CN116285986B - Luminescent material and luminescent device comprising same - Google Patents
Luminescent material and luminescent device comprising same Download PDFInfo
- Publication number
- CN116285986B CN116285986B CN202310055546.6A CN202310055546A CN116285986B CN 116285986 B CN116285986 B CN 116285986B CN 202310055546 A CN202310055546 A CN 202310055546A CN 116285986 B CN116285986 B CN 116285986B
- Authority
- CN
- China
- Prior art keywords
- luminescent material
- light
- equal
- excitation
- elements
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 82
- 230000005284 excitation Effects 0.000 claims abstract description 31
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 15
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims description 20
- 229910052746 lanthanum Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 229910017414 LaAl Inorganic materials 0.000 claims description 14
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- 229910052765 Lutetium Inorganic materials 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 13
- 230000006872 improvement Effects 0.000 abstract description 11
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 description 17
- 239000000843 powder Substances 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- 229910052761 rare earth metal Inorganic materials 0.000 description 10
- 238000000295 emission spectrum Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 238000005090 crystal field Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 4
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- -1 rare earth aluminosilicate Chemical class 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004471 energy level splitting Methods 0.000 description 2
- 238000002284 excitation--emission spectrum Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910003564 SiAlON Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000026058 directional locomotion Effects 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/77064—Aluminosilicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/77744—Aluminosilicates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The embodiment of the invention relates to a luminescent material and a luminescent device comprising the luminescent material, wherein the luminescent material comprises a component formula A a E e G g M m X x By selecting the element types and the content of the inorganic compound, a more stable environment is provided for the luminescence center of the formed luminescent material, so that the enhancement of light efficiency and the improvement of thermal stability are realized, the effective regulation and control of luminescence characteristics and spectral properties are realized, the absorption efficiency of doped elements in an excitation wavelength range is improved, and the improvement of emission intensity and external quantum efficiency is promoted. The inorganic compound provided by the embodiment of the invention can generate green light emission with the peak wavelength range of about 510-520 nm under the excitation of light with the wave band of 400-470nm, has higher emission intensity and narrower half-peak width, is matched with the excitation wave band of a blue light LED chip, and has good application prospect in the fields of backlight sources for ultrahigh color gamut display and the like.
Description
Technical Field
The embodiment of the invention relates to the technical field of luminescent materials, in particular to a luminescent material and a luminescent device containing the luminescent material.
Background
With the continuous development of information technology, flat panel display devices are increasingly developed toward light weight, high resolution, high color saturation, and the like. The liquid crystal display is still the mainstream flat panel display technology at present because of the advantages of stable performance, lower energy consumption, longer service life and the like. As one of the key technologies of LCD, the selection of backlight source plays a critical role in improving the display color gamut, such as image definition and color saturation. Compared with multi-chip composite, the white light LED with single chip combined with one or more fluorescent powder has the characteristics of long service life, small light attenuation, low cost, stable light color and the like, gradually replaces the cold cathode ray tube and other technologies of the traditional LCD backlight source, and becomes a main stream backlight source in the field of liquid crystal display. At present, the fluorescent conversion type white light LED mainly has the following three implementation modes, wherein the blue light LED chip is matched with the combination mode of red fluorescent powder and green fluorescent powder, and the types and the proportions of the red fluorescent powder and the green fluorescent powder can be regulated and controlled to meet the light source requirements of various application scenes, so that the blue light LED chip gradually develops into the mainstream LED white light implementation mode.
Color gamut (color gamut) is one of the main parameters evaluating display devices, and is represented by color reproduction capability to the real world. The larger the color gamut (color space), the larger the coverage of the representative colors, and the more vivid the color of the display. Compared with some novel display technologies, such as OLED and QLED, the liquid crystal display technology using LED as backlight source has the advantages of long service life, mature production process, low cost and the like, but the current color gamut is low, and the ever-increasing visual demands of people cannot be met. Therefore, further improvement of the color gamut is an important development direction in the field of liquid crystal display.
The working principle of liquid crystal display shows that the light of the backlight source needs to pass through a color filter to obtain 3 independent R, G, B spectrums, and then the spectrums are combined into different colors. Only the backlight source with the spectrum similar to that of the optical filter can better transmit, and the luminous intensity is not lost. Therefore, the half-widths of the emission spectra of the green and red phosphors constituting the white LED are required to be narrow, and to be matched with the wavelength of the filter. Red phosphors for display at present, e.g. K 2 SiF 6 :Mn 4+ And the half-peak width of the emission spectrum is about 5nm, the color coordinates are close to the right lower end of the horseshoe-shaped graph, and the improvement on the color gamut is close to the maximum value. However, the existing green fluorescent powder has lower color purity, wider emission spectrum and larger difference of color coordinate values corresponding to different half-peak widths and peak wavelengths, so that development of a novel narrow-band green fluorescent powder system is needed to realize further improvement of color gamut.
At present, the green fluorescent powder is mainly concentrated on Ce 3+ 、Eu 2+ Or Mn of 2+ In systems in which the ion is the active center, where Ce 3+ The excitation-emission of (2) belongs to the transition between f-d, because the energy level of the outer layer 4f only has one electron, when the excitation is to the energy level of 5d, the light-emitting performance is seriously influenced by the surrounding crystal field because of no shielding of the outer layer s and p electrons, the energy level is easy to split, the broad spectrum emission is presented, and the half-peak width is generally larger than 100nm. Eu (Eu) 2+ The 5d energy level of the ion is exposed to the outside and is easily influenced by the surrounding crystal field to generate energy level splitting, but Eu 2+ In some crystal structures with stronger rigidity, such as beta-SiAlON and the like, the energy level splitting degree is reduced, and the half-peak width of an emission spectrum can be reduced to about 50 nm. And Mn of 2+ Is 3d in electronic configuration 5 The blue light source generally presents 510-540 nm green luminescence in a tetrahedral crystal field, has narrower half-peak width (18-45 nm), concentrated energy and higher color purity, can be excited by a blue light chip, and can pass through the proportion of matrix elementsMn is promoted by means of regulation, doping substitution, sensitization and the like 2+ The luminous intensity is improved, but the current luminous efficiency is not high.
In summary, the problems of low overall luminous efficiency, wide half-peak width and the like of the green phosphor for ultra-high color gamut display at present still have a certain gap from practical production and application, and development of a novel narrow-band green phosphor capable of being excited by a blue light chip is needed to meet the application requirements of the field of backlight sources for ultra-high color gamut display.
Disclosure of Invention
Based on the above situation in the prior art, an object of an embodiment of the present invention is to provide a light emitting material and a light emitting device including the light emitting material, so as to solve the problems of low light emitting efficiency of a narrow band green phosphor and low color gamut of a light emitting device for display in the prior art.
To achieve the above object, according to one aspect of the present invention, there is provided a light emitting material comprising an inorganic compound including an a element, an E element, a G element, an M element, and an X element;
the A element comprises at least one of La, Y, gd and Lu elements; the E element comprises one or two of Al, ga and In elements, and at least comprises an Al element; the G element comprises one or two of Si and Ge elements and at least comprises Si element; the M element comprises one or two of O, N and F elements and at least comprises O element, and the X element comprises one or two of Mn, eu and Ce elements and at least comprises Mn element;
the inorganic compound has a structure similar to LaAl 3 SiO 8 The same crystal structure.
Further, the composition formula of the inorganic compound is A a E e G g M m X x Wherein a is more than or equal to 0.8 and less than or equal to 1.2, e is more than or equal to 2.2 and less than or equal to 3.2,0.8, g is more than or equal to 1.8,7.8, m is more than or equal to 8.2,0.001 and x is more than or equal to 0.3.
Further, e is more than or equal to 2.5 and less than or equal to 3, g is more than or equal to 0.8 and less than or equal to 1.5.
Further, the mole percentage of La, Y, gd or Lu element in the A element is b, and b is more than or equal to 50% and less than or equal to 100%.
Further, the molar ratio of the E element to the G element is c which is more than or equal to 1.7 and less than or equal to 3.5.
Further, a (1-b) is more than or equal to 0.8 and [2- (e-g) ]/2 is more than or equal to 1.2.
Further, the element A must contain La.
Further, the element A is La and Sr.
Further, the E element is an Al element, and the G element is an Si element.
Further, the element A is one or two of La, Y, gd and Lu.
Further, c is more than or equal to 2.8 and less than or equal to 3.2.
According to another aspect of the present invention, there is provided a light emitting device comprising an excitation light source and a luminescent material comprising a luminescent material according to the first aspect of the present invention.
Further, the excitation light source is a semiconductor chip with an emission peak wavelength range of 400-470 nm.
In summary, the embodiment of the invention provides a luminescent material and a luminescent device comprising the luminescent material, wherein the luminescent material comprises a composition formula A a E e G g M m X x By selecting the element types and the content of the inorganic compound, a more stable environment is provided for the luminescence center of the formed luminescent material, so that the enhancement of light efficiency and the improvement of thermal stability are realized, the effective regulation and control of luminescence characteristics and spectral properties are realized, the absorption efficiency of doped elements in an excitation wavelength range is improved, and the improvement of emission intensity and external quantum efficiency is promoted. The inorganic compound provided by the embodiment of the invention can generate green light emission with the peak wavelength range of about 510-520 nm under the excitation of light with the wave band of 400-470nm, has higher emission intensity and narrower half-peak width, is matched with the excitation wave band of a blue light LED chip, and has good application prospect in the fields of backlight sources for ultrahigh color gamut display and the like.
Drawings
Fig. 1 is a schematic view of a light emitting device according to an embodiment of the present invention;
FIG. 2 is an XRD diffraction pattern of a luminescent material sample prepared in example 1 of the present invention;
FIG. 3 is a graph showing excitation and emission spectra of a luminescent material sample prepared in example 1 of the present invention; FIG. 3 (a) is a 517nm excitation spectrum of the luminescent material sample prepared in example 1, and FIG. 3 (b) is a 450nm excitation emission spectrum of the luminescent material sample prepared in example 1.
Reference numerals illustrate:
1-semiconductor chip, 2-glue adds luminescent material, 3-pin, 4-base, 5-plastic lens.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
In an embodiment of the present invention, there is provided a light emitting material comprising an inorganic compound including an A element, an E element, a G element, an M element, and an X element, the composition formula being A a E e G g M m X x The method comprises the steps of carrying out a first treatment on the surface of the Wherein the A element comprises at least one of La, Y, gd and Lu elements; the E element comprises one or two of Al, ga and In elements, and at least comprises an Al element; the G element comprises one or two of Si and Ge elements and at least comprises Si element; the M element comprises one or two of O, N and F elements and at least comprises O element, and the X element comprises one or two of Mn, eu and Ce elements and at least comprises Mn element; the inorganic compound has a structure similar to LaAl 3 SiO 8 The same crystal structure. LaAl (Laal) 3 SiO 8 Is a novel crystal structure, mn 2+ Mainly occupy four-coordinate Al 3+ The bits are illuminated. In the luminescent material provided by the embodiment of the invention, trivalent rare earth element La which can be used as A 3+ Y 3+ />Gd 3+ />Lu 3+ />Is similar in ionic radius and serves as LaAl 3 SiO 8 Important components in the crystal structure can be replaced with each other without changing the matrix structure, and the luminous performance can be adjusted according to the requirement. In the material system, the mutual substitution phenomenon exists between the E element and the G element, so that the spectrum movement can be effectively realized, the phase purity of the main material can be basically maintained, but the difference of the radiuses of the main material can cause the expansion or contraction of an integral unit cell, and larger lattice distortion can be caused when the substitution concentration is increased, so that the stability of the structure is not beneficial to maintenance. Thus, the A element may also include, but is not limited to, tetravalent transition metal elements (e.g., hf, zr, ti, etc.), divalent alkaline earth metal elements (e.g., ba, sr, ca, etc.), and monovalent alkali metal elements (K, na, li, etc.). These elements can be substituted correspondingly according to the kind of rare earth element in the A element to relieve lattice distortion caused by E, G element substitution. By LuAl 3 SiO 8 For example, when small radius Si 4+ />Partially replacing large radius Al 3+ />In the case of using Ba 2+ Sr 2+ />Ca 2+ />Equal pair Lu 3+ Substitution is performed to suppress excessive cell shrinkage on the basis of charge balance. While for LaAl 3 SiO 8 In other words, the ratio La 3+ Sr with larger ionic radius 2+ 、Ba 2+ And the like, the distortion degree of the matrix crystal lattice is reduced, and a more stable environment is provided for the luminous center, so that the enhancement of light efficiency and the improvement of thermal stability are realized. Ga, in and Al In the E element are In the same main group, the element properties are similar, and the ion radius In of four coordination is 3+ />Ga 3+ />Close to Mn 2+ />The unit cell parameters and the crystal field characteristics can be adjusted by adopting proper In or Ga to replace Al according to the requirement, so that the regulation and control of the luminous characteristics are realized. Si in G element 4+ />And Ge (Ge) 4+ />The element properties are similar, and the Ge part does not cause larger structural distortion when replacing Si, so that the substitution proportion of Ge-Si can be regulated and controlled according to the requirement, and the effective regulation of the spectral performance is realized. And Al is 3+ 、Si 4+ With O 2- Respectively form [ AlO ] 4 ]And [ SiO ] 4 ]Tetrahedra, forming LaAl 3 SiO 8 Structural framework of material Mn 2+ Luminescence in a four-coordinate crystal field provides a suitable lattice site environment. In the M element, O, N, F is replaced by utilizing the electronegativity difference of anions to influence the crystal field environment of the luminescence centerThis feature allows for a spectrally controllable tuning. The Eu or Ce element in the X element is doped in an energy transfer mode, so that the absorption efficiency of the original singly doped Mn in the excitation wavelength range is improved, and the improvement of the emission intensity and the external quantum efficiency is promoted.
According to some embodiments, the values of the elements in the compositional formula of the inorganic compound may be: a is more than or equal to 0.8 and less than or equal to 1.2, e is more than or equal to 2.2 and less than or equal to 3.2,0.8, g is more than or equal to 1.8,7.8, m is more than or equal to 8.2,0.001 and x is more than or equal to 0.3. Within this condition, the luminescent material can remain substantially the same as LaAl 3 SiO 8 And the like crystal structures. Preferably, e is more than or equal to 2.5 and less than or equal to 3, g is more than or equal to 0.8 and less than or equal to 1.5,2.8 and c is more than or equal to 3.2. By refining the value range of the E element and the G element and the maximum mutual substitution quantity between the E-G elements, a unique substitution mode is defined, namely, the E, G content can be respectively lower than and higher than the corresponding stoichiometric ratio in the value range, the E element can be regarded as being partially substituted by the G element, and finally the spectrum movement is realized.
According to certain embodiments, the La, Y, gd or Lu element comprises b in the molar percentage of the A element, which is 50% or more and 100% or less. The use of divalent alkaline earth elements (such as Ba, sr, ca, etc.) to partially replace rare earth elements in element A can effectively balance the excess charges generated by the replacement between E and G, but the excessive replaced amount can cause the collapse of the main structure, so the replaced amount of La, Y, gd, lu in element A needs to be limited to less than 50 percent. The proportion of E, G elements can be regulated and controlled to change the crystal field intensity around the luminous center, so that the directional movement of the spectrum is realized, E, G belongs to non-equivalent substitution, and lattice defects such as vacancies and the like are increased along with the increase of doping amount, so that the crystal lattice defects can be reduced under the condition that the molar ratio of E to G elements is c and is not less than 1.7 and not more than 3.5, a purer phase structure can be ensured, and the crystal lattice defects can be further obtained, so that the crystal lattice structure has better luminous efficiency and thermal stability.
According to certain embodiments, the values of a, b, e and g satisfy: a (1-b) is more than or equal to 0.8%]And/2 is less than or equal to 1.2. Wherein a (1-b) is the content of the element A except La, Y, gd and Lu, and can be regarded as the original content of the pure La, Y, gd, lu rare earth element in the position of the element A replaced by other low-valence elements in the same lattice, and [2- (e-g)]And/2 represents a tetravalent G elementChanging the content of trivalent E element. The two substitution patterns described above create redundant negative and positive charges, respectively. In order to realize charge balance, avoid generating excessive lattice defects such as vacancies, interstitials and the like, the concentrations of the two substitution modes need to be matched with each other, and too much and too little can introduce impurity phase, thereby influencing Mn 2+ Is a light emitting property of the light emitting device. Thus satisfying 0.8.ltoreq.a (1-b) [2- (e-g)]Under the condition that the ratio of the crystal structure to the crystal structure is less than or equal to 1.2, the content of lattice defects of the main matrix is relatively less, the crystal structure is more stable, and the luminous intensity and the thermal stability are improved.
According to certain embodiments, the element a must contain the element La. Because La has larger ionic radius, the corresponding unit cell parameters of the novel matrix structure formed are larger, so that the influence degree of lattice shrinkage on the whole unit cell is smaller when E-G element substitution is carried out, the substitutional concentration is larger on the basis of keeping a pure phase, and the spectrum regulation performance is better. In addition, in La-containing systems, mn 2+ The lattice distortion caused by entering the E element lattice site has smaller influence on the stability of the whole unit cell structure, larger doping concentration and higher luminous intensity.
According to certain embodiments, the a element is a La and Sr element. The rare earth element is a pure La system, the original volume of the whole unit cell is large, and the main phase is relatively pure, thereby being beneficial to the subsequent structural optimization by means of element doping and the like. And Sr 2+ Is greater than La 3+ When the element substitution is carried out, the lattice distortion caused by the substitution of the element E by the element G can be effectively slowed down. Therefore, when the element A is La and Sr, the element A is matched with the element E-G in a substituted manner, so that the luminous intensity is better.
According to certain embodiments, the E element is an Al element and the G element is an Si element. The ionic radius of Al and Si elements is relatively small, [ AlO ] 4 ]And [ SiO ] 4 ]The three-dimensional network structure formed by tetrahedra is stable, and Al and Si occupy the same lattice site, which means that the proportion adjustment range between the two lattice sites is larger, and the lattice sites can be arranged in disorder. And Al and Si belong to adjacent main group elements in the same period, have similar chemical properties and relatively stable valence states, and have small degree of lattice distortion on a matrix structure when being mutually substituted.
According to certain embodiments, the A element is La. Y, gd and Lu element. The A element adopts La, Y, gd, lu pure rare earth element system, has smaller radius difference and similar chemical property, and the mutual substitution of the A element does not cause larger structural distortion, can be regarded as a similar crystal structure, and adopts Mn 2+ After being used as a luminous center, the luminous center has better overall luminous performance.
According to some embodiments, the molar ratio of E element to G element is c, 1.7.ltoreq.c.ltoreq.3.5. The content of the E element and the G element in the proportion can keep the matrix structure of the pure rare earth aluminosilicate fluorescent powder relatively stable, and the luminous intensity is higher.
According to some embodiments, in LaAl 3 SiO 8 The La element position in the type structure material can be partially or completely replaced by other trivalent ions, including but not limited to Y 3+ 、Gd 3+ 、Lu 3+ 、Sc 3+ 、Sm 3+ 、Dy 3+ 、Tb 3+ The chemical composition formula of the plasma rare earth ions can be regarded as LaAl 3 SiO 8 And the like crystal structures. In addition, under the above conditions, if the stoichiometric ratio of each element A, E, G, M is not strictly in accordance with the relationship of 1:3:1:8, it is regarded as being equivalent to LaAl on the basis of not changing the host crystal structure or not changing the fundamental properties of luminescence 3 SiO 8 And the like crystal structures.
In an embodiment of the present invention, there is also provided a method for preparing the above luminescent material, including the steps of:
according to formula A of inorganic matter contained in the luminescent material a E e G g M m X x Corresponding oxide, carbonate, nitrate, fluoride and the like are weighed according to the stoichiometric ratio as raw materials, and the symmetrically-taken raw materials are ground and mixed to obtain a raw material mixture.
Putting the ground raw material mixture into a high-temperature furnace, and introducing N 2 The method comprises the steps of carrying out a first treatment on the surface of the Then heating to 1250-1500 ℃ according to the heating rate of 1-15 ℃/min, preserving heat for 2-10 hours at 1250-1500 ℃, and then cooling to room temperature along with a furnace to obtain a sintered body; preferably, the temperature rising rate of the high temperature furnace is 5-8 ℃/min.
Grinding the cooled sintered body, washing with water, sieving, and drying to obtain the final product of luminescent material.
In an embodiment of the present invention, there is also provided a light emitting device including an excitation light source and a light emitting material including the light emitting material referred to in the above embodiment.
Preferably, the excitation light source is a semiconductor chip with an emission peak wavelength range of 400-470 nm. The luminescent material has a characteristic excitation peak at 450nm, and has higher excitation efficiency in the wavelength range.
Preferably, the luminescent material also comprises fluorescent powder with the emission wavelength ranging from 620 nm to 680nm, quantum dot material, semiconductor chip and the like. By utilizing the composite package of the luminescent material, the fluorescent powder with the wavelength of 620-680nm, the quantum dot material and the semiconductor chip, the color gamut of the luminescent device can be effectively improved. The luminescent material related to the embodiment is matched with the excitation light source and the material, so that the luminescent device emits light with high luminous efficiency and high color rendering, and the application requirements of the fields of ultra-high color gamut liquid crystal display backlights and the like are met.
In the embodiment of the present invention, there is further provided a light emitting device including the above light emitting material, the light emitting device including an excitation light source and the light emitting material related to the above embodiment, a schematic structural diagram of the light emitting device is shown in fig. 1, and as shown in fig. 1, the excitation light source is, for example, a semiconductor chip 1 with an emission peak wavelength range of 400-470nm, the semiconductor chip 1 is disposed on a base 4, the semiconductor chip 1 is wrapped inside by glue and the light emitting material 2, the outer part of the semiconductor chip 1 is covered with a plastic lens 5, and two ends of the base 4 respectively lead out pins 3. According to the light-emitting device provided by the embodiment of the invention, the light-emitting material has higher light-emitting intensity under the excitation of the blue light chip, and can meet the application requirements of the field of backlight sources for ultrahigh color gamut display.
Specific examples and comparative examples are described below.
Comparative example 1
Molecular formula is SrAl 1.98 Si 2 O 7.99 Mn 0.02 Of (a) compound (compositionThe elements are shown in Table 1), and the light emission intensity under excitation with 450nm blue light was set to 100.
Example 1
Using La 2 O 3 、Al 2 O 3 、SiO 2 、MnCO 3 As a raw powder to obtain a constitutive LaAl 2.98 SiO 7.99 Mn 0.02 The compound represented (composition elements are shown in Table 1) was weighed 43.19% by weight of La 2 O 3 40.28% by weight of Al 2 O 3 15.93% by weight of SiO 2 And 0.61% by weight of MnCO 3 Grinding and mixing the raw materials uniformly, loading the mixture into a crucible, and sintering the mixture in a high-temperature furnace at 1350 ℃ for 4 hours; cooling to room temperature along with a furnace to obtain a sintered sample; and ball milling, water washing and sieving the sample to obtain the luminescent material. The luminescent material obtained in example 1 was examined by X-ray spectroscopy (Co target), its XRD diffraction pattern was as shown in FIG. 2,2 theta diffraction angles corresponding to the triple peaks were 27.74 deg., 35.32 deg. and 33.16 deg., respectively, other background hetero peaks or some hetero-phase peaks far lower than the triple peak intensity were instrumental, and the main phase crystal structure in example 1 was still LaAl 3 SiO 8 . It should be noted that, when the diffraction angle positions corresponding to the three strong peaks in the XRD patterns of other luminescent materials are the same as the present invention, the diffraction angle positions and the relative intensities corresponding to the other peaks are slightly changed, or the XRD diffraction peak positions of other luminescent materials are left shifted or right shifted as a whole due to the expansion or contraction of the unit cell, they are regarded as the same type of crystal structure as the luminescent material according to the present invention. The luminescent material of example 1, which has a narrow-spectrum luminescence of green spectrum under excitation of 450nm blue light with a peak wavelength of 517nm and a relative luminescence intensity of 357, was analyzed by a fluorescence spectrometer. Fig. 3 shows excitation and emission spectra of the luminescent material sample prepared in this example, fig. 3 (a) shows 517nm excitation spectra of the luminescent material sample prepared in this example, and fig. 3 (b) shows 450nm excitation emission spectra of the luminescent material sample prepared in this example. As can be seen from FIG. 3, the luminescent material has high absorption intensity in the blue region and an emission spectrum in the range of 500About 560nm, and the half-width is about 35 nm.
Example 2
Use of SrCO 3 、La 2 O 3 、Al 2 O 3 、SiO 2 、MnCO 3 In order to obtain the composition formula (La 0.8 Sr 0.2 )Al 2.78 Si 1.2 O 7.99 Mn 0.02 The compound (the composition elements are shown in table 1) is prepared by weighing the corresponding raw materials according to the stoichiometric ratio, sintering in a high-temperature furnace and performing post-treatment. The luminescent material obtained in example 2 was analyzed by a fluorescence spectrometer, and the material had a narrow-spectrum luminescence of a green spectrum under excitation of 450nm blue light, and a peak wavelength of 516nm and a relative luminescence intensity of 314.
Example 3
Use of SrCO 3 、La 2 O 3 、Al 2 O 3 、SiO 2 、MnCO 3 In order to obtain the composition formula (La 0.7 Sr 0.3 )Al 2.68 Si 1.3 O 7.99 Mn 0.02 The compound (the composition elements are shown in table 1) is prepared by weighing the corresponding raw materials according to the stoichiometric ratio, sintering in a high-temperature furnace and performing post-treatment. The luminescent material obtained in example 3 was analyzed by a fluorescence spectrometer, and the material had a narrow-spectrum luminescence of a green spectrum under excitation of 450nm blue light, and the peak wavelength was 515nm and the relative luminescence intensity was 298.
The preparation of examples 4-29 was similar to that of examples 1-3 above, with the original powders and the final compounds employed as shown in Table 1. The compositions of comparative example 1, examples 1-29 and the emission peak wavelength and relative luminescence intensity under excitation at a 450nm light source are shown in Table 1.
Table 1 comparative examples and examples chemical formulas and luminous properties
As can be seen from table 1, compared with the comparative example, the luminescent material provided by the embodiment of the invention has significantly improved luminous intensity under excitation of the blue light chip, solves the problem of lower luminous efficiency of the narrow-band green fluorescent powder in the prior art, and meets the application requirements of the field of the backlight source for ultra-high color gamut display.
As can be seen from the data of table 1 above, the emission peak wavelengths of the luminescent materials having the compositions of the present application in examples 1 to 29 are all in the wavelength range of 510 to 520 nm; according to examples 2-6, the mode of simultaneously replacing La and Al with Sr and Si elements can effectively adjust the peak wavelength of the emission spectrum without changing the original LaAl 3 SiO 8 Under the condition of the matrix phase structure, compared with examples 24-29, the luminescent material obtained by adopting the scheme of the element combination has higher overall relative emission intensity. Furthermore, when the ratio of substitutional atoms between Sr-La and Si-Al are matched with each other, i.e., a (1-b) [2- (e-g)]At/2≡1, the luminous intensity reaches the peak value because of large radius Sr 2+ Substituted for La of small radius 3+ And small radius Si 4+ Substituted for large radius Al 3+ The double substitution process of (2) not only can reduce lattice distortion caused by single substitution, but also can maintain charge balance, and avoid the influence of Mn caused by the introduction of structural defects such as oxygen vacancies and the like 2+ Stable valence state, thereby alleviating Mn 2+ And a corresponding decrease in the light emission intensity. According to examples 1, 8-14, it can be seen that the relative luminous intensity of the luminescent material with pure rare earth element as element a can still be kept high, meanwhile, the occupation of different rare earth ions on the position a can affect the relative luminous intensity and the peak wavelength, and the mutual combination of different elements can be performed according to actual needs.
In summary, embodiments of the present invention relate to a luminescent material and a light-emitting device including the luminescent material, wherein the luminescent material includes a composition formula A a E e G g M m X x By selecting the element type and content of the inorganic compound, a more stable environment is provided for the luminous center of the formed luminous material, so that the enhancement of luminous efficiency and thermal stability are realized, and the luminous characteristic and spectrum are realizedThe performance is effectively regulated, and the absorption efficiency of the doping element in the excitation wavelength range can be improved, so that the improvement of the emission intensity and the external quantum efficiency is promoted. The inorganic compound provided by the embodiment of the invention can generate green light emission with the peak wavelength range of about 510-520 nm under the excitation of light with the wave band of 400-470nm, has higher emission intensity and narrower half-peak width, is matched with the excitation wave band of a blue light LED chip, and has good application prospect in the fields of backlight sources for ultrahigh color gamut display and the like.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (12)
1. A light-emitting material characterized by comprising an inorganic compound including an a element, an E element, a G element, an M element, and an X element;
the A element comprises at least one of La, Y, gd and Lu elements; the E element comprises one or two of Al, ga and In elements, and at least comprises an Al element; the G element comprises one or two of Si and Ge elements and at least comprises Si element; the M element comprises one or two of O, N and F elements and at least comprises O element, and the X element comprises one or two of Mn, eu and Ce elements and at least comprises Mn element; the composition formula of the inorganic compound is A a E e G g M m X x Wherein a is more than or equal to 0.8 and less than or equal to 1.2, e is more than or equal to 2.2 and less than or equal to 3.2,0.8, g is more than or equal to 1.8,7.8, m is more than or equal to 8.2,0.001 and x is more than or equal to 0.3;
the inorganic compound has a structure similar to LaAl 3 SiO 8 The same crystal structure.
2. The luminescent material according to claim 1, wherein e.ltoreq.2.5.ltoreq.3, g.ltoreq.0.8.ltoreq.1.5.
3. The luminescent material according to claim 2, wherein the molar percentage of the La, Y, gd and Lu elements in the A element is b, and b is 50% or more and 100% or less.
4. A luminescent material as claimed in claim 3, wherein the molar ratio of the element E to the element G is c, c being 1.7.ltoreq.c.ltoreq.3.5.
5. The luminescent material as claimed in claim 4, wherein 0.8.ltoreq.a (1-b) [2- (e-g) ]/2.ltoreq.1.2.
6. The light-emitting material according to claim 5, wherein the element a contains La.
7. The luminescent material according to claim 6, wherein the A element is La or Sr element.
8. The light-emitting material according to any one of claims 1 to 7, wherein the E element is an Al element and G is an Si element.
9. The light-emitting material according to any one of claims 1 to 4, wherein the element a is one or two of La, Y, gd, and Lu.
10. The luminescent material according to claim 4, wherein c is 2.8.ltoreq.c.ltoreq.3.2.
11. A light-emitting device comprising an excitation light source and a luminescent material, characterized in that the luminescent material comprises a luminescent material as claimed in any one of claims 1-10.
12. The light-emitting device according to claim 11, wherein the excitation light source is a semiconductor chip having an emission peak wavelength in a range of 400 to 470 nm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2022101066354 | 2022-01-28 | ||
| CN202210106635 | 2022-01-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116285986A CN116285986A (en) | 2023-06-23 |
| CN116285986B true CN116285986B (en) | 2024-02-27 |
Family
ID=86827672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310055546.6A Active CN116285986B (en) | 2022-01-28 | 2023-01-17 | Luminescent material and luminescent device comprising same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116285986B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013194078A (en) * | 2012-03-16 | 2013-09-30 | National Institute For Materials Science | Phosphor, method for producing the same, light-emitting device and image display device |
| CN107936963A (en) * | 2017-11-02 | 2018-04-20 | 杭州显庆科技有限公司 | A kind of green tribo-luminescence fluorescent powder and preparation method thereof |
| CN110713834A (en) * | 2019-11-02 | 2020-01-21 | 上海应用技术大学 | Molybdate fluorescent powder and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004134216A (en) * | 2002-10-10 | 2004-04-30 | Hitachi Displays Ltd | Cathode-ray tube |
-
2023
- 2023-01-17 CN CN202310055546.6A patent/CN116285986B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013194078A (en) * | 2012-03-16 | 2013-09-30 | National Institute For Materials Science | Phosphor, method for producing the same, light-emitting device and image display device |
| CN107936963A (en) * | 2017-11-02 | 2018-04-20 | 杭州显庆科技有限公司 | A kind of green tribo-luminescence fluorescent powder and preparation method thereof |
| CN108949170A (en) * | 2017-11-02 | 2018-12-07 | 杭州显庆科技有限公司 | A kind of ink |
| CN109054818A (en) * | 2017-11-02 | 2018-12-21 | 杭州显庆科技有限公司 | A kind of stress irradiance element |
| CN109054819A (en) * | 2017-11-02 | 2018-12-21 | 杭州显庆科技有限公司 | Stress irradiance element |
| CN110713834A (en) * | 2019-11-02 | 2020-01-21 | 上海应用技术大学 | Molybdate fluorescent powder and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Bo Yuan ,etc.Luminescence and tunable color properties of uniphase white‑emitting Sr 3 B 2 SiO 8 :Tm 3+ /Dy 3+ /Eu 3+ phosphors by energy transfer for UV‑excited white LEDs.《Optical and Quantum Electronics》.2021,第53卷494. * |
| Synthesis and phosphorescence properties of Mn4+ , La3+ and Ho3+ in MgAl2Si2O8;Nilgun Ozpozan Kalaycioglu，etc;《Journal of Alloys and Compounds》;第510卷;6-10 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116285986A (en) | 2023-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhong et al. | Enhanced luminescence of a Ba 2 GdSbO 6: Mn 4+ red phosphor via cation doping for warm white light-emitting diodes | |
| Dai et al. | Color tuning of (K 1− x, Na x) SrPO 4: 0.005 Eu 2+, y Tb 3+ blue-emitting phosphors via crystal field modulation and energy transfer | |
| Mehare et al. | Recent development in color tunable phosphors: A review | |
| CN106047341B (en) | A kind of rare earth doping fluorescent powder, its synthetic method and its application on the led device | |
| JP2012131969A (en) | Yellow phosphor having oxyapatite structure, production method, and white light emitting diode device thereof | |
| JP6002772B2 (en) | Nitride red light emitting material, light emitting element and light emitting device including the same | |
| Li et al. | Photoluminescence properties and energy transfer of a color tunable phosphor: Dy3+ and Tm3+ co-activated SrCaAl2SiO7 | |
| KR20120112691A (en) | White-light led red luminescent materials and preparation methods thereof | |
| Tao et al. | Blue emitting phosphor Sr0. 8Ca0. 2Al2+ ySi2-yO8: Ce3+: substitution of Al-Si, structural modification, luminescence property and application | |
| CN114644925B (en) | Near ultraviolet excited red fluorescent powder for LED and preparation method thereof | |
| Dai et al. | Preparation, structure, and luminescent properties of Dy3+-doped borate Ca3La3 (BO3) 5: Dy3+ for potential application in UV-LEDs | |
| Tang et al. | Luminescence enhancement of Ca3Sr3 (VO4) 4: Eu3+, Sm3+ red-emitting phosphor by charge compensation | |
| Xie et al. | Tunable photoluminescence and energy transfer of novel phosphor Sr 9 La 2 W 4 O 24: Sm 3+, Eu 3+ for near-UV white LEDs | |
| WO2019061004A1 (en) | Silicon-based oxynitride cyan phosphor with enhanced fluorescence and preparation method therefor | |
| CN114958351A (en) | Ultraviolet excited bluish violet fluorescent powder, preparation method and luminescent device | |
| Du et al. | Synthesis and photoluminescence properties of a novel white-light-emitting Dy 3+-activated Sr 3 Sc (PO 4) 3 phosphor | |
| CN116285986B (en) | Luminescent material and luminescent device comprising same | |
| CN114574204B (en) | Near ultraviolet excited red fluorescent powder for LED and preparation method thereof | |
| CN114605999B (en) | Near ultraviolet excited red fluorescent powder for LED and preparation method thereof | |
| CN114774116B (en) | Blue luminescent material, preparation method thereof and white light LED | |
| Singh et al. | Luminescence properties of reddish orange emitting BaLa2ZnO5: Sm3+ phosphor prepared by citric based sol-gel synthesis | |
| CN114395394B (en) | Near-infrared fluorescent powder and optical device comprising same | |
| CN116333729A (en) | Luminescent material and luminescent device comprising same | |
| CN110283588B (en) | Fluorescent powder for white light LED for illumination display and preparation and application thereof | |
| KR101510124B1 (en) | BLUISH GREEN EMITTING PHOSPHORS FOR HIGH COLOR RENDERING AND HIGH EFFICIENT WHITE LEDs AND LEDs USING THE SAME |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |