CN115437179B - Display device and liquid crystal display - Google Patents
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- CN115437179B CN115437179B CN202210958423.9A CN202210958423A CN115437179B CN 115437179 B CN115437179 B CN 115437179B CN 202210958423 A CN202210958423 A CN 202210958423A CN 115437179 B CN115437179 B CN 115437179B
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 120
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 230000005284 excitation Effects 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 6
- 238000000295 emission spectrum Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 abstract description 15
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052910 alkali metal silicate Inorganic materials 0.000 abstract description 11
- 239000000843 powder Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 26
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 15
- 238000000149 argon plasma sintering Methods 0.000 description 13
- 230000004907 flux Effects 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000084 colloidal system Substances 0.000 description 9
- 238000010304 firing Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
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- 239000000741 silica gel Substances 0.000 description 7
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 229910017855 NH 4 F Inorganic materials 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 229910052706 scandium Inorganic materials 0.000 description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
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- 229910003564 SiAlON Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/1336—Illuminating devices
- G02F1/133614—Illuminating devices using photoluminescence, e.g. phosphors illuminated by UV or blue light
-
- 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77342—Silicates
-
- 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77344—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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/774—Borates
-
- 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
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/77922—Silicates
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/1336—Illuminating devices
- G02F1/133602—Direct backlight
- G02F1/133603—Direct backlight with LEDs
Abstract
The application discloses a display device and a liquid crystal display, comprising an excitation source and a wavelength conversion layer; the excitation source generates blue light with emission wavelength of 440nm to 465 nm; the wavelength conversion layer comprises a green photoluminescent material and a red photoluminescent material, wherein the green photoluminescent material is selected from any one of substances shown in a formula I. The green photoluminescent material and the red photoluminescent material of the specific europium-activated alkali metal silicate are used together, so that the color gamut range of the display device is improved, the NTSC color gamut value can reach more than 100%, and meanwhile, the excellent luminous performance is ensured.
Description
Technical Field
The present disclosure relates to the field of luminescent materials, and more particularly, to a display device and a liquid crystal display.
Background
The liquid crystal display device (Liquid Crystal Display, abbreviated as LCD) is a commonly used display at present, and since the liquid crystal layer has no light emitting function, a light source is required to be provided for the LCD to realize image display, and the backlight device of the display is the key of "lighting" the LCD display, so that the NTSC color gamut range of the common CCFL backlight and the white LED backlight display is only about 70% and the light emitting performance is low.
In the prior art, a display backlight device uses blue excitation light to excite a wavelength conversion layer, and the conversion layer comprises green fluorescent powder with peak emission of 530-545nm (specifically europium-activated beta-SIALON green fluorescent powder) and red fluorescent powder with peak emission of 600-650 nm; however, the preparation of the europium-activated beta-SIALON green fluorescent powder requires high temperature and high pressure (more than 2000 ℃ and more than 10 Mpa), has poor economic performance, and meanwhile, the half-peak width of the green fluorescent powder is wider (about 55 nm), so that the color gamut of the liquid crystal display can only reach about 90, and the excellent color display effect can not be realized.
In the prior art, a wavelength conversion layer is excited by using blue excitation light, the conversion layer contains sulfide green fluorescent powder with 525-545nm peak emission and red fluorescent powder with 610-650nm peak emission, but the used sulfide green fluorescent powder has poor chemical stability, S is easily decomposed and separated out to corrode the light-emitting device, and meanwhile, the half-width of the emission peak of the used sulfide green fluorescent powder is about 48-50nm, and the half-width of the emission peak is still too wide for high-color-gamut backlight, so that the color gamut value of the display is still low.
Disclosure of Invention
The embodiment of the application provides a display device, which can solve the problems of low color gamut value, poor display color effect and poor luminous performance of a display backlight device in the prior art.
In a first aspect, embodiments provide a display device including an excitation source and a wavelength conversion layer; the excitation source generates blue light with emission wavelength of 440nm to 465 nm; the wavelength conversion layer comprises a green photoluminescent material and a red photoluminescent material, wherein the green photoluminescent material is selected from any one of substances shown in a formula I;
A 1-x [Li 3 Si 1-a D a O 4-b E b ]:xEu 2+ i
Wherein A is at least one of alkali metal elements, D is at least one of IIIA group elements and/or scandium subgroup elements, and E is at least one of halogens; x is more than or equal to 0.001 and less than or equal to 0.1; a is more than 0 and less than or equal to 0.2; b is more than or equal to 0 and less than or equal to 0.1, and x=a-b is satisfied; the green photoluminescent material is a europium-activated alkali metal silicate green photoluminescent material.
Specifically, the value of x can be 0.001, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1;
the value of a can be 0.002, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15 and 0.2;
the value of b can be 0, 0.001, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1.
At A 1-x [Li 3 SiO 4 ]:xEu 2+ Eu in (1) 2+ The position of A is replaced by Eu, since A is a monovalent metal 2+ The substitution of (a) causes an imbalance in valence state to generate vacancies of a in the crystal matrix to achieve electroneutrality of the whole crystal, and the presence of vacancy defects breaks a to some extent 1-x [Li 3 SiO 4 ]:xEu 2+ Thereby resulting in a decrease in light emission performance and long-term performance; eu can be suppressed by substituting tetravalent Si element with a partially 3-valent D element 2+ The generation of vacancy defects after A is replaced, so that the fluorescent powder has better luminous performance and luminous stability. Meanwhile, by introducing part of halogen elements into the matrix material, the structural rigidity of the fluorescent powder crystal can be improved, and the crystallization performance can be greatly improved.
Eu is used as a luminescence center, the content of Eu has great influence on the luminescence performance of the fluorescent powder, and too low content can cause too low luminescence brightness of the fluorescent powder and too large dosage in the use process; and excessive content can quench the concentration of luminescence generated by the fluorescent powder, thereby reducing the luminescence intensity. In the structural formula of the green phosphor of the present invention, the molar content of Eu as a luminescence center is selected from 0.001 to 0.1mol, preferably from 0.01 to 0.08mol, and more preferably from 0.02 to 0.05mol, for obtaining more excellent luminescence effect.
The main function of introducing the D element into the fluorescent powder matrix lattice is to compensate charges, and the dosage is influenced by the Eu content of the luminescence center and the lattice stabilizing element E. The introduced molar content of the E element is less than or equal to 0.1mol, and the structural strength of the fluorescent powder crystal can be improved by a proper amount of the E element; however, because of the large difference between the ionic radius and electronegativity of the E element and the oxygen element, the solid solubility of the E element in the phosphor lattice is limited, and excessive E element can cause the phosphor lattice to generate large distortion so as to influence the luminescence performance of the phosphor. The preferable content of E element is 0.02 to 0.05mol.
Optionally, a is at least one of Li element, na element, K element, rb element, cs element; d is at least one selected from B element, al element, ga element, in element and Sc element; e is at least one selected from F element and Cl element.
For example, the chemical expression of the green fluorescent powder is Na 0.23 K 0.5 Li 0.25 [Li 3 Si 0.97 Al 0.03 O 3.99 F 0.01 ]:0.02Eu 2+ 、Na 0.2 K 0.5 Li 0.25 [Li 3 Si 0.93 B 0.07 O 3.98 F 0.02 ]:0.05Eu 2+ 、Na 0.25 K 0.68 [Li 3 Si 0.9 Al 0.1 O 3.97 F 0.03 ]:0.07Eu 2+ Or Rb 0.43 Li 0.5 [Li 3 Si 0.9 Al 0.1 O 3.97 F 0.03 ]:0.07Eu 2+ 。
In some exemplary embodiments, the green photoluminescent material is selected from any of the substances having the formula i-1;
Na 0.25-x K 0.5 Li 0.25 [Li 3 Si 1-a D a O 4-b E b ]:xEu 2+ i-1
Wherein D is at least one of IIIA group elements and/or scandium subgroup elements, and E is at least one of F element and Cl element; the method comprises the steps of,
x is more than or equal to 0.001 and less than or equal to 0.1; a is more than 0 and less than or equal to 0.2; b is more than or equal to 0 and less than or equal to 0.1;
and x=a-b;
optionally, D is at least one selected from B element, al element, ga element, in element, sc element;
specifically, in one example, D is an Al element; or In another example, D contains Al element and also contains at least one of B element, ga element, in element, sc element.
Optionally, in one example, E is an F element; or in another example, E is an element of Cl; still or in other examples E contains an F element and also contains a Cl element.
In some exemplary embodiments, D is selected from an Al element or a B element;
for example, the green photoluminescent material is selected from any one of those having the formula I-1-A or those having the formula I-1-B;
Na 0.25-x K 0.5 Li 0.25 [Li 3 Si 1-a Al a O 4-b F b ]:xEu 2+ formula I-1-A;
Na 0.25-x K 0.5 Li 0.25 [Li 3 Si 1-a B a O 4-b F b ]:xEu 2+ formula I-1-B.
x is more than or equal to 0.01 and less than or equal to 0.08; a is more than 0 and less than or equal to 0.2; b is more than or equal to 0.01 and less than or equal to 0.05; and x=a-b.
Specifically, the value of x can be 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08;
the value of a can be 0.002, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15 and 0.2;
b can be 0.01, 0.02, 0.03, 0.04 and 0.05;
however, it should be noted that a cannot take 0 because if a takes 0, substitution of E element does not play a role in balancing charges because E element is in a-1 valence state.
For example, the green photoluminescent material having the formula I-1 is Na 0.23 K 0.5 Li 0.25 [Li 3 Si 0.97 Al 0.03 O 3.99 F 0.01 ]:0.02Eu 2+ 、Na 0.2 K 0.5 Li 0.25 [Li 3 Si 0.93 B 0.07 O 3.98 F 0.02 ]:0.05Eu 2+ Or Na 0.18 K 0.5 Li 0.25 [Li 3 Si 0.9 Al 0.1 O 3.97 F 0.03 ]:0.07Eu 2+ 。
In some exemplary embodiments, the green photoluminescent material is selected from any of the substances having the formula i-2;
Na c K 1-c-x [Li 3 Si 1-a D a O 4-b E b ]:xEu 2+ i-2
Wherein D is at least one of IIIA group elements and/or scandium subgroup elements, and E is at least one of F element and Cl element; x is more than or equal to 0.001 and less than or equal to 0.1; a is more than 0 and less than or equal to 0.2; b is more than or equal to 0 and less than or equal to 0.1; c is more than or equal to 0.1 and less than or equal to 0.25; and x=a-b is satisfied.
Optionally, D is at least one selected from the group consisting of B element, al element, ga element, in element, and Sc element.
In some exemplary embodiments, D is selected from an Al element or a B element; the method comprises the steps of,
x is more than or equal to 0.01 and less than or equal to 0.08; b is more than or equal to 0.01 and less than or equal to 0.05.
For example, the green photoluminescent material is selected from any one of those having the formula I-2-A or those having the formula I-2-B;
Na c K 1-c-x [Li 3 Si 1-a Al a O 4-b F b ]:xEu 2+ a compound of formula I-2-A;
Na c K 1-c-x [Li 3 Si 1-a B a O 4-b F b ]:xEu 2+ formula I-2-B.
x is more than or equal to 0.01 and less than or equal to 0.08; a is more than 0 and less than or equal to 0.2; b is more than or equal to 0.01 and less than or equal to 0.05; c is more than or equal to 0.1 and less than or equal to 0.25; and x=a-b is satisfied.
Specifically, the value of x can be 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08;
the value of a can be 0.002, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15 and 0.2;
b can be 0.01, 0.02, 0.03, 0.04 and 0.05;
the value of c can be 0.1, 0.15, 0.2 and 0.25;
for example, the chemical expression of the green fluorescent powder is Na 0.1 K 0.88 [Li 3 Si 0.97 Al 0.03 O 3.99 F 0.01 ]:0.02Eu 2+ 、Na 0.25 K 0.68 [Li 3 Si 0.9 Al 0.1 O 3.97 F 0.03 ]:0.07Eu 2+ 。
In some exemplary embodiments, the green photoluminescent material is selected from any of the substances having the formula i-3;
Rb 0.5-x A 0.5 [Li 3 Si 1-a D a O 4-b E b ]:xEu 2+ i-3
Wherein A is one of Li element or Na element, D is at least one of IIIA group element and/or scandium subgroup element, E is at least one of F element and Cl element;
x is more than or equal to 0.001 and less than or equal to 0.1; a is more than 0 and less than or equal to 0.2; b is more than or equal to 0 and less than or equal to 0.1;
and x=a-b.
Alternatively, in one example, a may be Li element; alternatively, in another example, a may be a Na element.
Optionally, D is at least one selected from the group consisting of B element, al element, ga element, in element, and Sc element.
In some exemplary embodiments, D is selected from an Al element or a B element; the method comprises the steps of,
x is more than or equal to 0.01 and less than or equal to 0.08; a is more than 0 and less than or equal to 0.2; b is more than or equal to 0.01 and less than or equal to 0.05; and x=a-b.
For example, the green photoluminescent material is selected from any one of those having the formula I-3-A or those having the formula I-3-B;
Rb 0.5-x A 0.5 [Li 3 Si 1-a Al a O 4-b F b ]:xEu 2+ a compound of formula I-3-A;
Rb 0.5-x A 0.5 [Li 3 Si 1-a B a O 4-b F b ]:xEu 2+ formula I-3-B.
Wherein A is one of Li element or Na element.
Alternatively, x may have a value of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08;
the value of a can be 0.002, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15 and 0.2;
b can be 0.01, 0.02, 0.03, 0.04 and 0.05;
specifically, in one example, a is a Li element, or in another example, a is a Na element, or in other examples, a contains a Li element and also contains a Na element;
for example, the green photoluminescent material has the chemical formula Rb 0.48 Li 0.5 [Li 3 Si 0.97 Al 0.03 O 3.99 F 0.01 ]:0.02Eu 2+ 、Rb 0.45 Na 0.5 Li 0.25 [Li 3 Si 0.93 B 0.07 O 3.98 F 0.02 ]:0.05Eu 2+ 、Rb 0.43 Li 0.5 [Li 3 Si 0.9 Al 0.1 O 3.97 F 0.03 ]:0.07Eu 2+ 。
In some exemplary embodiments, the peak of the emission spectrum of the substance of formula I corresponds to a wavelength in the range of 525nm to 540nm, has an emission peak half-width of 40nm to 50nm, and is excited by 300nm to 470nm light, the optimal excitation wavelength being 430 nm to 460nm, and the substance of formula I is matched with commercially available K 2 SiF 6 :Mn 4+ The red phosphor, NTSC color gamut value may be as high as 100%.
In some exemplary embodiments, the peak of the excitation spectrum of the substance of formula i corresponds to a wavelength in the range of 350nm to 500 nm.
In some exemplary embodiments, the crystal structure of the material of formula I is monoclinic, C2/m space group.
In some exemplary embodiments, the mass ratio of the green photoluminescent material to the red photoluminescent material is from 10 to 40:60 to 90;
preferably, the mass ratio of the green photoluminescent material to the red photoluminescent material is 20-35: 65-80.
In some exemplary embodiments, the peak of the emission spectrum of the red photoluminescent material corresponds to a wavelength in the range of 610nm to 650 nm.
The peak value of the excitation spectrum of the red photoluminescent material corresponds to the wavelength in the range of 300nm to 500 nm.
In some exemplary embodiments, the red photoluminescent material is selected from K 2 SiF 6 :Mn 4+ (KSF)、CaAlSiN 3 Eu (CASN) or SrLiAl 3 N 4 ：Eu 2+ At least one of (a) and (b);
preferably, the red photoluminescent material is KSF.
In some exemplary embodiments, the wavelength conversion layer further includes an organic colloid including one or more of a silica gel, a silicone resin, or an epoxy-based resin;
preferably, the organic colloid is selected from at least one of silica gel and silicone resin.
In some exemplary embodiments, the mass ratio of the total amount of photoluminescent material to the organic colloid is 20 to 60: 40-80, for obtaining the best light emitting effect.
Of course, it should be noted that the total amount of the photoluminescent material is:
in the wavelength conversion layer, the total mass of the green photoluminescent material and the red photoluminescent material; or,
in the wavelength conversion layer, the total mass of the green photoluminescent material, the red photoluminescent material, and the other photoluminescent materials contained.
In some exemplary embodiments, the wavelength conversion layer further comprises a light scattering material selected from ZnO, siO 2 、MgO、BaSO 4 Or Al 2 O 3 One or more of the following; preferably, the light scattering material is SiO 2 。
In some exemplary embodiments, the mass ratio of total photoluminescent material to light scattering material is 95 to 99.9:0.1 to 5.
In some exemplary embodiments, the green photoluminescent material has a median particle size D50 of 15 to 35 μm, the red photoluminescent material has a median particle size of 10 to 35 μm, and the light scattering material has a median particle size D50 of 0.1 to 5 μm. The green photoluminescent material, the red photoluminescent material and the light scattering material in the particle size range are mixed for use, so that the effect of high luminous brightness and uniform light angle colors at different positions can be achieved.
In some exemplary embodiments, the wavelength conversion layer is a separate film fabricated separately from the other components, the green photoluminescent material, the red photoluminescent material, and the light scattering material being uniformly dispersed in the separate film;
the average thickness of the independent film is 10-50 um, the effect is to fix the fluorescent material in the film layer, the independent film can be arranged above the blue light LED chip (or whole row) excitation source after solidification and forms a certain distance with the chip (or whole row), so that the influence of the working temperature of the chip on the fluorescent powder material is minimized.
In a second aspect, embodiments of the present application provide a liquid crystal display, where the liquid crystal display includes a display device as described in any one of the above.
The technical scheme provided by some embodiments of the present application has the beneficial effects that at least includes:
1) The emission peak wavelength of the green photoluminescent material is 525-540 nm, and the emission peak wavelength of the green photoluminescent material is 630nm 2 SiF 6 :Mn 4+ Collocation, encapsulation white light LEDIn the liquid crystal backlight source, the NTSC color gamut value of the liquid crystal display can reach 100%, and more colors can be displayed and the colors are gorgeous;
2) The emission peak of the green photoluminescent material and the transmission spectrum of a green color filter (mainly transmitting a wave band mainly comprising 530nm green light) in the liquid crystal display have high overlap ratio, so that more green spectrum components can be transmitted, and the display has higher brightness;
3) The green photoluminescent material of europium-activated alkali metal silicate has good chemical stability and can effectively prolong the service life of the display device.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic cross-sectional view of a display device prepared in an embodiment of the present application;
fig. 2 is a schematic cross-sectional view of a display device prepared according to another embodiment of the present application;
fig. 3 is a schematic structural diagram of a reflective film layer in a display device prepared in an embodiment of the present application;
FIG. 4 is an emission spectrum of a display device prepared according to an embodiment of the present application;
fig. 5 is a color gamut coverage comparison of display devices prepared in example 1 and comparative example 3 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
The display device of the present application may refer specifically to the schematic diagram in fig. 1.
In fig. 1, the display device comprises an excitation source 101 and a wavelength converting layer 104, the excitation source 101 exciting the wavelength converting layer 104 such that photoluminescent material in the wavelength converting layer 104 generates specific light 105;
in particular, the display device comprises a light guide 103, one end of the light guide 103 (back side of the light guide) being arranged adjacent to the excitation source 101, the excitation source 101 may be arranged one or more, the excitation source 101 being configured to couple excitation light 102 onto at least one edge of the light guide 103, the wavelength converting layer 104 being arranged at the other end of the light guide 103 (front side of the light guide), the wavelength converting layer 104 being in direct contact with the light guide 103;
furthermore, referring to fig. 1, in the display device described in the application, the excitation source 101 is disposed in a direct illumination manner, that is, the wavelength conversion layer 104 is disposed at a distance directly above the excitation source 101, typically, a longitudinal distance between the excitation source 101 and the wavelength conversion layer 104 is 0.1-2 mm, the excitation light 102 emitted by the excitation source 101 passes through the light guide 103 to reach the wavelength conversion layer 104, the photoluminescent material in the wavelength conversion layer 104 can generate light 105 with other wavelengths through excitation of the excitation light 102, in the direct illumination manner shown in fig. 1, a diffuse reflection film layer 106 is disposed on a side, away from the excitation source 101, of the wavelength conversion layer 104, the diffuse reflection film layer 106 is directly contacted with the wavelength conversion layer 104, a light emitting surface 107 is disposed on a side, away from the wavelength conversion layer 104, of the excitation light 102 emitted by the excitation source 101 in operation is converted into light with other wavelengths, and the light is emitted through the light emitting surface 107, and the diffuse reflection film 106 is disposed on the light emitting surface. A brightness enhancement film layer 108 is disposed between the wavelength conversion layer 104 and the light guide 103, the brightness enhancement film layer 108 is in direct contact with the wavelength conversion layer 104, and the brightness enhancement film layer 108 is used for reflecting light emitted from the fluorescent powder in the wavelength conversion layer 104 in the light guide direction back to the diffuse reflection film layer 106 direction, so as to improve the brightness of the display device. The brightness enhancing film layer 108 may transmit the excitation light emitted by the excitation source 101 so as not to affect the effect of exciting the wavelength conversion layer 104.
In other embodiments of the present application, referring to fig. 2, the excitation source 101 in the display device may also be arranged in a side-lit arrangement, i.e. the excitation source 101 is positioned along one or more edges of the light guide 103, the excitation source 101 being configured such that in operation excitation light 102 is generated, the excitation light 102 being coupled into one or more edges of the light guide 103 and then guided through the entire light guide 103 by total internal reflection, the wavelength converting layer 104 being arranged at one end of the light guide 103 (the front side of the light guide 103), the wavelength converting layer 104 being in direct contact with the light guide 103, the wavelength converting layer 104 in operation converting the excitation light 102 through the entire light guide 103 into white light and exiting through the light emitting face 107; in order to improve the uniformity of light emission, a diffuse reflection film layer 106 is further disposed between the wavelength conversion layer 104 and the light emitting surface 107, and the diffuse reflection film layer 106 is in direct contact with the wavelength conversion layer 104. A brightness enhancement film layer 108 is disposed between the wavelength conversion layer 104 and the light guide 103, the brightness enhancement film layer 108 is in direct contact with the wavelength conversion layer 104, the brightness enhancement film layer 108 is used for reflecting light emitted from fluorescent powder in the wavelength conversion layer 104 in the light guide direction back to the diffuse reflection film layer 106 direction, so that the brightness of the display device is improved, and the brightness enhancement film layer 108 can transmit the excitation light emitted from the excitation source 101, so that the effect of exciting the wavelength conversion layer 104 is not affected.
In other embodiments of the present application, as shown in fig. 3, i.e. based on the structure shown in fig. 1, the display device may further include a light reflection layer 109, where the light reflection layer 109 is disposed on an inner side surface of the light guide 103, and the brightness enhancement film layer 108 is disposed between the light reflection layer 109 and the light guide 103, where the brightness enhancement film layer 108 is in direct contact with the light guide 103, and where the light reflection layer is in direct contact with an edge of the brightness enhancement film layer 108. The effect of this arrangement is to reflect all the light emitted from the excitation source 101 toward the wavelength conversion layer 104, so as to enhance the effect of exciting the wavelength conversion layer 104 and enhance the brightness of the backlight device.
Preparation of europium-activated alkali metal silicate green photoluminescent material:
s100, mixing an A source, a Li source, a Si source, a Eu source and a D source and/or an E source according to the stoichiometric ratio meeting the formula I to obtain a mixture;
s200, burning the mixture at 700-1100 ℃ for 1-10 hours in a reducing atmosphere to obtain the europium-activated alkali metal silicate green photoluminescent material;
specifically, the mixture is placed in a reducing atmosphere furnace and burned for 1 to 10 hours at the temperature of 700 to 1100 ℃ to obtain a burned product.
And S300, grinding the burning product, and washing and drying to obtain the green photoluminescent material.
Optionally, the source a is carbonate containing element a, the source D is oxide containing element D, the source E is ammonium salt containing element E, the source Li is carbonate containing element Li, the source Si is oxide containing element Si, and the source Eu is oxide containing element Eu;
specifically, the carbonate containing the A element comprises Na 2 CO 3 、K 2 CO 3 、Li 2 CO 3 、Rb 2 CO 3 、Cs 2 CO 3 One or more of the following;
the oxide containing D element comprises Al 2 O 3 、B 2 O 3 、Ga 2 O 3 、In 2 O 3 、Sc 2 O 3 One or more of the following;
the ammonium salt containing E element comprises NH 4 Cl、NH 4 One or more of F;
the carbonate containing Li element comprises Li 2 CO 3 The oxide containing Si element comprises SiO 2 The oxide containing Eu element comprises Eu 2 O 3 。
Preferably, the oxide containing D element is Al 2 O 3 。
Preferably, the E-element-containing ammonium saltIs NH 4 F。
In the second step, the firing process includes:
a first temperature rising stage: the temperature range is 25-700 ℃, and the heating rate is not more than 5 ℃/min and not more than 15 ℃/min; and, a second temperature increasing stage: the temperature is higher than 700 ℃ and the heating rate is less than 0 ℃/min and less than or equal to 3 ℃/min.
Specifically, the firing process includes:
a first temperature rising stage: the upper limit of the temperature rising rate is any one value selected from 8 ℃/min, 10 ℃/min, 12 ℃/min and 15 ℃/min in the temperature range of 25-700 ℃; the lower limit of the heating rate is selected from any one value of 5 ℃/min, 8 ℃/min, 10 ℃/min and 12 ℃/min
A second temperature rising stage: the temperature is higher than 700 ℃ in a temperature interval, and the heating rate is any value selected from 1 ℃/min, 2 ℃/min and 3 ℃/min.
The present application is further illustrated by the following examples.
Example 1
Preparation of europium-activated alkali metal silicate Green photoluminescent Material used in example 1
According to chemical composition formula Na 0.249 K 0.5 Li 0.25 [Li 3 Si 0.998 Al 0.002 O 3.999 F 0.001 ]:0.001Eu 2+ Weighing the raw materials with the corresponding weight: 13.196g Na 2 CO 3 、34.55g K 2 CO 3 、120.088g Li 2 CO 3 、59.95g SiO 2 、0.102g Al 2 O 3 、0.037g NH 4 F and 0.176g Eu 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Mixing the materials, placing the mixture into a reducing atmosphere furnace, heating to 700 ℃ at a heating rate of 5 ℃/min in a temperature range of 25-700 ℃, heating to 1100 ℃ at a heating rate of 3 ℃/min, burning for 1h, cooling to room temperature along with the furnace, and discharging; and ball milling, washing and drying the firing product. The main emission peak of the green fluorescent powder is positioned at 525nm; the half-width was 41nm.
Example 2
Preparation of europium-activated alkali silicate Green photoluminescent Material used in example 2
According to chemical composition formula Na 0.24 K 0.5 Li 0.25 [Li 3 Si 0.8 B 0.2 O 3.95 Cl 0.05 ]:0.01Eu 2+ Weighing the raw materials with the corresponding weight: 12.72g Na 2 CO 3 、34.55g K 2 CO 3 、120.088g Li 2 CO 3 、48.06g SiO 2 、12.366g B 2 O 3 、2.675g NH 4 Cl and Eu 1.76g 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Mixing the materials, placing the mixture into a reducing atmosphere furnace, heating to 700 ℃ at a heating rate of 15 ℃/min in a temperature range of 25-700 ℃, burning for 10 hours, cooling to room temperature along with the furnace, and discharging; and ball milling, washing and drying the firing product. The main emission peak of the green fluorescent powder is positioned at 540nm; half-width 49nm.
Example 3
Preparation of europium-activated alkali metal silicate Green photoluminescent Material used in example 3
According to chemical composition formula Na 0.225 K 0.5 Li 0.25 [Li 3 Si 0.97 In 0.03 O 3.995 F 0.005 ]:0.025Eu 2+ Weighing the raw materials with the corresponding weight: 11.925g Na 2 CO 3 、34.55g K 2 CO 3 、120.088g Li 2 CO 3 、58.278g SiO 2 、4.165g In 2 O 3 、0.185NH 4 F and 4.4g Eu 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Mixing the materials, placing the mixture into a reducing atmosphere furnace, heating to 700 ℃ at a heating rate of 8 ℃/min in a temperature range of 25-700 ℃, heating to 900 ℃ at a heating rate of 2 ℃/min, burning for 6 hours, cooling to room temperature along with the furnace, and discharging; and ball milling, washing and drying the firing product. The main emission peak of the green fluorescent powder is positioned at 530nm; the half-width was 42nm.
Example 4
Preparation of europium-activated alkali metal silicate Green photoluminescent Material used in example 4
According to chemical composition Rb 0.45 Na 0.5 [Li 3 Si 0.91 Sc 0.09 O 3.96 Cl 0.04 ]:0.05Eu 2+ Weighing the raw materials with the corresponding weight: 26.5g Na 2 CO 3 、51.963g Rb 2 CO 3 、110.85g Li 2 CO 3 、54.673g SiO 2 、6.206g Sc 2 O 3 、2.14g NH 4 Cl and 8.8g Eu 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Mixing the materials, placing the mixture into a reducing atmosphere furnace, heating to 700 ℃ at a heating rate of 7 ℃/min in a temperature range of 25-700 ℃, heating to 840 ℃ at a heating rate of 2.5 ℃/min, burning for 6 hours, cooling to room temperature along with the furnace, and discharging; and ball milling, washing and drying the firing product. The main emission peak of the green fluorescent powder is at 534nm; half-width 43nm.
Example 5
Preparation of europium-activated alkali metal silicate Green photoluminescent Material used in example 5
According to chemical composition formula Na 0.26 K 0.7 [Li 3 Si 0.94 B 0.06 O 3.98 F 0.02 ]:0.04Eu 2+ Weighing the raw materials with the corresponding weight: 13.78g Na 2 CO 3 、48.37g K 2 CO 3 、110.85g Li 2 CO 3 、56.475g SiO 2 、0.06g B 2 O 3 、0.74g NH 4 F and 7.04g Eu 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Mixing the materials, placing the mixture into a reducing atmosphere furnace, heating to 700 ℃ at a heating rate of 8 ℃/min in a temperature range of 25-700 ℃, heating to 820 ℃ at a heating rate of 2 ℃/min, burning for 6 hours, cooling to room temperature along with the furnace, and discharging; and ball milling, washing and drying the firing product. The main emission peak of the green fluorescent powder is at 532nm; the half-width was 45nm.
Example 6
Preparation of europium-activated alkali metal silicate Green photoluminescent Material used in example 6
According to chemical composition Rb 0.47 Li 0.5 [Li 3 Si 0.95 Al 0.05 O 3.98 F 0.02 ]:0.03Eu 2+ Weighing the raw materials with the corresponding weight: 54.272g Rb 2 CO 3 、129.325g Li 2 CO 3 、57.076g SiO 2 、3.448g Al 2 O 3 、0.741g NH 4 F and 5.28g Eu 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Mixing the materials, placing the mixture into a reducing atmosphere furnace, heating to 700 ℃ at a heating rate of 8 ℃/min in a temperature range of 25-700 ℃, heating to 790 ℃ at a heating rate of 2 ℃/min, burning for 8 hours, cooling to room temperature along with the furnace, and discharging; and ball milling, washing and drying the firing product. The main emission peak of the green fluorescent powder is positioned at 533nm; the half-width was 46nm.
Other materials used in the examples herein are commercially available.
Example 1
40g of Na 0.249 K 0.5 Li 0.25 [Li 3 Si 0.998 Al 0.002 O 3.999 F 0.001 ]:0.001Eu 2+ (Green photoluminescent Material), 60g of K 2 SiF 6 :Mn 4+ (red photoluminescent material), 0.1g of MgO (light scattering material) and 120g of silica gel (organic colloid) were mixed to obtain a mixture.
And coating the mixture on a support body with a light projection material, wherein the support body is a high-transmittance organic film with the thickness of 0.1-0.5mm and is uniformly distributed throughout the support body, so that the wavelength conversion layer can be obtained.
And then combining and mounting other components shown in fig. 1 with the wavelength conversion layer to obtain the display device.
Example 2
20g of Na 0.24 K 0.5 Li 0.25 [Li 3 Si 0.8 B 0.2 O 3.95 Cl 0.05 ]:0.01Eu 2+ (Green photoluminescent Material), 80g of K 2 SiF 6 :Mn 4+ (red photoluminescent material), 0.2g of SiO 2 (light scattering material) and 400g of a high refractive index silicone resin encapsulant (organic colloid) were mixed to obtain a mixture.
The mixture is coated on a support having a light projecting material and uniformly distributed throughout the support, thereby obtaining a wavelength converting layer.
And then combining and mounting other components shown in fig. 1 with the wavelength conversion layer to obtain the display device.
Example 3
35g of Na 0.225 K 0.5 Li 0.25 [Li 3 Si 0.97 In 0.03 O 3.995 F 0.005 ]:0.025Eu 2+ (Green photoluminescent Material), 65g of K 2 SiF 6 :Mn 4+ (red photoluminescent material), 0.5g of BaSO 4 (light scattering material) and 66.6g of an epoxy resin encapsulating compound (organic colloid) were mixed to obtain a mixture.
The mixture is coated on a support having a light projecting material and uniformly distributed throughout the support, thereby obtaining a wavelength converting layer.
And then combining and mounting other components shown in fig. 1 with the wavelength conversion layer to obtain the display device.
Example 4
30g of Rb 0.45 Na 0.5 [Li 3 Si 0.91 Sc 0.09 O 3.96 Cl 0.04 ]:0.05Eu 2+ (Green photoluminescent Material), 70g of K 2 SiF 6 :Mn 4+ (Red photoluminescent material), 1g of SiO 2 (light scattering material) and 100g of silica gel (organic colloid) were mixed to obtain a mixture.
The mixture is coated on a support having a light projecting material and uniformly distributed throughout the support, thereby obtaining a wavelength converting layer.
And then combining and mounting other components shown in fig. 1 with the wavelength conversion layer to obtain the display device.
Example 5
25g of Na 0.26 K 0.7 [Li 3 Si 0.94 B 0.06 O 3.98 F 0.02 ]:0.04Eu 2+ (Green photoluminescent Material), 75g of K 2 SiF 6 :Mn 4+ (red photoluminescence)Material), 0.3g of MgO (light scattering material) and 150g of silica gel (organic colloid) were mixed to obtain a mixture.
The mixture is coated on a support having a light projecting material and uniformly distributed throughout the support, thereby obtaining a wavelength converting layer.
And then combining and mounting other components shown in fig. 2 with the wavelength conversion layer to obtain the display device.
Example 6
30g of Rb 0.47 Li 0.5 [Li 3 Si 0.95 Al 0.05 O 3.98 F 0.02 ]:0.03Eu 2+ (Green photoluminescent Material), 70g of K 2 SiF 6 :Mn 4+ (red photoluminescent material), 0.8g of SiO 2 (light scattering material) and 130g of silica gel (organic colloid) were mixed to obtain a mixture.
The mixture is coated on a support having a light projecting material and uniformly distributed throughout the support, thereby obtaining a wavelength converting layer.
And then combining and mounting other components shown in fig. 3 with the wavelength conversion layer to obtain the display device.
Comparative example 1
Unlike example 1, na was used 0.2 K 0.5 Li 0.25 [Li 3 SiO 4 ]:0.05Eu 2+ As green photoluminescent material, the rest are the same.
Comparative example 2
Unlike example 1, sulfide SrGa is used 2 S 4 ：Eu 2+ The green phosphor is used as a green photoluminescent material, and the rest are the same.
Comparative example 3
The wavelength conversion layer in commercially available display backlight devices is configured from photoluminescent materials as follows:
1) 28g of green photoluminescent material: beta-SiAlON green powder Si 6-z Al z O z N 8-z ：Eu 2+ The emission peak wavelength is 535nm, and the half-width is 55nm;
2) 72g of red photoluminescent material: k (K) 2 SiF 6 :Mn 4+ Emission peak wavelength is 630nm, half width is 10nm;
3) 0.5g of light scattering material: mgO with an average particle size of 1um;
4) 150g of silica gel;
the remainder was the same as in example 1.
The display devices prepared in examples 1 to 6 and comparative examples 1 to 3 of the present application were subjected to tests of luminous flux and NTSC color gamut values, and the test results are filled in table 1.
The application tests the luminous flux and color gamut values of the display device by:
light flux test: the display devices prepared in examples 1 to 6 and comparative examples 1 to 3 were turned on, and the whole was put into an integrating sphere, and the luminous flux was measured using a spectrum analysis system.
NTSC color gamut value test: and (3) testing the display device, deriving the light-emitting spectrum of the backlight device, filtering the spectrum obtained by the test by using filter functions of red, green and blue color filters used by the backlight display, calculating color coordinate values of three primary colors, calculating an actual color gamut value by the color coordinate values of the three primary colors, and comparing the actual color gamut value with an NTSC standard color gamut.
TABLE 1
Referring to the data in Table 1 and in conjunction with FIG. 1, the green photoluminescent materials shown in examples 1-3 are all of formula I-1 (Na 0.25-x K 0.5 Li 0.25 [Li 3 Si 1-a D a O 4-b E b ]:xEu 2+ ) One of the materials shown, the color gamut values of the prepared display device can reach 100%, compared with example 1, in example 2 and example 3The mass ratio of the green photoluminescent material to the red photoluminescent material is in a better range (i.e., the green photoluminescent material: the red photoluminescent material=20 to 35:65 to 80), which is advantageous for improving the color gamut value of the display device, and as can be seen from the data of table 1, the color gamut values of both example 2 and example 3 are higher than the color gamut value of example 1 (about 2% higher), and at the same time, since the green photoluminescent material in example 2 is a more optimal formula (i.e., na) of formula I-1 0.25-x K 0.5 Li 0.25 [Li 3 Si 1-a D a O 4-b E b ]:xEu 2+ The method comprises the following steps: d is Al or B, x is more than or equal to 0.01 and less than or equal to 0.08, and B is more than or equal to 0.01 and less than or equal to 0.05, which is beneficial to improving the luminous flux of the display device, and the luminous flux of the embodiment 2 is 2285lm which is obviously higher than the luminous flux 2159lm of the embodiment 1 and the luminous flux 2265lm of the embodiment 3;
example 5 another embodiment of the present invention provides a display device, particularly as shown in fig. 2, in which the excitation source 101 is positioned differently from the position shown in fig. 1, the excitation source 101 in fig. 1 is arranged in a direct illumination mode, the excitation source 101 in fig. 2 is arranged in a side illumination mode, and the green photoluminescent material shown in example 5 is of formula I-2 (Na c K 1-c-x [Li 3 Si 1-a D a O 4-b E b ]:xEu 2+ ) One of the substances is matched with a proper amount of red photoluminescent material to prepare a display device with a color gamut value of 101% and a luminous flux of 2234 as shown in fig. 2; it should be noted that the green photoluminescent material according to the present invention may be applied to display devices with different structures, and of course, it should be noted that the structures shown in fig. 1 and fig. 2 are only exemplary structures, and the present invention is not limited thereto;
the green photoluminescent materials in examples 4 and 6 are both of formula I-3 (Rb 0.5-x A 0.5 [Li 3 Si 1-a D a O 4-b E b ]:xEu 2 + ) One of the substances shown in example 6 shows that the color gamut of the prepared display device can reach 100% or more, and compared with example 4, the green photoluminescent material in example 6 has a formula of formula I-3 (i.e. Rb 0.5-x A 0.5 [Li 3 Si 1- a D a O 4-b E b ]:xEu 2+ The method comprises the following steps: d is Al or B, x is more than or equal to 0.01 and less than or equal to 0.08 and B is more than or equal to 0.01 and less than or equal to 0.05), and in combination with the illustration of FIG. 3, FIG. 3 is a schematic diagram of a part of the structure of the display device prepared in the embodiment 6, specifically, the display device shown in FIG. 3 further comprises a light reflection layer 109 on the basis of the structure shown in FIG. 1, the light reflection layer 109 is arranged on the inner side surface of the light guide 103, and another brightness enhancement film layer 108 is arranged between the light reflection layer 109 and the light guide 103, so that the luminous flux of the display device is further improved, and as can be seen from the data in Table 1, the luminous flux of the embodiment 6 is up to 2290lm, which is significantly higher than that of the display device with the structures shown in FIG. 1 and FIG. 2;
compared with example 1, comparative example 1 is a display device manufactured by silicate green phosphor without structural improvement, and the overall luminous flux of the display device is obviously reduced by 1909lm compared with examples 1-6 due to lower luminous efficiency of the green phosphor, and the color gamut value is not more than 98%; comparative example 2, although a higher luminous flux 2212lm can be obtained, has a color gamut value of only 96%; comparative example 3 is a phosphor scheme currently used in commercial high color gamut backlights using primarily beta-SiAlON green phosphor that encapsulates the display device with an NTSC color gamut value of only 90%.
Fig. 4 is an emission spectrum of the display device prepared in example 1 of the present application, and fig. 5 is a color gamut coverage comparison of the display devices prepared in example 1 and comparative example 3 of the present application.
The same or similar reference numerals in the drawings of the present embodiment correspond to the same or similar components; in the description of the present application, it should be understood that, if there is an azimuth or positional relationship indicated by terms such as "upper", "lower", "left", "right", etc., based on the azimuth or positional relationship shown in the drawings, this is for convenience of description and simplification of the description, but does not indicate or imply that the apparatus or element to be referred must have a specific azimuth, be constructed and operated in a specific azimuth, and thus terms describing the positional relationship in the drawings are merely used for illustration and are not to be construed as limitations of the present patent, and that the specific meaning of the terms described above may be understood by those of ordinary skill in the art according to the specific circumstances.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.
Claims (6)
1. A display device comprising an excitation source and a wavelength conversion layer;
the excitation source generates blue light with emission wavelength of 440nm to 465 nm;
the wavelength conversion layer comprises a green photoluminescent material and a red photoluminescent material, wherein the green photoluminescent material is selected from any one of substances shown in a formula I;
A 1-x [Li 3 Si 1-a D a O 4-b E b ]:xEu 2+ i
Wherein A is at least one of alkali metal elements, D is at least one of B element and Al element, and E is at least one of F element and Cl element; the method comprises the steps of,
x is more than or equal to 0.01 and less than or equal to 0.08; a is more than or equal to 0.05 and less than or equal to 0.1; b is more than or equal to 0.01 and less than or equal to 0.05;
and x=a-b;
the crystal structure of the substance shown in the formula I is monoclinic system and C2/m space group.
2. A display device as claimed in claim 1, characterized in that the green photoluminescent material is selected from any one of the substances having the formula i-1;
Na 0.25-x K 0.5 Li 0.25 [Li 3 Si 1-a D a O 4-b E b ]:xEu 2+ formula I-1.
3. A display device as claimed in claim 1, characterized in that the green photoluminescent material is selected from any one of the substances having the formula i-2;
Na c K 1-c-x [Li 3 Si 1-a D a O 4-b E b ]:xEu 2+ i-2
Wherein, the value range of c is more than or equal to 0.1 and less than or equal to 0.25.
4. A display device as claimed in claim 1, characterized in that the green photoluminescent material is selected from any one of the substances having the formula i-3;
Rb 0.5-x A 0.5 [Li 3 Si 1-a D a O 4-b E b ]:xEu 2+ i-3
Wherein A is one of Li element or Na element.
5. The display device according to claim 1, wherein the peak of the emission spectrum of the substance represented by formula i corresponds to a wavelength in a range of 525nm to 540nm, and has an emission peak half-width of 40nm to 50 nm.
6. A liquid crystal display, characterized in that the liquid crystal display comprises a display device as claimed in any one of claims 1 to 5.
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