example 1
A red luminescent material with the chemical formula of GdGaSr 1.9 O 5 ：0.1Eu 3+ . The preparation method of the red luminescent material comprises the following steps:
according to the chemical formula GdGaSr 1.9 O 5 :0.1Eu 3+ The Gd is accurately weighed according to the stoichiometric ratio of (A) 2 O 3 、Ga 2 O 3 、SrCO 3 、Eu 2 O 3 The raw materials are placed in a grinder, ground for 20min and then transferred to an alumina crucible, the alumina crucible is placed in a high-temperature muffle furnace to be sintered for 8h at 1300 ℃, the furnace is cooled to room temperature (25 ℃), and the obtained roasted product is crushed and ground to obtain the red luminescent material. The peak wavelength of the emission spectrum of the red luminescent material is 588nm, an X-ray diffractometer is used for analyzing a sample, the XRD diffraction pattern of the red luminescent material is shown in figure 2, a fluorescence spectrometer is used for carrying out excitation and emission spectrum tests on the sample, and the emission spectrum of the red luminescent material is shown in figure 3.
Examples 2 to 5
A red luminescent material has the chemical formula shown in Table 1, except that Eu 3+ The preparation method was the same as example 1 except that the doping concentration was different from example 1.
Example 6
A red luminescent material with the chemical formula of GdGa 0.8 Al 0.2 Sr 1.9 O 5 :0.1Eu 3+ . The preparation method of the red luminescent material comprises the following steps:
according to the formula GdGa 0.8 Al 0.2 Sr 1.9 O 5 ：0.1Eu 3+ The Gd is accurately weighed according to the stoichiometric ratio of (1) 2 O 3 、Ga 2 O 3 、Al 2 O 3 、SrCO 3 、Eu 2 O 3 The raw materials are placed in a grinding machineAnd grinding for 20min, transferring to an alumina crucible, sintering in a high-temperature muffle furnace at 1300 ℃ for 8h, cooling to room temperature (25 ℃) along with the furnace, and crushing and grinding the obtained roasted product to obtain the red luminescent material.
The peak wavelength of the emission spectrum of the red luminescent material is 588nm, an X-ray diffractometer is used for analyzing a sample, the XRD diffraction pattern of the red luminescent material is shown in figure 2, a fluorescence spectrometer is used for carrying out excitation and emission spectrum tests on the sample, and the emission spectrum of the red luminescent material is shown in figure 3.
Examples 7 to 8
A red luminescent material has the chemical formula shown in the following table 1, and the preparation method is the same as that of example 6 except that the Ga site of the cation site is doped with different elements and the relative content is different from that of example 6.
Examples 9 to 13
A red luminescent material has the chemical formula shown in the following table 1, and the preparation method is the same as that of example 6 except that the Gd site of the cationic site is doped with different elements and the relative content is different from that of example 6.
Example 14
A red luminescent material with the chemical formula of GdGaSr 1.7 Ca 0.2 O 5 :0.1Eu 3+ . The preparation method of the red luminescent material comprises the following steps:
according to the chemical formula GdGaSr 1.7 Ca 0.2 O 5 :0.1Eu 3+ The Gd is accurately weighed according to the stoichiometric ratio of (A) 2 O 3 、Ga 2 O 3 、CaCO 3 、SrCO 3 、Eu 2 O 3 The raw materials are placed in a grinder, ground for 20min and then transferred to an alumina crucible, the alumina crucible is placed in a high-temperature muffle furnace to be sintered for 8h at 1300 ℃, the furnace is cooled to room temperature (25 ℃), and the obtained roasted product is crushed and ground to obtain the red luminescent material.
The peak wavelength of the emission spectrum of the red luminescent material is 588nm, an X-ray diffractometer is used for analyzing a sample, the XRD diffraction pattern of the red luminescent material is shown in figure 2, a fluorescence spectrometer is used for carrying out excitation and emission spectrum tests on the sample, and the emission spectrum of the red luminescent material is shown in figure 3.
Examples 15 to 17
A red luminescent material, whose chemical formula is shown in Table 1 below, was prepared in the same manner as in example 14, except that the Sr site of the cation lattice was doped with different elements and the relative content was different from that of example 14.
Example 18
A red luminescent material with the chemical formula of GdGaSr 2 (O,F) 5 :0.1Eu 3+ . The preparation method of the red luminescent material comprises the following steps:
according to the chemical formula GdGaSr 2 (O,F) 5 :0.1Eu 3+ The Gd is accurately weighed according to the stoichiometric ratio of (A) 2 O 3 、Ga 2 O 3 、SrCO 3 、SrF 2 、Eu 2 O 3 The raw materials are placed in a grinder, ground for 20min and then transferred to an alumina crucible, the alumina crucible is placed in a high-temperature muffle furnace to be sintered for 8h at 1300 ℃, the furnace is cooled to room temperature (25 ℃), and the obtained roasted product is crushed and ground to obtain the red luminescent material.
The peak wavelength of the emission spectrum of the red luminescent material is 588nm, an X-ray diffractometer is used for analyzing a sample, the XRD diffraction pattern of the red luminescent material is shown in figure 2, a fluorescence spectrometer is used for carrying out excitation and emission spectrum tests on the sample, and the emission spectrum of the red luminescent material is shown in figure 3.
Example 19
A red luminescent material, whose chemical formula is shown in Table 1 below, was prepared in the same manner as in example 18, except that the anion site O site was doped with different elements and the relative contents were different from those in example 18.
Comparative example 1
A red fluorescent powder with chemical formula of NaGdSiO 4 :Eu 3+ . The preparation method of the red fluorescent powder comprises the following steps:
according to the chemical formula NaGdSiO 4 :Eu 3+ Stoichiometric ratio of (2), accurately weighing Na 2 CO 3 、Gd 2 O 3 、SiO 2 、Eu 2 O 3 The raw materials are placed in a grinding mill, ground for 20min and transferred to an alumina crucible, and then placed in a high-temperature muffle 13Sintering at 50 deg.C for 8h, furnace cooling to room temperature (25 deg.C), crushing the obtained roasted product, and grinding to obtain red fluorescent powder.
And (3) relevant performance test analysis:
the chemical formulas of the samples of examples 1-19 and comparative example 1 and the associated test data are shown in table 1 below.
TABLE 1
As can be seen from Table 1 above, the red phosphors provided in examples 1-19 of the present application have significantly higher luminous intensity, device lumen efficiency, and color rendering index than the red phosphors provided in comparative example 1, which indicates that rare earth ion Eu is adopted in the present application 3+ Excitation A m D n E q M z The red luminescent material can emit bright red light under the excitation of ultraviolet light, and has high luminous efficiency and good chemical stability.
Fig. 2 is an XRD spectrum of the red luminescent material provided in examples 1, 6, 14 and 18 of the present application. As shown in FIG. 2, the XRD diffraction peaks of the red phosphors provided in examples 1, 6, 14 and 18 correspond to that of standard card ICSD # 1183, which is GdGaSr 2 O 5 Pure phase, indicating that the doped ions have little effect on the overall structure of the matrix.
Fig. 3 shows emission spectra of the red luminescent materials provided in examples 1, 6, 14 and 18 of the present application under excitation at 380 nm. As shown in FIG. 3, the emission spectra of the red phosphors provided in examples 1, 6, 14 and 18 each consist of several sharp peaks, the peak wavelengths of which are substantially uniform, and the main emission peak is at 588nm, which is Eu 3+ Characteristic peak of emission.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A red luminescent material is characterized in that the chemical general formula of the red luminescent material is A m D n E q M z ：xEu 3+ Wherein A comprises at least one of La, Gd, Lu and Y elements, D comprises at least one of Al, Ga and In elements, E comprises at least one of Ca, Sr and Ba elements, and M comprises O element; m is more than or equal to 0.9 and less than or equal to 1.1, n is more than or equal to 0.9 and less than or equal to 1.1, q is more than or equal to 1.9 and less than or equal to 2.1, z is more than or equal to 4.8 and less than or equal to 5.2, and x is more than 0 and less than or equal to 0.2.
2. A red light-emitting material according to claim 1, wherein A is the same as or different from A m D n E q M z ：xEu 3+ In the formula, m is more than or equal to 0.95 and less than or equal to 1.05, n is more than or equal to 0.95 and less than or equal to 1.05, q is more than or equal to 1.9 and less than or equal to 2.0, z is more than or equal to 4.9 and less than or equal to 5.1, and x is more than or equal to 0.05 and less than or equal to 0.15.
3. A red light-emitting material according to claim 1, wherein A is the same as or different from A m D n E q M z ：xEu 3+ Wherein A includes Gd element, and the A further includes at least one of La element, Lu element, and Y element, D includes Ga element, and the D further includes at least one of Al element and In element, E includes Sr element, and the E further includes at least one of Ca element and Ba element, and M further includes at least one of F element and N element.
4. A red luminescent material according to claim 3, wherein the atomic ratio of the Gd element in A to the total amount of the other elements in A is 1: (0.01 to 0.25); and/or
The atomic ratio of the Ga element in D to the total amount of the other elements in D is 1: (0.01-0.2).
5. A red light-emitting material according to claim 3, wherein an atomic ratio of the Sr element in the E to the total amount of the other elements in the E is 1: (0.01 to 0.1); and/or
The atomic ratio of the O element in the M to the total amount of other elements in the M is 1: (0.001-0.08).
6. A red luminescent material according to any one of claims 1 to 5, wherein A is m D n E q M z ：xEu 3+ Wherein a is Gd element, D is Ga element, E is Sr element, M is O element, and M is 1, n is 1, q is 1.9, z is 5, and x is 0.1.
7. The red luminescent material as claimed in any one of claims 1 to 5, wherein the excitation wavelength of the red luminescent material is 320 to 400nm, and the peak wavelength of the emission spectrum is 585-590 nm.
8. A preparation method of a red luminescent material is characterized by comprising the following steps:
a red luminescent material according to any one of claims 1 to 7 having the chemical formula A m D n E q M z ：xEu 3+ Weighing compound raw materials of each element according to the metering ratio, and mixing and grinding the compound raw materials to obtain a raw material mixture;
and sintering the raw material mixture, and crushing to obtain the red luminescent material.
9. The method according to claim 8, wherein the sintering temperature is 1200-1350 ℃ and the sintering time is 7-9 h.
10. A light-emitting device comprising a light source and a luminescent material excited by the light source, wherein the luminescent material comprises the red luminescent material according to any one of claims 1 to 7 or the red luminescent material produced by the method for producing a red luminescent material according to any one of claims 8 to 9.
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