WO2017201982A1 - 一种用于增广色域的复合光学材料及其制备方法与应用 - Google Patents

一种用于增广色域的复合光学材料及其制备方法与应用 Download PDF

Info

Publication number
WO2017201982A1
WO2017201982A1 PCT/CN2016/105761 CN2016105761W WO2017201982A1 WO 2017201982 A1 WO2017201982 A1 WO 2017201982A1 CN 2016105761 W CN2016105761 W CN 2016105761W WO 2017201982 A1 WO2017201982 A1 WO 2017201982A1
Authority
WO
WIPO (PCT)
Prior art keywords
light
wavelength range
color gamut
predetermined wavelength
phosphor
Prior art date
Application number
PCT/CN2016/105761
Other languages
English (en)
French (fr)
Inventor
肖蔓达
明天
徐荣
肖慧
刘纪宏
Original Assignee
武汉保丽量彩科技有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from CN201610347549.7A external-priority patent/CN106019638A/zh
Priority claimed from CN201610693659.9A external-priority patent/CN106328635A/zh
Application filed by 武汉保丽量彩科技有限公司 filed Critical 武汉保丽量彩科技有限公司
Publication of WO2017201982A1 publication Critical patent/WO2017201982A1/zh

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • 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

Definitions

  • the invention relates to the field of materials, in particular to a composite optical material for modulating a light source spectrum and a widening display color gamut in a display field, and a preparation method and application thereof.
  • color displays have become more and more important in everyday life, including televisions, desktops, laptops, tablets, cell phones, and more.
  • smartphones with color displays have taken a lot of time in people's lives. People's food, housing, travel, work, and communication between people have greatly relied on visually obtaining information from color displays. And all kinds of displays are one of the important tools for people to entertain. It is foreseeable that in the near future, the total demand for human displays will continue to increase.
  • the display visual effects of the display are primarily determined by time resolution, spatial resolution, and color resolution.
  • the higher temporal resolution provides smoother images
  • the higher spatial resolution provides clear picture quality
  • the higher color resolution makes the picture more natural and vivid.
  • the color resolution displayed by the display is primarily dependent on the color composition and purity of the light emitted by the display source.
  • Existing mainstream color displays are liquid crystal displays (LCDs) or active array organic light emitting diode displays (AMOLEDs).
  • LCDs liquid crystal displays
  • AMOLEDs active array organic light emitting diode displays
  • WLEDs white light emitting diodes Due to the low color purity of the red, green and blue primary colors, the light source can be displayed in a narrower color gamut, and can only reach about 70% of the National Color System Committee standard color gamut. Therefore, the display color of such a display is darker and distorted than the original object.
  • the luminescent substance of the AMOLED display is an organic electroluminescent dye.
  • Such a dye has a broad luminescence peak and a low color purity in an aggregate state, resulting in a color gamut of only about 85%.
  • a “selective light absorbing material” is described in Chinese patent CN1221625C. This material "absorbs light reflected from the display and intermediate light outside the three primary colors, thereby enhancing color purity and contrast.”
  • the inventors of the present application have discovered that the biggest problem with such methods is the absorption of the display source. The light causes the brightness of the display to be significantly reduced, and the viewing effect is significantly deteriorated.
  • a liquid crystal display terminal color gamut enhancement method is disclosed in Chinese Patent Application No. CN105467674A. This method "filters the visible light spectrum energy of the excess band except the three primary color bands in the visible light band, and enhances the visible light purity of the three primary color bands.”
  • the inventors of the present application have found that such a method also has the disadvantage that part of the light in the display light source is “filtered", resulting in a significant decrease in brightness of the display and a marked deterioration in the viewing effect.
  • the inventors of the present application have found that the existing methods and materials for improving the color gamut of the display terminal bring about a decrease in the brightness of the display and affect the display effect.
  • the LED is illuminated by a blue light-emitting chip plus green and red phosphors, or a blue light-emitting chip plus a yellow phosphor, that is, all of the basic light of the LED is blue light, and the other two primary colors of the three primary colors are required to pass fluorescence. Material conversion is obtained. At present, the efficiency of conversion is often between 80% and 90%, that is, the luminescence loss that exists in the luminescence process of the LED.
  • the color temperature of the existing display terminal is generally about 6000-8000K.
  • the inventors of the present application found that the high color temperature does not necessarily represent high performance. In terms of the visual sense of the human body, appropriately lowering the color temperature tends to bring more Softer and more natural display, the usual way to reduce the color temperature is to increase the phosphor content, but this method also tends to increase the loss.
  • the phosphor In the LED package, the phosphor is often mixed with an organic resin such as silica gel as a phosphor paste and coated on the chip. In white LEDs, the position and distribution of the phosphor has a large effect on the quality of the LED.
  • the traditional LED package is that the phosphor and the encapsulant are uniformly mixed and solidified on the LED chip.
  • the invention also improves the design of the package structure, further improves the illumination quality of the LED backlight, and improves the heat dissipation structure.
  • the present invention is intended to provide a composite optical material that can enhance the color gamut of a display terminal without affecting or less affecting display brightness. Thereby, a color display effect of high color gamut and high brightness is provided.
  • the present invention is intended to provide a composite optical material capable of enhancing the color gamut of a display terminal, increasing light conversion efficiency, and capable of adjusting color temperature.
  • the present invention provides a composite optical material for augmented color gamut, wherein the composite optical material comprises a transparent substrate and a light wavelength conversion material, the light wavelength conversion material being discretely distributed Within the transparent substrate, the optical wavelength converting material is adapted to convert at least a portion of the light in the first predetermined wavelength range to light in the second predetermined wavelength range.
  • the first predetermined wavelength range includes: 0-430 nm, 470 nm-500 nm, 560 nm-610 nm, 660 nm-750 nm, and any one or more wavelength bands in the above wavelength range;
  • the second predetermined wavelength range includes: 430 nm -470 nm, 500 nm to 560 nm, 610 nm to 660 nm, and any one or more of the above wavelength ranges.
  • the first predetermined wavelength range does not include its node wavelength
  • the second predetermined wavelength range includes its node wavelengths of 430 nm, 470 nm, 500 nm, 560 nm, 610 nm, and 660 nm.
  • the optical wavelength conversion material is an organic molecular fluorescent dye
  • the organic molecular fluorescent dye is a mixture of one or more of Sulforhodamine 101, Rhodamine 101, and HR101.
  • the light wavelength conversion material is a rare earth ion doped up-conversion crystal powder.
  • the composite optical material further comprises scattering particles dispersed discretely in the transparent matrix.
  • the composite optical material further comprises a white balance compensation material.
  • the scattering particles are one or both of inorganic particles and organic polymer microspheres.
  • a method of preparing a composite optical material characterized in that the preparation method comprises:
  • Step A) preparing a liquid matrix material and a light wavelength conversion material
  • Step B) adding a light wavelength conversion material to the liquid matrix material in a predetermined ratio, and mixing uniformly;
  • Step C arranging the mixed solution into a predetermined shape or confining within a predetermined shape
  • the light wavelength conversion material is capable of converting at least a portion of the light in the first predetermined wavelength range into light in a second predetermined wavelength range, preferably, the first predetermined wavelength range comprises: 0-430 nm, 470 nm-500 nm 560 nm to 610 nm, 660 nm to 750 nm, and any one or more of the above wavelength ranges; the second predetermined wavelength range includes: 430 nm to 470 nm, 500 nm to 560 nm, 610 nm to 660 nm, and any one of the above wavelength ranges or
  • the optical wavelength conversion material is an organic molecular fluorescent dye, and the organic molecular fluorescent dye is a mixture of one or more of Sulforhodamine 101, Rhodamine 101, and HR101.
  • the preparation method is for preparing a composite optical material film, and the step C) comprises coating the mixed solution on a predetermined base film.
  • the present invention provides a high color gamut display device, characterized in that the high color gamut display device comprises a display screen comprising a diaphragm made of the composite optical material or the display At least one layer of the screen is made of the composite optical material.
  • the "transparent substrate” described herein may be: glass, acrylate resin, modified polyacrylate, polyurethane, modified polyurethane, epoxy resin, polycarbonate, silicone resin, silicone resin.
  • the matrix material is cured by UV curing or heat curing.
  • At least a portion can refer to at least a portion of a different wavelength component, and can also refer to at least a portion of the intensity of light of a particular wavelength.
  • Light wavelength conversion materials include, but are not limited to, semiconductor materials, semiconductor nanomaterials, metal nanomaterials, surface plasmon materials, ion doped metal oxides, ion doped metal nitrides, ions Doped metal oxynitride, ion doped metal fluoride, ion doped silicate, organic small molecule dye, organic macromolecular dye.
  • the "white balance compensation material" refers to the change of the light of the three primary colors by converting the light in the three primary color gaps into one or more of the three primary colors by using the optical wavelength conversion material of the present invention.
  • the ratio between the two causes a white balance shift, and in order to return the white balance to the white curve, there is no compensation for enhancing or enhancing the weaker light in the three primary colors due to the conversion of the light wavelength conversion material (ie, increasing the primary light) Content).
  • the white balance compensation material compensates for the non-converted optical band of the optical wavelength conversion material in the three primary colors, preferably, if the converted light of the optical wavelength conversion material belongs to a green primary color or The red primary color compensates for the other of the green or red primary colors. In this case, through the light wavelength conversion material and Baiping By combining the compensation materials, it is possible to achieve an increase in color gamut, a decrease in color temperature, and an improvement in conversion efficiency. If the converted light of the light wavelength conversion material belongs to the blue primary color, both the green primary color and the red primary color are compensated.
  • the target wavelength of the optical wavelength conversion material of the present invention is set in the range of the green primary color (500 nm to 560 nm) or the red primary color (610 nm to 660 nm), which we call the target primary color, and the white balance compensation
  • the compensation band of the material is set in the wavelength band of the non-target primary color in the green base color or the red base color, so that the light effect can be ensured while the color temperature is lowered.
  • the conversion may refer to the use of a luminescent material, through Einstein stimulated excitation and Einstein's spontaneous radiation process or by other means to turn photons into another photon of different wavelengths.
  • the other photon may be longer than the wavelength of the absorbed photons, ie, the energy is low, ie, optical down conversion.
  • the other photon may be shorter than the wavelength of the absorbed photons, ie, the energy is high, ie, optically upconverted.
  • the optical down-conversion may refer to conversion of light having a wavelength of 380 nm to 430 nm to light having a wavelength of 430 nm to 470 nm, or light having a wavelength of 500 nm to 560 nm, or light having a wavelength of 610 nm to 660 nm.
  • the optical down-conversion may refer to conversion of light having a wavelength of 470 nm to 500 nm to light having a wavelength of 500 nm to 560 nm, or light having a wavelength of 610 nm to 660 nm.
  • the optical down-conversion may refer to conversion of light having a wavelength of 560 nm to 610 nm into light having a wavelength of 610 nm to 660 nm.
  • the optical up-conversion may refer to conversion of light having a wavelength of 660 nm to 750 nm to light having a wavelength of 430 nm to 470 nm, or light having a wavelength of 500 nm to 560 nm, or light having a wavelength of 610 nm to 660 nm.
  • the optical up-conversion may refer to conversion of light having a wavelength of 560 nm to 610 nm to light having a wavelength of 430 nm to 470 nm, or light having a wavelength of 500 nm to 560 nm.
  • the optical up-conversion may refer to conversion of light having a wavelength of 470 nm to 500 nm to light having a wavelength of 430 nm to 470 nm.
  • the product of the present invention can be formed into a film shape, and the color gamut of the color display can be effectively augmented by simply attaching the film directly to the light source path of the display.
  • the invention can increase the optical path of the light through the composite optical material, improve the utilization ratio of the light wavelength conversion material, and improve the light conversion efficiency, thereby effectively reducing the cost.
  • the product incorporating the diffusing particles of the present invention can simultaneously provide both light conversion and atomization functions, which can reduce the complexity and thickness of the display module, because the diffusion particles added to the composite optical material can cause light to be scattered. Shot, thereby increasing the optical path of light in the optical material while producing an atomizing effect.
  • One difficulty with the present invention is how to maintain a higher light efficiency while filtering out the primary color light.
  • it tends to filter out the primary color light because of the reduction of the color gamut caused by the non-primary light, but it is often caused that the primary color light which is closer to the wavelength of the non-primary light is also filtered out at the same time, resulting in a decrease in light efficiency.
  • the non-primary light is converted to the primary light, that is, the non-primary light is reduced, and the luminance of the primary light can be increased, thereby improving the light efficiency.
  • the invention is also capable of varying the color temperature, preferably reducing the color temperature.
  • the present invention also provides a wide color gamut light emitting device, which aims to solve the problem that the existing light emitting device exhibits a low color gamut and a poor color display effect when applied to the display field.
  • the present invention provides a wide color gamut light emitting device, wherein the wide color gamut light emitting device comprises: a light emitting chip, a package device, and a spectral conversion layer, wherein the light emitting device is placed In the package device, the spectral conversion layer is disposed in the package device, in front of the light emitting chip, the light emitting chip is configured to emit first primary color light, and the spectral conversion layer includes a fluorescent conversion material and light modulation a material for fluorescence conversion of at least a portion of the first primary color light, the fluorescently converted target light comprising at least a second primary color light, the light modulation material for using a first predetermined wavelength At least a portion of the light within the range is converted to light in a second predetermined wavelength range, or light absorbed in the first predetermined wavelength range is converted to thermal energy.
  • the wide color gamut light emitting device comprises: a light emitting chip, a package device, and a spectral conversion layer, wherein the light emitting device is placed In the
  • the first predetermined wavelength range includes: 0-430 nm, 470 nm-500 nm, 560 nm-610 nm, 660 nm-750 nm, and any one or more wavelength bands in the above wavelength range;
  • the predetermined wavelength range includes: 430 nm to 470 nm, 500 nm to 560 nm, 610 nm to 660 nm, and any one or more of the above wavelength ranges.
  • the second predetermined wavelength range further includes 750 nm to 1 mm and any of the ranges. One or more bands.
  • the light emitting chip is a blue light emitting chip
  • the first primary color light is blue light.
  • the fluorescent converted target light comprises a wavelength ranging from 610 nm to 660 nm and 500 nm to 560 nm.
  • the light modulating material for converting at least a portion of the light in the first predetermined wavelength range to one or more wavelength bands in the range of 500 nm to 560 nm, 610 nm to 660 nm.
  • the light emitting chip is an LED light emitting chip
  • the packaging device is a package cup.
  • the spectral conversion layer includes a fluorescence conversion layer and a light modulator layer, the fluorescence conversion layer has a fluorescent conversion material therein, and the light modulation layer has a light modulation material therein, wherein the fluorescence
  • the conversion layer is disposed above the light emitting chip, and the light modulation layer is disposed above the fluorescent conversion layer.
  • the fluorescent conversion material comprises a red phosphor and a green phosphor
  • the light modulation material comprises: anthrapy and its derivatives, anthracene and its derivatives, xanthene and A mixture of one or more of a derivative, triarylmethane and its derivatives, phthalocyanine and its derivatives, tetraazapine and its derivatives, coumarin and its derivatives.
  • the fluorescent conversion material comprises a broad-band yellow phosphor
  • the light-modulating material comprises anthrapyridone and a derivative thereof, an anthracene and a derivative thereof, a xanthene and a derivative thereof a mixture of one or more of phthalocyanine and its derivatives, tetraazapine base and its derivatives, coumarin and its derivatives.
  • one surface of the light modulation layer is a planar or curved surface, and the curved surface is preferably a spherical surface, an ellipsoidal surface or a paraboloid.
  • the present invention provides a method of fabricating a wide color gamut light emitting device, the method comprising the steps of:
  • the light emitting chip is configured to emit light of a first primary color
  • the fluorescent conversion material is configured to perform fluorescence conversion on at least a portion of the first primary color light, the fluorescently converted target light comprising at least a second primary color light
  • the light modulating material is configured to convert at least a portion of the light in the first predetermined wavelength range to light in a second predetermined wavelength range, the first predetermined wavelength range comprising: 0-430 nm, 470 nm-500 nm, 560 nm- 610 nm, 660 nm to 750 nm, and any one or more of the above wavelength ranges;
  • the second predetermined wavelength range includes: 430 nm to 470 nm, 500 nm to 560 nm, 610 nm to 660 nm, and any one or more of the above wavelength ranges
  • the second predetermined wavelength range further comprises 750 nm - 1 mm and any one or more of the bands within the range.
  • the present invention provides a method of fabricating a wide color gamut light emitting device, the method comprising the steps of:
  • the first predetermined wavelength range includes: 0-430 nm, 470 nm-500 nm, 560 nm-610 nm, 660 nm-750 nm, and any one or more of the above wavelength ranges;
  • the second predetermined wavelength range includes: 430 nm-470 nm, 500 nm to 560 nm, 610 nm to 660 nm, and any one or more of the above wavelength ranges, preferably, the second predetermined wavelength range further includes 750 nm to 1 mm and any one or more
  • the invention utilizes a light modulating material (or light modulating agent) to absorb light which affects the color purity in the first predetermined wavelength range, so that the color coordinates of the three primary colors are closer to the spectral trajectory at the position of the chromaticity diagram, and the enclosed triangular area Increase to increase the color gamut of the LED lighting device.
  • a light modulating material or light modulating agent
  • the light modulating agent described in the present invention includes, but is not limited to, a semiconductor material, a metal nanomaterial, a surface plasmon material, an ion doped metal oxide, an ion doped metal oxynitride, an ion doped metal fluoride.
  • a semiconductor material a metal nanomaterial, a surface plasmon material, an ion doped metal oxide, an ion doped metal oxynitride, an ion doped metal fluoride.
  • the light modulating agent may be an organic dye: anthrapyridone and its derivatives, hydrazine and its derivatives, xanthene and its derivatives, triarylmethane and its derivatives, phthalocyanine and its derivatives a mixture of one or more of tetraazapine and its derivatives, coumarin and derivatives thereof.
  • the mass ratio of the light modulating agent in the fluorescence conversion layer ranges from 0.0001% to 0.1%, the color gamut of the obtained LED device reaches an optimum value, and the brightness is not significantly affected.
  • the red fluorescent material has an emission wavelength mainly between 600 and 650 nm, and may be K 2 SiF 6 :Mn 4+ , K/Na 2 TiF 6 :Mn 4+ , nitride, silicate, quantum dot. a mixture of one or more of the green fluorescent materials; the emission wavelength of the green fluorescent material is mainly between 510 and 550 nm.
  • the green fluorescent powder may be a nitrogen oxide, a silicate or an aluminum oxide of the ⁇ -SiAlON type. a mixture of one or more of an acid salt or a quantum dot.
  • the quantum dots include CdSe, CdSe-ZnS, CsPbBr 3 , CsPbBr x I 3-x and the like.
  • the encapsulant is epoxy resin or silica gel
  • the phosphor paste has a thickness of 0.2 mm - 3 mm.
  • the wide color gamut light emitting device can be applied to backlight modules required for various liquid crystal displays, and specifically includes a side-in and a direct-type backlight module.
  • the amount of the fluorescent conversion material corresponding to the target optical band of the light modulation agent can be appropriately reduced, so that the brightness and the augment can be improved without changing the luminous intensity of the light-emitting chip.
  • the gamut even reduces the color temperature.
  • the light-emitting device of the present invention has a narrow half-width of light emitted by the light-modulating agent which selectively absorbs strongly in the first predetermined wavelength range, thereby improving one of them or
  • the color purity of a variety of primary colors provides a higher color gamut and a more realistic display.
  • the light modulator introduced in the present invention can be used in combination with various phosphors, and is perfectly compatible with the existing LED color matching scheme.
  • the wide color gamut light emitting device provided by the present invention has an NTSC of 100% or more.
  • the different kinds of light modulators provided by the invention can be combined with different types of phosphors and light-emitting chips to form a backlight, which is suitable for different types of color display devices, and has a wide range of uses.
  • the light-emitting device of the present invention is mainly applied in the field where the display color gamut has certain requirements, especially for use as a light source of a display device, and is most suitable as a backlight of a display device.
  • the light-emitting device of the present invention is particularly effective when a blue light-emitting chip is used.
  • it is not excluded to apply the wide color gamut light emitting device of the present invention to other forms of illumination.
  • the display device of other illumination forms does not contradict the principle of the augmented color gamut of the present invention, other application forms are also included in the scope of the present invention.
  • Figure 1 is a gamut diagram corresponding to different luminescence spectra in a chromaticity space
  • FIG. 2 is a view showing a comparison of luminescence spectra corresponding to two different gamut triangles in FIG. 1;
  • FIG. 3 is a schematic diagram showing the principle of augmenting a color gamut by adjusting a spectrum of a light source according to the present invention
  • Embodiment 4 is a schematic structural view of a composite optical material in Embodiment 1 of the present invention.
  • Figure 5 is the absorption spectrum 501 and the emission spectrum 502 of Sulforhodamine 101;
  • Figure 6 is a photograph of a composite optical material film prepared in Example 1 of the present invention.
  • Figure 7 is a schematic view showing the composite optical material prepared in Example 1 of the present invention during use
  • Figure 8 is a comparison chart of spectra before and after color gamut augmentation using the composite optical material of the present invention.
  • Fig. 9 is a color gamut comparison diagram before and after color gamut augmentation using the composite optical material of the present invention.
  • FIG. 10 is a schematic structural view of a wide color gamut LED light emitting device of the present invention.
  • FIG. 11 is a spectrum diagram of an LED light-emitting device prepared by using a K2SiF6: Mn4+ red phosphor, a SiAlON:Eu2+ green phosphor, and a blue LED chip;
  • Figure 12 is a comparison diagram of the spectrum of the LED light-emitting device of Example 5, which is the same as that of the light-emitting device of the same fluorescent material as in Example 1 except that the light-modulating agent is not contained;
  • Figure 13 is a comparison diagram of the spectrum of the LED light-emitting device of Example 6 and the spectrum of the light-emitting device of the same fluorescent material as that of Example 2 containing no light-modulating agent;
  • FIG. 14 is a spectrum diagram of an LED light-emitting device prepared by using a nitride red phosphor, a rare earth doped silicate green phosphor, and a blue LED chip;
  • Figure 15 is a comparison diagram of spectra of the LED light-emitting device of Example 7 and the same fluorescent material as that of Example 3 except that the light-emitting device does not contain a light-modulating agent;
  • Figure 16 is a comparison diagram of spectra of the LED light-emitting device of Example 8 and the same fluorescent material as that of Example 4, except that the light-emitting device does not contain a light-modulating agent;
  • 17 is a spectrum diagram of an LED light-emitting device prepared by using a YAG yellow phosphor with a blue LED chip;
  • Figure 18 is a comparison diagram of spectra of the LED light-emitting device of Example 9 and the same fluorescent material as that of Example 5, which only contains no light-modulating agent;
  • Embodiment 19 is a schematic structural view of a wide color gamut LED light emitting device in Embodiment 10.
  • FIG. 20 is a schematic structural view of a wide color gamut LED light emitting device in Embodiment 11.
  • Figure 2 shows a comparison of the luminescence spectra corresponding to the two different gamut triangles of Figure 1.
  • the light source used by both is a white light source.
  • line 201 is a spectrum having a high color gamut source
  • line 202 is a spectrum having a low color gamut source.
  • the difference between the spectral line 201 and the spectral line 202 is that the intensity of the spectral line 201 in the non-red, green and blue primary color bands is low.
  • Figure 3 is a schematic illustration of the use of the light source spectrum to amplify the color gamut employed in the present invention.
  • the core of the augmented color gamut of the present invention is to convert the light of the non-red, green and blue primary colors of the gray marker band into the red, green and blue primary colors of the white marker band.
  • the specific manner of converting the light of the non-red, green and blue primary colors of the gray mark band into the light of the red, green and blue primary colors of the white mark band includes: converting the light of the 301 area into the light of the 302 area, or the 304 area, or the 306 area .
  • the light of zone 303 is converted to light of zone 302, zone 304, or zone 306.
  • the light of zone 305 is converted to light of zone 302, zone 304, or zone 306.
  • Light from zone 307 is converted to light in zone 302, or zone 304, or zone 306.
  • Fig. 4 is a view showing the structure of a composite optical material of Embodiment 1 of the present invention.
  • the composite optical material includes a transparent substrate 401 and a plurality of optical wavelength conversion materials 402 discretely (preferably uniformly) distributed in the matrix and scattering particles 403 discretely distributed in the transparent substrate 401.
  • the scattering particles 403 are used to scatter incident light within the matrix to increase the optical path of the light through the composite optical material.
  • the composite optical material of the present invention is capable of converting light of three primary colors of non-red, green and blue into light of three primary colors of red, green and blue.
  • the area of the gamut triangle that can be displayed by the display is increased, as shown in FIG. It should be noted that in FIG. 4, in order to more clearly illustrate the relationship of the components in the composite optical material, the respective portions are not drawn to scale.
  • the transparent substrate 401 may be one or more of the following materials: acrylate resin, modified polyacrylate, polyurethane, modified polyurethane, epoxy resin, polycarbonate, silicone resin, Silicone resin, organosiloxane resin, modified silicone resin, polypropylene, polyethylene, polyvinyl chloride, polystyrene.
  • the matrix material is cured by UV curing or heat curing.
  • the optical wavelength conversion material 402 is an organic molecular fluorescent dye, which may be Sulforhodamine 101, Rhodamine 101 or HR101, or two or three of the three may be employed.
  • Sulforhodamine 101 can absorb light of three primary colors of red, green, and blue, that is, light of 560 to 600 nm (such as the 501 spectral curve in FIG. 5), and convert the absorbed light into The light of the red, green and blue primary colors is specifically light of 605 to 660 nm (as shown in the 502 spectral curve in Fig. 5).
  • the mass fraction of Sulforhodamine 101 in the composite optical material is from 0.0001% to 10%, preferably from 0.001% to 1%, preferably from 0.01% to 0.1%.
  • Rhodamine 101 or HR101 can also convert 560-600 nm non-primary light into 600-650 nm primary light.
  • the diffusion particles 403 are one or both of inorganic particles and organic polymer microspheres.
  • the inorganic particles may be one or more of BaSO4, TiO2, and SiO2.
  • the organic polymer microspheres may be one or more of polymethyl methacrylate PMMA, polystyrene PS, and silicone polymers.
  • the diffusion particles 403 have a diameter of 0.1 to 30 ⁇ m, preferably 0.5 to 20 ⁇ m.
  • the mass fraction of the diffusing particles in the composite optical material is from 0.01% to 20%, preferably from 0.1% to 10%, preferably from 1% to 5%.
  • the compensation is made by adding a green-emitting phosphor to the composite optical material.
  • green-emitting phosphors include green fluorescent quantum dots, beta-SiAlON phosphors, and the like.
  • the luminescence peak of such quantum dots should be between 510 and 540 nm, and the half-width of the luminescence peak should be less than 40 nm.
  • the quantum dot material may be CdSe, CdTe, or a core-shell structure quantum dot CdSe/CdS, CdSe/ZnS, CdTe/CdS, CdTe/ZnS, or a core-shell structure quantum dot CdSe/CdS/ZnS, CdTe/ CdS/ZnS.
  • the luminescent peak of the phosphor should be between 510 and 540, and the luminescence peak width should be less than 50 nm.
  • the present invention can also apply two other ways to adjust the white balance of the display light, including: 1. adjusting the encapsulation material of the white LED, changing the proportion of the mixed phosphor therein, or changing the thickness of the same proportion of the phosphor encapsulation material. 2. Adjust the switching ratio of the liquid crystal switch on the red, green and blue pixels in the liquid crystal module. For mode 1. When the green primary light needs to be compensated, the proportion of the green phosphor in the white LED encapsulant can be increased, or the thickness of the encapsulation layer can be increased by reducing the proportion of the red phosphor. For mode 2. When it is necessary to compensate for the green primary light, The transmittance of the blue and red pixel liquid crystal windows can be reduced.
  • the present invention compensates only for the green of the three primary colors.
  • the inventors of the present invention unexpectedly discovered that the white light after the composite optical material treatment has not only the white balance is not shifted, and the color gamut Augmentation, conversion efficiency is improved, and the reduction of color temperature is achieved.
  • the high color temperature white with an original color temperature of 6800-7000K can be converted into a low color temperature white of 5500-6000K.
  • FIG. 5 shows the absorption spectrum 501 and the emission spectrum 502 of the Sulforhodamine 101.
  • an acrylate monomer is used as a matrix precursor
  • Sulforhodamine 101 is used as a light wavelength conversion material
  • 2-hydroxy-2-methyl-1-phenylacetone is used as a matrix precursor polymerization photoinitiator.
  • Sulforhodamine 101 1 part by mass of Sulforhodamine 101 was added to 969 parts by mass of an acrylate monomer liquid at 20 ° C under a standard atmospheric pressure, and mixed by a shear disperser at a number of revolutions of 1000 rpm for 30 minutes. After the Sulforhodamine 101 was uniformly dispersed in the acrylate monomer, 30 parts by mass of 2-hydroxy-2-methyl-1-phenylacetone was further added, and the mixture was further mixed by a shear disperser for 10 minutes to obtain a slurry mixed solution. .
  • the flat PET base film is laid on a flat glass substrate having a base film thickness of 10 to 300 ⁇ m, preferably 188 ⁇ m.
  • a film coating machine to form a film having a thickness of 20 ⁇ m on a PET base film by a coating method using the slurry mixed solution obtained above, by controlling the feed speed of the above slurry mixed solution and the height and speed of the coating blade The film thickness was adjusted, and the glass substrate and the PET base film were exposed to an ultraviolet lamp together with the film.
  • the UV lamp can be a mercury lamp.
  • the ultraviolet light power is from 0.1 to 100 watts per square centimeter, preferably from 1 to 10 watts per square centimeter.
  • the exposure time is from 0.5 to 300 seconds, preferably from 1 to 100 seconds, preferably from 1 to 10 seconds.
  • the PET base film is removed from the glass substrate along with the composite optical material film and cut to the desired size.
  • Figure 6 there is shown a composite optical material film of the invention for use in a 55' television set.
  • the transparent matrix is doped with scattering particles
  • scattering particles are for increasing the optical path and the contact with the optical wavelength conversion material, in other embodiments. In some or specific situations or applications, scattering particles may be omitted, or other means of increasing the contact of light with the wavelength conversion material of light.
  • a display terminal in this embodiment, includes a light source and a display screen, and a film of the composite optical material in Embodiment 1 is disposed between the light source and the display screen. It should be understood by those skilled in the art that the display terminal also has other auxiliary devices such as a control panel, a processor, and the like. Since these auxiliary devices are existing components, they will not be described here.
  • a composite optical material film 702 having an area size conforming to the white planar light source 701 is laid on a light path from the light source to the outside of the screen in the color display, and the white light spectrum emitted by the white planar light source is modulated by the composite optical material film, wherein The light of the non-red, green, and blue primary colors, specifically the light of 560 to 610 nanometers, is converted into light of a red primary color, specifically light of 610 to 660 nanometers.
  • the spectrum of the thus modulated light source shows a wider color gamut.
  • the solid line 801 is the emission spectrum of the white light source of the color display
  • the dashed line 802 is the spectrum after the light from the white light source passes through the composite optical material film.
  • the gray areas indicate that light in the 560 to 610 nm wavelength range of the non-red, green, and blue primary color bands is absorbed by Sulforhodamine 101 and converted into light in the 610 to 660 nm band.
  • the solid triangle is the initial color gamut of the color display, specifically 79% NTSC.
  • the dotted triangle is the color gamut after the composite optical material is used, specifically 96% NTSC.
  • its color gamut coverage can be increased from 88% to 102%.
  • the color gamut of the color display has a significant increase, indicating that the composite optical material of the present invention can turn a common color gamut color display into a high color gamut high value-added color display.
  • the basic structure of the composite optical material in this embodiment is similar to that of Embodiment 1, and includes a transparent substrate, a light wavelength conversion material, and scattering particles.
  • the composite optical material of the present embodiment uses the rare earth ion doped up-conversion crystal powder as the optical wavelength conversion material.
  • the rare earth ion doped upconversion crystal may be a hexagonal phase of NaY (1-xy) F 4 :Er x ,Yb y having a crystallite size of 0.5 to 50 ⁇ m, preferably 1 to 10 ⁇ m.
  • the upconverting crystal powder is added in an amount of from 0.01% to 10% by mass based on the total mass of the composite. It is preferably from 0.1% to 1%.
  • the crystal grains can absorb red non-primary light of 650 to 670 nanometers, and convert the wavelength photons into green primary color light of 520 to 560 nanometers.
  • the red-emitting phosphor includes a red fluorescent quantum dot, which may also be a K 2 SiF 6 :Mn 4+ red phosphor.
  • the luminescence peak of such quantum dots should be between 610-640 nm, and the half-width of the luminescence peak should be less than 40 nm.
  • the quantum dot material may be CdSe, CdTe, or a core-shell structure quantum dot CdSe/CdS, CdSe/ZnS, CdTe/CdS, CdTe/ZnS, or a core-shell structure quantum dot CdSe/CdS/ZnS, CdTe/ CdS/ZnS.
  • the luminescent peak of the phosphor should be between 610 and 640, and the luminescence peak width should be less than 40 nm.
  • the transparent substrate and the diffusion particles in this embodiment are the same as those in Embodiment 1, and are not described herein again.
  • the basic structure of the composite optical material in this embodiment is similar to that of Embodiment 1, and includes a transparent substrate, a light wavelength conversion material, and scattering particles.
  • the composite optical material of the present embodiment uses a surface plasmon material as a light wavelength conversion material.
  • the surface plasmon material may be a gold nano-pyramid or a silver nanorod.
  • the size of the nanoparticles is from 10 to 500 nm, preferably from 20 to 200 nm.
  • the surface-isolated elementary nanoparticles are added in an amount of from 0.001% to 1%, preferably from 0.01% to 0.1%, based on the total mass of the composite.
  • the surface-isolated elementary nanoparticles can absorb non-red, green, and blue primary colors of 560 to 610 nanometers and convert them into heat.
  • the transparent substrate and the diffusion particles in this embodiment are the same as those in Embodiment 1, and are not described herein again.
  • the inventors of the present application have found that the use of surface-isolated elementary nanoparticles results in a scattering effect, which can reduce the optical path by reducing or even not using scattering particles.
  • the application of the isotactic element material has the special advantages of reducing the non-primary light: large absorption cross section, less material consumption and cost.
  • the phosphor paste is uniformly mixed from the following parts by weight:
  • the red phosphor may be one or more of K 2 SiF 6 :Mn 4+ , K/Na 2 TiF 6 :Mn 4+ , nitride, silicate;
  • the green phosphor may be one or more of ⁇ -SiAlON type nitrogen oxides, silicates, and aluminates;
  • the light modulator may be an anthrapy and its derivatives, anthraquinone and its derivatives, xanthene and its derivatives, triarylmethane and its derivatives, phthalocyanine and its derivatives, and tetraazapine a mixture of one or more of its derivatives, coumarin and its derivatives;
  • component A is silica gel or epoxy resin
  • component B is an acid anhydride curing agent
  • Select one of the A and B components and preferentially select the lower viscosity of the A and B components, and mix the red phosphor, the green phosphor and the light modulator in the above ratio to make the phosphor and the light modulator uniform. Distributed discretely. Then add another component and mix well again. This is done to: 1. Make the fluorescent material and the light modulating agent easier to distribute evenly; 2. Prevent the A component and the B component from reacting in advance to crosslink, and the fluorescent material and the light modulating agent cannot be uniformly distributed therein; 3. Producing less The bubbles make the bubble removal process easier.
  • the obtained glue is removed under vacuum to remove air bubbles, so that the residual air in the rubber is removed, so as not to affect its airtightness and optical performance.
  • the LED package cup with the blue chip is prepared, and the defoamed phosphor glue is filled through a syringe or a dispenser, and then heated and solidified after the filling, the curing method is: 1. at 90 ° C - 110 ° C Pre-cured for 1 hour; 2. Continued curing at 120-150 ° C for 3 hours.
  • the wide color gamut LED light emitting device obtained by the above steps is shown in FIG.
  • the embodiment provides an LED light emitting device, which comprises a package cup 101.
  • the bottom of the package cup is provided with a blue LED chip module 102.
  • the LED chip uses a blue LED chip with a peak emission of 445-458 nm, and the package cup is provided.
  • a fluorescent conversion layer 203 is provided therein, and the fluorescent conversion layer 203 is doped with a nickel-coordinated laverine derivative (i), and the fluorescent conversion layer is K 2 SiF 6 :Mn 4+ red phosphor, SiAlON:Eu 2 + Green phosphor and silica gel are mixed in a specific ratio and solidified in a sealed cup by heating.
  • the SiAlON:Eu 2+ green phosphor has a fluorescence peak wavelength of 525-535 nm and a half-value width of 50-60 nm; and the K 2 SiF 6 :Mn 4+ red phosphor has a fluorescence peak wavelength of 630 nm and a half-peak.
  • the width is 20nm.
  • the light modulating agent (i) has a strong absorption in a range of a first predetermined wavelength of 580 nm to 600 nm, and is converted into light in a range of a second predetermined wavelength of 620 nm to 660 nm and is emitted as heat energy.
  • the color light-emitting point of the LED light-emitting device prepared in this embodiment is (0.27, 0.26), and the required light modulation agent (i), SiAlON: Eu 2+ green phosphor and K 2 SiF 6 : Mn 4+ red in the fluorescent conversion layer.
  • the phosphors accounted for 0.01%, 15%, and 15% of the mass ratio of the encapsulant, respectively, and the carrier or matrix of the fluorescent conversion layer was silica gel.
  • the light modulator added in the fluorescence conversion layer of the present embodiment can effectively absorb the yellow-green light emitted by the SiAlON:Eu 2+ green phosphor in the 580-600 nm band.
  • the excitation emission spectrum of the LED device is shown by the line 501 in FIG. 11-13.
  • the color gamut of the produced LED light emitting device is 95% NTSC.
  • the color gamut of the LED light emitting device of the embodiment can be up to 110% NTSC, and the color gamut coverage is determined by the DCI-P3 color gamut standard. The rate can be increased from 104% to around 116%.
  • the excitation emission spectrum of the obtained LED light-emitting device before and after the addition of the light modulation agent is as shown by 602 in Fig. 12, wherein for the convenience of comparison, the spectrum 501 when no modulator is added is also shown.
  • the effect of the present invention is particularly preferable because when this combination is employed, the light modulator can The light between the primary colors is converted into the non-blue primary light (if the color is converted to the blue range, the color temperature will increase), and the effects of enhancing brightness, augmenting the color gamut, and reducing the color temperature can be achieved.
  • This example is substantially the same as Example 1, except that the light modulating agent used is a copper-coordinated laverine derivative (ii) and a hydrazine-coordinated laverine derivative (iii).
  • the light modulating agent (ii) can effectively absorb the orange-yellow light in the range of the first predetermined wavelength of 570 nm to 590 nm, and convert it into light in the range of the second predetermined wavelength of 610 nm to 660 nm and emit it in the form of heat energy;
  • the light modulating agent (iii) It can effectively absorb the orange light in the range of the first predetermined wavelength of 590-610 nm, and convert it into the light of the second predetermined wavelength range of 610 nm-660 nm and emit it in the form of heat energy, and the combination of the two can significantly improve the red and green colors.
  • the LED device prepared in this embodiment has a color coordinate point of (0.28, 0.28), and the required light modulator (ii), light modulator (iii), SiAlON:Eu 2+ green phosphor and K 2 SiF in the fluorescence conversion layer. 6 : The mass ratio of Mn 4+ red phosphor to the encapsulant is 0.01%, 0.012%, 20%, 20%, and the matrix or carrier of the fluorescent conversion layer is silica gel. As shown in FIG.
  • the excitation emission spectrum of the LED light-emitting device is 501, and the NTSC of the obtained LED light-emitting device is 95%, according to the DCI-P3 color gamut standard, its color gamut coverage can be increased from 104% to about 116%.
  • the excitation emission spectrum of the obtained LED light-emitting device is 702.
  • the color gamut of the LED lighting device of this embodiment can also reach 110% NTSC.
  • the LED package structure of this embodiment is similar to that of Embodiment 5, except that the phosphor used in this embodiment is Sr 3 SiO 5 :Ce 3+ green phosphor and CaAlSiN 3 :Eu 2+ red phosphor.
  • the green phosphor uses silicate phosphor, which has significant absorption of blue light and high light conversion efficiency.
  • the red phosphor uses nitride phosphor powder, which has rich luminescent color and stable physical and chemical properties. Although the gamut green phosphor and the nitride red phosphor have lower gamut coverage than SiAlON:Eu 2+ green phosphor and K 2 SiF 6 :Mn 4+ red phosphor, they can also meet LED due to their physicochemical properties.
  • the blue LED chip is matched with the nitride red phosphor and the silicate green phosphor, and its color gamut can reach 85% NTSC, and its white spectrum is shown by the 801 line in FIG.
  • the red and green phosphors are mixed with the light-modulating agent ⁇ -dispersed laverin derivative (iii) in a certain mass ratio into the encapsulant, uniformly dispersed and covered in the LED packaging cup, and finally heated and solidified. 100% NTSC color gamut LED light emitting device.
  • the red phosphor, the green phosphor, and the light modulator (iii) used in the present embodiment account for 3%, 10%, and 0.02% by mass of the encapsulant, and the matrix of the fluorescent conversion layer is a silica resin.
  • the light modulator (iii) has strong absorption in the range of the first predetermined wavelength of 590-610 nm, and is converted into light in the range of 630 nm to 660 nm of the second predetermined wavelength and is emitted in the form of heat energy.
  • the light modulating agent (iii) effectively absorbs the orange light between the red light and the green light, and can narrow the emission peak modulation of the red and green phosphors, and improve the color purity of the red and green lights to obtain the color of the LED light-emitting device.
  • the field value is increased to above 100% NTSC.
  • the color gamut coverage can be increased from 94% to about 105%.
  • This high color gamut white LED light-emitting device is used in the display backlight. The color reproduction capability of the display is greatly improved.
  • a white light spectrum comparison chart before and after light modulation in this embodiment is shown in FIG.
  • the spectral line 801 when no modulator is added, and the spectral line 902 after the addition of the light modulator (iii) are shown in FIG.
  • the intensity of the spectral line 902 in the 590-610 nm band is significantly lower than the spectral line 801, that is, the orange light of the band is absorbed and converted, so that the half-width of the red and green light is narrowed, thereby realizing the color gamut of the LED light-emitting device. aims.
  • the phosphor used in this embodiment is the same as that of Example 7, and the phosphor used is CaAlSiN 3 :Eu 2+ red phosphor and Sr 3 SiO 5 :Ce 3+ green phosphor, except that the light modulator used is nickel. Coordinating laverine derivative (i), triarylmethane derivative (iv), red phosphor, green phosphor, light modulating agent (i), light modulating agent (iv) in the proportion of encapsulating mass ratio 3 %, 10%, 0.01%, 0.01%, mixed into the encapsulated silica gel, uniformly dispersed and solidified.
  • the light modulator (iv) has strong absorption in the first predetermined wavelength range of 480 nm - 500 nm, effectively absorbs cyan light between blue light and green light, and is converted into a second predetermined wavelength range of 500 nm - 530 nm and 610 nm - 660 nm.
  • the light inside and the heat are emitted;
  • the light modulator (i) has a strong absorption in the first predetermined wavelength range of 590 nm to 610 nm, and effectively absorbs the orange light between the red light and the green light, and is converted into the first
  • the light in the range of two predetermined wavelengths of 610 nm to 660 nm is emitted in the form of heat energy.
  • the combination of two kinds of light modulation agents can simultaneously narrow the spectral waveform modulation of the three primary colors of red, green and blue, and improve the color purity of the three primary colors.
  • the excitation emission spectrum of the obtained LED device is as shown by 1002 in Fig. 14, and the line 801 in Fig. 14 is the same as Fig. 9
  • the LED color gamut of this embodiment can be up to 105% NTSC, and the color gamut coverage of the DCI-P3 can reach 115%.
  • the LED package structure of the present embodiment is similar to Example 5, except that the phosphor used in the present embodiment is YAG: Ce 3+ yellow phosphor, YAG: Ce 3+ determines garnet structure having excellent optical Its characteristics, its half-wave width can reach 110-120nm, white light can be realized with only one kind of phosphor, and it is the most widely used fluorescent material in white LED.
  • YAG: Ce 3+ phosphors can be used with appropriate light-modulating materials to significantly increase color gamut.
  • the light-modulating agent nickel-coordinated laverine derivative (i), the ruthenium-coordinated laverine derivative (iii), and the YAG:Ce 3+ yellow phosphor are mixed into the encapsulant in a certain mass ratio. After being uniformly dispersed, it is covered in a package cup of the LED, and finally heated to cure.
  • the light modulating agent (i) has strong absorption in a range of a first predetermined wavelength of 580 nm to 600 nm, and is converted into light in a range of a second predetermined wavelength of 620 nm to 660 nm and is emitted in the form of heat energy; the light modulating agent (iii) It can effectively absorb orange light in the wavelength range of 590-610 nm of the first predetermined wavelength, and convert it into light in the range of 610 nm-660 nm of the second predetermined wavelength and emit it in the form of heat energy, the light modulating agent (i) and the light modulating agent (iii) The combination of the two can be used to modulate the entire yellow spectrum of the YAG:Ce 3+ phosphor into a spectrum of red and green peaks, which is also to improve the purity of the red and green primary colors.
  • the YAG:Ce 3+ yellow phosphor, the light modulator (i), and the light modulator (iii) used in the present embodiment account for 10%, 0.005%, and 0.005% by mass of the encapsulant, and the matrix of the fluorescent conversion layer is Silicone resin.
  • the technical solution of the present invention is not used, when only YAG:Ce 3+ yellow phosphor is added to the fluorescent conversion layer, the excitation emission spectrum of the LED device is shown by the line 1101 in FIG. 11, and the NTSC of the obtained LED device is 68%.
  • the excitation emission spectrum of the obtained LED device is as shown by line 1202 in FIG.
  • the spectral line 1101 when no light modulator is added is also depicted in FIG.
  • the color gamut of the LED light-emitting device of this embodiment can be up to 85% NTSC, and the color gamut coverage of the DCI-P3 can reach 94%.
  • the color gamut of 85% NTSC is realized by using a single yellow phosphor, and the color gamut achieved by the conventional light-emitting device with two kinds of phosphors added with red and green phosphors is achieved.
  • the technical solution in this embodiment can significantly reduce the cost and simplify the complexity of the process under the same conditions.
  • the inventors of the present application have improved the structure thereof on the basis of the fifth embodiment.
  • the light modulating agent used in this embodiment is similar to that of Embodiment 5 and will not be described again here.
  • the inventors have noticed that in an LED light-emitting device, if a light modulator is added by doping in a fluorescent material, the distance between the light modulator and the chip is very close, and the heat released during the operation of the chip is easily light-adjusted. The absorption of the preparation, long-term heat radiation will affect the service life of the light modulator.
  • the inventors separated the light modulating agent from the red and green phosphors, and made the fluorescent conversion material into a fluorescent conversion layer, and the light modulating agent was made into a light modulating agent layer and arranged to contain red and green fluorescent particles.
  • FIG 19 A schematic diagram of the structure of an LED light emitting device according to Embodiment 10 of the present invention is shown.
  • 1301 is a light modulation layer
  • 1302 is a fluorescence conversion layer.
  • the mutual influence between the phosphor and the light modulating agent can be reduced, and the light conversion efficiency and the light absorbing efficiency can be improved.
  • the overall luminous efficiency and color gamut of the LED light-emitting device by separating the fluorescent conversion layer (phosphor layer) from the light absorbing layer (light modulating layer), the mutual influence between the phosphor and the light modulating agent can be reduced, and the light conversion efficiency and the light absorbing efficiency can be improved.
  • the nickel compound-coordinated laverine derivative (i), K 2 SiF 6 :Mn 4+ red phosphor, and SiAlON:Eu 2+ green phosphor in the phosphor layer have a mass ratio of the encapsulant.
  • the color gamut of the LED light-emitting device can reach 110% NTSC, and the color gamut coverage of DCI-P3 can reach 116%.
  • the organic resin such as silica gel can play the role of blocking water and oxygen, avoiding the contact of the phosphor with the outside world, and on the other hand, acting as an optical lens.
  • the shape of the lens is for the light intensity of the package. Distribution and spatial color uniformity have important implications.
  • This embodiment is similar to the embodiment 10 in that the light modulating agent is separated from the red and green phosphors. The difference is that the light modulating layer of the uppermost layer is formed into an ellipsoidal curved shape in this embodiment, and the structure diagram is as shown in FIG. 20 . As shown in Fig.
  • 1301 is a light modulation layer
  • 1302 is a fluorescence conversion layer, except that the light modulation layer is an ellipsoidal surface type.
  • the light modulation layer is an ellipsoidal surface type.
  • the nickel compound-coordinated laverine derivative (i), K 2 SiF 6 :Mn 4+ red phosphor, and SiAlON:Eu 2+ green phosphor in the phosphor layer have a mass ratio of the encapsulant.
  • the color gamut of the obtained LED light-emitting device can reach 110% NTSC, and the color gamut coverage of DCI-P3 can reach 116%.
  • the present invention has been described by taking an LED light emitting chip as an example in the above embodiments, those skilled in the art should understand that the light emitting device of the present invention is not limited to using an LED as a light emitting source, and other monochrome colors may be used. Illuminating light source.

Abstract

一种用于增广色域的复合光学材料及其制备方法与应用。复合光学材料包括透明基质（401）和离散分布在透明基质（401）内的光波长转化材料（402）。复合光学材料中还离散地设置若干散射粒子（403）。复合光学材料能够吸收预定波长范围内的光并将所吸收的光至少部分转化成另一波长范围内的光。复合光学材料使用于彩色显示器中，可将色域增广至使用前的120％或以上，同时几乎不会影响光源亮度，进而保持较高的光效。

Description

一种用于增广色域的复合光学材料及其制备方法与应用
相关申请
本申请主张于2016年8月18日提交的、名称为“一种广色域的发光器件及其制备方法”的中国发明专利申请201610693659.9的优先权，以及于2016年5月24日提交的、名称为“一种用于增广色域的复合光学材料及其制备方法与应用”的中国发明专利申请201610347549.7的优先权。
技术领域
本发明涉及材料领域，具体涉及用于在显示领域中调制光源光谱、增广显示色域的复合光学材料及其制备方法与应用。
背景技术
自20世纪90年代晚期开始，彩色显示器在日常生活中有了越来越广泛而重要的应用，包括电视、台式电脑、笔记本电脑、平板电脑、手机等等。至2010年左右，带有彩色显示器的智能手机已在人们的生活中占据大量时间。人们的食、住、行、工作、以及人与人之间交流，都已极大的依赖通过视觉从彩色显示器上获取信息。而各类显示器更是人们娱乐的重要工具之一。可以预见，在不远的将来，人类对显示器的总需求会有持续的提升。
显示器的显示视觉效果主要由时间分辨率、空间分辨率和色彩分辨率决定。其中较高的时间分辨率提供流畅的画面，较高的空间分辨率提供清晰的画质，较高的色彩分辨率则使画面更自然、更鲜艳。
显示器所显示的色彩分辨率主要取决于显示器光源所发出光的颜色成分和纯度。现有的主流彩色显示器为液晶显示器(LCD)或主动阵列有机发光二极管显示器(AMOLED)。其中液晶显示器主要使用白光发光二极管(WLED)作为光源。此类光源由于红、绿、蓝三基色色彩纯度低，导致所能显示的颜色局限在较窄色域，仅能达到美国国家电视系统委员会标准色域的70％左右。因此，此类显示器所显示的画面颜色较原始物体暗淡，失真。与此同时，AMOLED显示器的发光物质为有机电致发光染料，此类染料在聚集状态下发光峰较宽，色彩纯度低，导致此类显示器色域仅为85％左右。如何低成本地扩大彩色平板显示器的色域，使色域增广至100％NTSC或以上，是目前 的一个研发热点。
中国专利CN1221625C中介绍了一种“选择性吸光材料”。这种材料“吸收显示器中反射的光和三种主色外的中间光，由此增强颜色纯度和对比度。”但本申请的发明人发现，此种方法最大的问题在于吸收掉显示器光源中的光，导致显示器亮度明显降低，观赏效果明显变差。
中国专利申请CN105467674A中公开了一种“液晶显示终端色域提升方法”。这种方法“过滤可见光波段中除三基色波段之外的过度波段的可见光频谱能量，提升该三基色波段的可见光纯度”。本申请的发明人发现，此种方法同样有显示器光源中的部分光被“过滤”掉，而导致显示器亮度明显降低，观赏效果明显变差的缺点。
因此，本申请的发明人发现，目前现有的提升显示终端色域的方法和材料均会带来显示器亮度的降低，影响显示效果。
此外，LED的发光方式为蓝色发光芯片加绿色和红色荧光粉，或蓝色发光芯片加黄色荧光粉，即，LED的所有基础光均为蓝光，三基色中的其他两基色均需要通过荧光材料转化得到。目前，转化的效率往往在80％-90％，即，在LED的发光过程中，本身就存在的发光损耗。
现有显示终端的色温一般在6000-8000K左右，但是，本申请的发明人发现，实际上高色温并不一定代表着高性能，就人体的视觉感官而言，适当降低色温往往会带来更柔和更自然的显示效果，目前降低色温所采用的通常方式是增加荧光粉的含量，但是这种方式往往也会带来损耗的增加。
此外，对于发光器件而言，尽管高色域荧光粉近来发展迅速，但这仍不能满足行业内对高色域显示器(色域大于100％NTSC)的追求。目前在主流高色域LED背光中，限制其色域达到100％NTSC及以上的主要因素在于荧光粉的发射峰半峰宽太宽(大于50nm)，如何减少荧光粉半峰宽对NTSC色域值的限制从而获得更广色域的背光源器件，成为目前亟需解决的技术问题。
在LED封装中，荧光粉经常与硅胶等有机树脂混合在一起作为荧光粉胶，涂敷在芯片上。在白光LED中，荧光粉的位置和分布对LED的发光质量有很大影响。传统的LED封装是荧光粉与封装胶均匀混合后固化在LED芯片上。本发明除了对现有的荧光粉光谱进行调制以外，还从封装结构的设计上做出了改进，进一步提升LED背光源的发光质量，并改善其散热结构。
发明内容
针对上述问题，本发明希望提供一种既能够增强显示终端的色域，又不会影响或者较少地影响显示亮度的复合光学材料。从而，提供高色域和高亮度的彩色显示效果。
更优选地，本发明希望提供一种能够增强显示终端的色域、增加光转化效率，并且能够调节色温的复合光学材料。
具体而言，一方面，本发明提供一种用于增广色域的复合光学材料，其特征在于，所述复合光学材料包括透明基质和光波长转化材料，所述光波长转化材料离散地分布在所述透明基质内，所述光波长转化材料用于将第一预定波长范围内的光中的至少部分转化为第二预定波长范围内的光。
优选地，所述第一预定波长范围包括：0-430nm、470nm-500nm、560nm-610nm、660nm-750nm以及上述波长范围内的任意一个或多个波段；所述第二预定波长范围包括：430nm-470nm、500nm-560nm、610nm-660nm以及上述波长范围内的任意一个或多个波段。
需要说明的是，所述第一预定波长范围不包含其节点波长，而所述第二预定波长范围包含其节点波长430nm、470nm、500nm、560nm、610nm、660nm。
优选地，所述光波长转化材料为有机分子荧光染料，所述有机分子荧光染料为Sulforhodamine101、Rhodamine101以及HR101中的一种或多种的混合物。
优选地，所述光波长转化材料为稀土离子掺杂的上转换晶体粉末。
优选地，所述复合光学材料还包括散射粒子，所述散射粒子离散地分布在所述透明基质中。
优选地，所述复合光学材料还包括白平衡补偿材料。
优选地，所述散射粒子为无机粒子和有机聚合物微球中的一种或两种。
另一方面，一种复合光学材料的制备方法，其特征在于，所述制备方法包括：
步骤A)、准备液态基质材料和光波长转化材料；
步骤B)、将光波长转化材料按预定比例加入到所述液态基质材料中，并混合均匀；
步骤C)、将混合溶液布置成预定形状或限制在预定形状内；
步骤D)、对混合溶液进行固化，
所述光波长转化材料能够将第一预定波长范围内的光中的至少部分转化为第二预定波长范围内的光，优选地，所述第一预定波长范围包括：0-430nm、470nm-500nm、560nm-610nm、660nm-750nm以及上述波长范围内的任意一个或多个波段；所述第二预定波长范围包括：430nm-470nm、500nm-560nm、610nm-660nm以及上述波长范围内的任意一个或多个波段，优选地，所述光波长转化材料为有机分子荧光染料，所述有机分子荧光染料为Sulforhodamine101、Rhodamine101以及HR101中的一种或多种的混合物。
优选地，所述制备方法用于制备复合光学材料薄膜，所述步骤C)包括将所述混合溶液涂覆在预定基膜上。
另一方面，本发明提供一种高色域显示设备，其特征在于，所述高色域显示设备包括显示屏，所述显示屏包含所述的复合光学材料制成的膜片或者所述显示屏的至少一层由所述的复合光学材料制成。
需要说明的是，本文中所述的“透明基质”可以是：玻璃、丙烯酸酯类树脂、改性聚丙烯酸酯、聚氨酯、改性聚氨酯、环氧树脂、聚碳酸酯、硅树脂、硅氧树脂、有机硅氧烷类树脂、改性有机硅树脂、聚丙烯、聚乙烯、聚氯乙烯以及聚苯乙烯中的一种、或两种、或两种以上的叠加或组合。基质材料固化方式为UV固化或热固化。
本文中所述的“至少部分”可以指不同波长成分的至少部分，同时也可以指某一特定波长的光的强度的至少部分。
本文中所述的“光波长转化材料”包括但不限于半导体材料、半导体纳米材料、金属纳米材料、表面等离基元材料、离子掺杂的金属氧化物、离子掺杂的金属氮化物、离子掺杂的金属氮氧化物、离子掺杂的金属氟化物、离子掺杂的硅酸盐、有机小分子染料、有机大分子染料。
本发明所述的“白平衡补偿材料”指的是由于采用本发明的光波长转化材料将三基色间隙中的光转化成了三基色光中的一种或多种，改变了三基色光之间的比例，造成白平衡偏移，为了使白平衡返回到白色曲线上而对三基色光中没有因光波长转化材料的转化而增强或增强较弱的光进行补偿(即，增加该基色光的含量)。在本发明的一种优选实现方式中，所述白平衡补偿材料对三基色光中的光波长转化材料的非转化光波段进行补偿，优选地，如果光波长转化材料的转化光属于绿基色或红基色，则对绿基色或红基色中的另一个进行补偿。在这种情况下，通过光波长转化材料以及白平 衡补偿材料二者的配合，即可以实现提高色域、降低色温并且提高转化效率，一举三得。如果光波长转化材料的转化光属于蓝基色，则对绿基色和红基色二者进行补偿。
因此，优选地，本发明的光波长转化材料的目标波长设定在绿基色(500nm-560nm)或者红基色(610nm-660nm)波段范围内，我们将该基色称为目标基色，而白平衡补偿材料的补偿波段设定在绿基色或者红基色中非目标基色所在波段中，这样，在光源发光强度不变的情况下，能够既保证光效，又降低色温。
所述转化，可指利用发光材料，通过爱因斯坦受激激发和爱因斯坦自发辐射发过程或通过其他方式将光子变成波长不同的另一种光子。所述另一种光子可以比所吸收光子的波长长，即能量低，即光学下转换。所述另一种光子可以比所吸收光子波长短，即能量高，即光学上转换。
所述光学下转换，可指从波长为380nm至430nm的光，转化为波长430nm至470nm的光，或波长500nm至560nm的光，或波长610nm至660nm的光。
所述光学下转换，可指从波长为470nm至500nm的光，转化为波长500nm至560nm的光，或波长610nm至660nm的光。
所述光学下转换，可指从波长为560nm至610nm的光，转化为波长610nm至660nm的光。
所述光学上转换，可指从波长为660nm至750nm的光，转化为波长430nm至470nm的光，或波长500nm至560nm的光，或波长610nm至660nm的光。
所述光学上转换，可指从波长为560nm至610nm的光，转化为波长430nm至470nm的光，或波长500nm至560nm的光。
所述光学上转换，可指从波长为470nm至500nm的光，转化为波长430nm至470nm的光。
本发明的技术方案与现有技术相比具有以下优点：
本发明的产品可以制成薄膜状，通过简单地将该薄膜直接帖附在显示器的光源路径中，就可以有效增广彩色显示器的色域。
本发明能够增加光线通过复合光学材料的光程，提高光波长转化材料的利用率，提高光转化效率，从而有效降低成本。
本发明加入了扩散粒子的产品可以同时提供光转化和雾化两种功能，可以降低显示器模组的复杂程度和厚度，这是因为加入复合光学材料中的扩散粒子会导致光的散 射，从而增加光在光学材料中的光程，同时产生雾化的效果。
本发明的一个难点是如何在滤除非基色光的同时保持较高的光效。以往技术往往倾向于滤除非基色光，因为担心非基色光所导致的色域降低，但由此往往导致部分与非基色光波长较接近的基色光也同时被滤掉，导致光效降低。而本发明，则通过将非基色光，向基色光转化的方式，即削减了非基色光，又能提高基色光的亮度，从而提高光效。
而且，在上面提到的优选实现方式中，本发明还能够改变色温，优选降低色温。
此外，本发明还提供了一种广色域的发光器件，旨在解决现有发光器件在应用于显示领域时显示色域较低、色彩显示效果不佳的问题。
具体而言，一方面，本发明提供一种广色域的发光器件，其特征在于，所述广色域的发光器件包括：发光芯片、封装器件和光谱转换层，所述发光器件置于所述封装器件内，所述光谱转换层设置于在所述封装器件内、所述发光芯片的前方，所述发光芯片用于发出第一基色光，所述光谱转换层中包括荧光转换材料和光调制材料，所述荧光转换材料用于对所述第一基色光中的至少部分进行荧光转换，所述荧光转换的目标光至少包括第二基色光，所述光调制材料用于将第一预定波长范围内的光中的至少部分转化为第二预定波长范围内的光，或者将吸收的第一预定波长范围内的光转换成热能。
优选地，所述发光器件中，所述第一预定波长范围包括：0-430nm、470nm-500nm、560nm-610nm、660nm-750nm以及上述波长范围内的任意一个或多个波段；所述第二预定波长范围包括：430nm-470nm、500nm-560nm、610nm-660nm及上述波长范围内的任意一个或多个波段，优选地，所述第二预定波长范围还包括750nm-1mm及该范围内的任意一个或多个波段。
优选地，所述发光器件中，所述发光芯片为蓝光发光芯片，所述第一基色光为蓝光，优选地，所述荧光转换的目标光包括波长在610nm-660nm和500nm-560nm范围内的光，所述光调制材料用于将所述第一预定波长范围内的光的至少部分转换到500nm-560nm、610nm-660nm范围内的一个或多个波段。
优选地，所述发光器件中，所述发光芯片为LED发光芯片，所述封装器件为封装杯。
优选地，所述发光器件中，所述光谱转换层包括荧光转换层和光调制剂层，所述荧光转换层内具有荧光转换材料，所述光调制层内具有光调制材料，其中，所述荧光转换层设置于所述发光芯片上方，所述光调制层设置于所述荧光转换层上方。
优选地，所述发光器件中，所述荧光转换材料包括红色荧光粉和绿色荧光粉，所述光调制材料包括：蒽吡啶酮及其衍生物、蒽醌及其衍生物、氧杂蒽及其衍生物、三芳基甲烷及其衍生物、酞菁及其衍生物、四氮杂紫菜碱及其衍生物、香豆素及其衍生物中的一种或多种的混合物。
优选地，所述发光器件中，所述荧光转换材料包括宽谱带黄色荧光粉，所述光调制材料包括蒽吡啶酮及其衍生物、蒽醌及其衍生物、氧杂蒽及其衍生物、酞菁及其衍生物、四氮杂紫菜碱及其衍生物、香豆素及其衍生物中的一种或多种的混合物。
优选地，所述发光器件中，所述光调制层的一侧表面为平面或者曲面构造，所述曲面优选为球面、椭球面或抛物面。
另一方面，本发明提供一种制备广色域的发光器件的方法，其特征在于，所述方法包括下述步骤：
(1)按预定比例准备基质、荧光转换材料、光调制材料；
(2)将所述基质、荧光转换材料、光调制材料混合均匀制成荧光粉胶；
(3)准备发光芯片和封装器件，将所述发光芯片设置于所述封装器件底部；
(4)将所述荧光粉胶注入到所述封装器件中所述发光芯片上方；
(5)对所述封装器件内的荧光粉胶进行固化，
其中，所述发光芯片用于发出第一基色光，所述荧光转换材料用于对所述第一基色光中的至少部分进行荧光转换，所述荧光转换的目标光至少包括第二基色光，所述光调制材料用于将第一预定波长范围内的光中的至少部分转化为第二预定波长范围内的光，所述第一预定波长范围包括：0-430nm、470nm-500nm、560nm-610nm、660nm-750nm以及上述波长范围内的任意一个或多个波段；所述第二预定波长范围包括：430nm-470nm、500nm-560nm、610nm-660nm及上述波长范围内的任意一个或多个波段，优选地，所述第二预定波长范围还包括750nm-1mm及该范围内的任意一个或多个波段。
另一方面，本发明提供一种制备广色域发光器件的方法，其特征在于，所述方法包括下述步骤：
(1)按预定比例准备荧光转换层基质、荧光转换材料，将该荧光转换层基质、荧光转换材料混合均匀制成荧光粉胶；
(2)按预定比例准备光调制剂层基质、光调制材料，将该光调制剂层基质、光调制材料混合制成光调制剂；
(3)准备发光芯片和封装器件，将所述发光芯片设置于所述封装器件底部；
(4)将所述荧光粉胶注入到所述封装器件中所述发光芯片上方形成荧光粉层；
(5)将所述光调制剂注入到所述封装器件中所述荧光粉层的上方，形成光调制层；
(6)对所述封装器件内的荧光粉层和光调制层进行固化，其中，所述发光芯片用于发出第一基色光，所述荧光转换材料用于对所述第一基色光中的至少部分进行荧光转换，所述荧光转换的目标光至少包括第二基色光，所述光调制材料用于将第一预定波长范围内的光中的至少部分转化为第二预定波长范围内的光，所述第一预定波长范围包括：0-430nm、470nm-500nm、560nm-610nm、660nm-750nm以及上述波长范围内的任意一个或多个波段；所述第二预定波长范围包括：430nm-470nm、500nm-560nm、610nm-660nm及上述波长范围内的任意一个或多个波段，优选地，所述第二预定波长范围还包括750nm-1mm及该范围内的任意一个或多个波段。
本发明利用光调制材料(或称光调制剂)将第一预定波段范围内影响色纯度的光吸收，使三基色的色坐标在色度图的位置更靠近光谱轨迹，所围成的三角形面积增大，以此来增加LED发光器件的色域。
本发明中所述的光调制剂包括但不限于半导体材料、金属纳米材料、表面等离基元材料、离子掺杂的金属氧化物、离子掺杂的金属氮氧化物、离子掺杂的金属氟化物、离子掺杂的硅酸盐、有机小分子染料、有机大分子染料。
优选地，所述光调制剂可以是有机染料：蒽吡啶酮及其衍生物、蒽醌及其衍生物、氧杂蒽及其衍生物、三芳基甲烷及其衍生物、酞菁及其衍生物、四氮杂紫菜碱及其衍生物、香豆素及其衍生物中的一种或多种的混合物。
所述光调制剂在荧光转换层中所占质量比例范围在0.0001％-0.1％时，制得的LED器件色域达到最佳值，且不明显影响亮度。
优选地，所述红色荧光材料的发射波长主要在600–650nm之间，可以是K2SiF6：Mn4+、K/Na2TiF6：Mn4+、氮化物、硅酸盐、量子点中的一种或几种的混合物；所述 绿色荧光材料的发射波长主要在510-550nm之间，具体的，所述绿色荧光粉可以是β-SiAlON类型的氮氧化物、硅酸盐、铝酸盐、量子点中的一种或几种的混合物。其中，所述量子点包括CdSe、CdSe-ZnS、CsPbBr3、CsPbBrxI3-x等。
优选地，所述封装胶为环氧树脂类、硅胶类；
优选地，所述荧光粉胶的厚度为0.2mm–3mm。
优选地，所述广色域发光器件可应用于各种液晶显示器所需的背光模组中，具体包括侧入式和直下式的背光模组。
本发明在发光器件中添加光调制剂之后，可以适当减少光调制剂的目标光波段所对应的荧光转换材料的用量，这样，在不改变发光芯片发光强度的情况下，可以提高亮度、增广色域，甚至降低色温。
本发明发光器件具有以下有益效果：
1、本发明的发光器件由于引入了在第一预定波段范围有选择性强吸收的光调制剂，因此发射的蓝光、绿光或红光具有较窄的半峰宽，提高了其中一种或多种基色光的色彩纯度，从而具备了更高的色域和更逼真的显示效果。
2、本发明中引入的光调制剂可与各种荧光粉搭配使用，与现有的LED配色方案可完美兼容。
3、本发明提供的广色域发光器件其NTSC可达100％或以上。
4、本发明提供的不同种类的光调制剂，可搭配不同类型的荧光粉和发光芯片制成背光源，适用于不同型号的彩色显示设备，使用范围十分广泛。
需要说明的是，本发明的发光器件主要是应用在显示色域有一定要求的领域，尤其是用于作为显示设备的光源，并且最适合用作显示设备的背光源。本发明的发光器件在采用蓝光发光芯片时，效果尤佳。当然，不排除将本发明的广色域发光器件应用于其它照明形式上。只要其它照明形式的显示设备与本发明增广色域的原理不相违背，其它的应用形式也包含在本发明范围内。
附图说明
图1是不同发光光谱在色度空间中所对应的色域图；
图2是与图1中两种不同色域三角形所对应的发光光谱的对比情况视图；
图3为本发明所采用的通过调整光源光谱来增广色域的原理示意图；
图4为本发明实施例1中的复合光学材料的结构示意图；
图5为Sulforhodamine101的吸收谱501和发光谱502；
图6为本发明实施例1所制备的复合光学材料薄膜的照片；
图7为本发明实施例1所制备的复合光学材料在使用过程中的示意图；
图8为利用本发明的复合光学材料进行色域增广前后的光谱对比图；
图9为利用本发明的复合光学材料进行色域增广前后的色域对比图。
图10为本发明的广色域LED发光器件的结构示意图；
图11为采用K2SiF6:Mn4+红色荧光粉、SiAlON:Eu2+绿色荧光粉搭配蓝光LED芯片所制备的LED发光器件的光谱图；
图12为实施例5中的LED发光器件的光谱与采用实施例1相同荧光材料仅不包含光调制剂的发光器件的光谱的对比图；
图13为实施例6中的LED发光器件的光谱与采用实施例2相同荧光材料仅不包含光调制剂的发光器件的光谱的对比图；
图14为采用氮化物红色荧光粉、稀土掺杂的硅酸盐绿色荧光粉搭配蓝光LED芯片制备得到的LED发光器件的光谱图；
图15为实施例7中的LED发光器件的光谱与采用实施例3相同的荧光材料仅不包含光调制剂的发光器件的光谱的对比图；
图16为实施例8中的LED发光器件的光谱与采用实施例4相同的荧光材料仅不包含光调制剂的发光器件的光谱的对比图；
图17为采用YAG黄色荧光粉搭配蓝光LED芯片所制备的LED发光器件的光谱图；
图18为实施例9中的LED发光器件与采用实施例5相同的荧光材料仅不包含光调制剂的发光器件的光谱的对比图；
图19为实施例10中的广色域LED发光器件的结构示意图；
图20为实施例11中的广色域LED发光器件的结构示意图。
具体实施方式
以下结合附图及其实施例对本发明进行详细说明，但并不因此将本发明的保护范围限制在实施例描述的范围之中。
在对具体实施例进行具体描述之前，首先介绍一下本发明的复合光学材料进行色域增广的原理。
如图1所示，该图中示出了具有小色域(小三角形)和大色域(大三角形)的两种不同光谱之间的色域对比。从图中可以看出两个光谱对应的色域差距明显。
图2示出了与图1中两种不同色域三角形所对应的发光光谱的对比情况。二者所采用的光源同为白色光源。如图所示，谱线201为具有高色域光源的光谱，谱线202为具有低色域光源的光谱。谱线201与谱线202的区别在于，谱线201在非红绿蓝三基色波段的强度较低。
图3示出了本发明所采用的通过调整光源光谱来增广色域的示意图。如图所示，本发明增广色域的核心为将灰色标记波段的非红绿蓝三基色的光转化为白色标记波段的红绿蓝三基色的光。将灰色标记波段的非红绿蓝三基色的光转化为白色标记波段的红绿蓝三基色的光的具体方式包括：将301区的光转为302区、或304区、或306区的光。将303区的光转化为302区、或304区、或306区的光。将305区的光转化为302区、或304区、或306区的光。将307区的光转化为302区、或304区、或306区的光。
实施例1：
图4示出了本发明实施例1的复合光学材料的结构示意图。如图所示，在本实施例中复合光学材料包括透明基质401及若干离散地(优选均匀地)分布于基质中的光波长转化材料402以及离散地分布于透明基质401中的散射粒子403。散射粒子403用于对基质内的入射光线进行散射，增加光线通过复合光学材料的光程。本发明的复合光学材料能够将非红绿蓝三基色的光转化为红绿蓝三基色的光。进而增广显示器所能显示的色域三角形的面积，如图1所示。需要说明的是，图4中为了更清晰地示意出复合光学材料中各成分的关系，各部分之间并非完全按比例绘制。
在本实施例中，透明基质401可以采用下述材料中的一种或多种：丙烯酸酯类树脂、改性聚丙烯酸酯、聚氨酯、改性聚氨酯、环氧树脂、聚碳酸酯、硅树脂、硅氧树脂、有机硅氧烷类树脂、改性有机硅树脂、聚丙烯、聚乙烯、聚氯乙烯、聚苯乙烯。基质材料固化方式为UV固化或热固化。
在本实施例中，光波长转化材料402采用有机分子荧光染料，可以是Sulforhodamine101、Rhodamine101或HR101，或者可以采用三者中的两种或三种。具体而言，本申请的发明人经过研究发现Sulforhodamine101可以吸收非红绿蓝三基色的光，即560至600纳米波段的光(如图5中501光谱曲线)，并且将所吸收的光转化为红绿蓝三基色的光，具体为605至660纳米波段的光(如图5中502光谱曲线)。Sulforhodamine101在该复合光学材料中的质量分数为0.0001％至10％，优选为0.001％至1％，优选为0.01％至0.1％。
类似地，本发明的发明人发现Rhodamine101或HR101也可以将560-600nm的非基色光转化为600-650nm的基色光。
扩散粒子403采用无机粒子、有机聚合物微球中的一种或两种。无机粒子可以是BaSO4、TiO2以及SiO2中的一种或多种。有机聚合物微球可以是聚甲基丙烯酸甲酯PMMA、聚苯乙烯PS、有机硅聚合物中的一种或多种。扩散粒子403的直径为0.1至30微米，优选为0.5至20微米。扩散粒子在该复合光学材料中的质量分数为0.01％至20％，优选为0.1％至10％，优选为1％至5％。
在通过将560-600nm波段的非红绿蓝三基色光转化为600-650nm波段红色基色后，需要对510-560nm波段的绿色基色光做出补偿，用以将白平衡点调回白平衡白色曲线上(优选地调回到更低色温位置处的白平衡曲线上)。做出补偿的方式为，在复合光学材料中添加发射绿光的荧光粉。这种发射绿光的荧光粉包括绿色荧光量子点，beta-SiAlON荧光粉，等。对于用绿色荧光量子点作为绿光补偿荧光粉，这种量子点的发光峰位应位于510-540nm之间，发光峰半峰宽应小于40nm。这种量子点材料可以是CdSe,CdTe，或者是核壳结构量子点CdSe/CdS，CdSe/ZnS，CdTe/CdS，CdTe/ZnS，或者是核壳壳结构量子点CdSe/CdS/ZnS，CdTe/CdS/ZnS。对于用绿色荧光粉做绿光补偿材料，这种荧光粉的发光峰位应在510-540之间，发光峰宽应小于50nm。
本发明还可应用另两种方式来调节显示光的白平衡，包括：1.调节白色LED的封装材料，改变其中混合荧光粉的比例，或改变同比例荧光粉封装材料的厚度。2.调节液晶模组中，红绿蓝像素上液晶开关的开关比。对于方式1.，在需要对绿色基色光进行补偿时，可以增加白色LED封装材料中绿色荧光粉的比例，也可以通过降低红色荧光粉的比例同时增加封装层的厚度。对于方式2.在需要对绿色基色光进行补偿时， 可以减小蓝色和红色像素液晶窗口的透过率。
在本实施例中，本发明仅对三基色中的绿色进行了补偿，采用这种方式，本发明的发明人意外发现，经复合光学材料处理后的白光不仅白平衡没有发生偏移，色域增广，转化效率提升，而且，实现了对色温的降低。可将原始色温为6800-7000K的高色温白转化为5500-6000K的低色温白。
下面以光波长转化材料Sulforhodamine101为例介绍本实施例的复合光学材料的薄膜制备方法，图5示出了Sulforhodamine101的吸收光谱501和发射光谱502。在本实施例中，以丙烯酸酯单体为基质前驱体，以Sulforhodamine101为光波长转化材料，以2-羟基-2-甲基-1-苯基丙酮为基质前驱体聚合光引发剂。
首先在20摄氏度，1标准大气压的条件下，将1份质量的Sulforhodamine101加入到969份质量的丙烯酸酯单体液体中，用剪切分散机在1000转每分钟的转速下混合30分钟。待Sulforhodamine101均匀分散于丙烯酸酯单体中后，再加入30份质量的2-羟基-2-甲基-1-苯基丙酮，继续用剪切分散机混合10分钟至均匀，获得浆状混合溶液。
在平整玻璃基板上铺覆平整PET基膜，基膜厚度为10至300微米，优选为188微米。使用涂膜机通过涂膜法利用上面获得的浆状混合溶液在PET基膜上生成厚度为20微米的薄膜，可通过控制以上浆状混合溶液的供料速度和涂膜刮刀的高度及速度来调节膜厚，将玻璃基板、PET基膜与薄膜一同置于紫外灯下曝光。该紫外灯可以是汞灯。紫外灯光功率为0.1至100瓦每平方厘米，优选为1至10瓦每平方厘米。曝光时间为0.5至300秒，优选为1至100秒，优选为1至10秒。
将PET基膜随同复合光学材料薄膜从玻璃基板上取下，并按所需尺寸切割。参看附图6，即为裁切为55’电视机用的该发明复合光学材料薄膜。
需要说明的是，虽然本实施例中，在透明基质中掺杂了散射粒子，但是本领域技术人员应该理解，添加散射粒子是为了增加光程以及与光波长转化材料的接触，在其他实施例中或者一些特定情况或应用场景中，可以省去散射粒子，或者采用其他增加光与光波长转化材料的接触的方式。
实施例2：
在本实施例中，提供一种显示终端，该显示终端包括光源和显示屏，在光源和显示屏之间设置实施例1中的复合光学材料的薄膜。本领域技术人员应该理解，显示终端还具有控制面板、处理器等其他辅助设备，鉴于这些辅助设备均为现有部件，这里不再累述。
参看附图7，其示出了复合光学材料的薄膜的用法。将面积尺寸与白色面状光源701一致的复合光学材料薄膜702铺设在彩色显示器中从光源到荧幕外方向的光线路径上，白色面状光源发出的白色光光谱经过复合光学材料薄膜调制，其中的非红绿蓝三基色的光，具体为560至610纳米波段的光，被转化为红色基色的光，具体为610至660纳米波段的光。这样调制过的光源的光谱，显示色域更广。
参看附图8，其中实线801为彩色显示器白色光源的发光谱，虚线802为白色光源发出的光经过复合光学材料薄膜之后的光谱。灰色区域表明在非红绿蓝三基色波段的560至610纳米波长区间内的光被Sulforhodamine101吸收，并转化成610至660纳米波段的光。
参看附图9，其中实线三角形为彩色显示器的初始色域，具体为79％NTSC。虚线三角形为使用复合光学材料后的色域，具体为96％NTSC。以DCI-P3色域标准来看，其色域覆盖率可从88％提升至102％左右。彩色显示器的色域有明显增广，说明本发明的复合光学材料可以将一台普通色域彩色显示器变成一台高色域高附加值彩色显示器。
实施例3
本实施例中的复合光学材料的基本结构与实施例1类似，包括透明基质、光波长转化材料和散射粒子。与实施例1不同的是，本实施例的复合光学材料选用稀土离子掺杂的上转换晶体粉末为光波长转化材料。这种稀土离子掺杂的上转换晶体可以是六方相的NaY(1-x-y)F4:Erx,Yby，其晶粒尺寸为0.5至50微米，优选为1至10微米。该上转换晶体粉末的添加量为复合材料总质量的0.01％至10％。优选为0.1％至1％。该晶粒可以吸收650至670纳米的红色非基色光，将该波段光子转化为520至560纳米的绿色基色光。
在通过将650-670nm波段的非红绿蓝三基色光转化为520-560nm波段绿色基色 后，需要对600-650nm波段的红色基色光做出补偿，用以将白平衡点调回白平衡白色曲线上。做出补偿的方式为，在复合光学材料中添加发射红光的荧光粉。这种发射红光的荧光粉包括红色荧光量子点，也可以是K2SiF6:Mn4+红色荧光粉。对于用红色荧光量子点作为红光补偿荧光粉，这种量子点的发光峰位应位于610-640nm之间，发光峰半峰宽应小于40nm。这种量子点材料可以是CdSe,CdTe，或者是核壳结构量子点CdSe/CdS，CdSe/ZnS，CdTe/CdS，CdTe/ZnS，或者是核壳壳结构量子点CdSe/CdS/ZnS，CdTe/CdS/ZnS。对于用红色荧光粉做红光补偿材料，这种荧光粉的发光峰位应在610-640之间，发光峰宽应小于40nm。
本实施例中透明基质和扩散粒子与实施例1相同，在此不再进行赘述。
实施例4
本实施例中的复合光学材料的基本结构与实施例1类似，包括透明基质、光波长转化材料和散射粒子。与实施例1不同的是，本实施例的复合光学材料选用表面等离基元材料为光波长转化材料。这种表面等离基元材料可以是金纳米双棱锥，也可以是银纳米棒。其纳米颗粒的尺寸为10至500纳米，优选为20至200纳米。该表面等离基元纳米颗粒的添加量为复合材料总质量的0.001％至1％，优选为0.01％至0.1％。该表面等离基元纳米颗粒可以吸收560至610纳米波段的非红绿蓝三基色光，将其转化为热。本实施例中透明基质和扩散粒子与实施例1相同，在此不再进行赘述。
本申请的发明人发现，采用表面等离基元纳米颗粒会带来散射效果，可以减少甚至不使用散射粒子就能够达到增加光程的目的。另外应用等离基元材料实现对非基色光的削减有其特殊的优势：吸收截面大，用量少节省材料和成本等。
在对广色域LED发光器件的实施例进行具体描述之前，首先介绍一下本发明的广色域LED发光器件的制作过程。
首先准备荧光粉胶的原料，荧光粉胶由下述重量份数的原料均匀混合而成：
Figure PCTCN2016105761-appb-000001
Figure PCTCN2016105761-appb-000002
其中，红色荧光粉可以采用K2SiF6：Mn4+、K/Na2TiF6：Mn4+、氮化物、硅酸盐中的一种或几种；
其中，绿色荧光粉可以采用β-SiAlON类型的氮氧化物、硅酸盐、铝酸盐中的一种或几种；
其中，光调制剂可以采用蒽吡啶酮及其衍生物、蒽醌及其衍生物、氧杂蒽及其衍生物、三芳基甲烷及其衍生物、酞菁及其衍生物、四氮杂紫菜碱及其衍生物、香豆素及其衍生物中的一种或多种的混合物；
其中，A组分为硅胶或者环氧类树脂；B组分为酸酐类固化剂。当然，由于A组分和B组分仅仅是作为基质使用的，本领域技术人员在实际制备过程中可以根据需要适当调整其成分。
选取A、B组分中的一种，优先选取A、B组分中粘度较低者，与红色荧光粉、绿色荧光粉、光调制剂按上述比例混合均匀，使荧光粉和光调制剂均匀、离散地分布其中。然后加入另一组分，并再次混合均匀。这样做是为了：1.使荧光材料和光调制剂更容易均匀分布；2.防止A组分和B组分提前反应而交联，荧光材料和光调制剂无法均匀分布在其中；3.产生更少的气泡，使除气泡过程更容易。
然后将得到的胶置于真空条件下脱除气泡，使胶料中残留的空气脱除干净，以免影响其气密性和光学性能。之后准备好带蓝光芯片的LED封装杯，将上述脱泡后的荧光粉胶通过针筒或者点胶机灌装，灌装完毕后加热固化，固化方法为：1、在90℃–110℃下预固化1小时；2、在120–150℃下继续固化3小时。按以上步骤得到的广色域LED发光器件如图3所示。
实施例5
如图10所示，本实施例提供一种LED发光器件，其包含封装杯101，封装杯底部设有蓝光LED芯片模组102，LED芯片使用发射峰值为445–458nm的蓝光LED芯片，封装杯内设有荧光转换层203，荧光转换层203中掺杂光调制剂镍配位的紫菜碱衍生物(i)，荧光转换层采用K2SiF6:Mn4+红色荧光粉、SiAlON:Eu2+绿色荧光粉和硅胶以特 定比例混合而成，通过加热固化在封装杯内。
本实施例中，SiAlON:Eu2+绿色荧光粉的荧光峰值波长为525-535nm，半峰宽为50–60nm；K2SiF6:Mn4+红色荧光粉的荧光峰值波长为630nm，半峰宽为20nm。光调制剂(i)在第一预定波长580nm–600nm范围内具有较强吸收，并转换为第二预定波长620nm-660nm范围内的光和以热能的形式散发。本实施例制备的LED发光器件其色坐标点为(0.27，0.26)，荧光转换层中所需光调制剂(i)、SiAlON:Eu2+绿色荧光粉与K2SiF6:Mn4+红色荧光粉占封装胶的质量比例分别为0.01％、15％、15％，荧光转换层的载体或者基质为硅胶。本实施例的荧光转换层中所添加的光调制剂可以有效吸收580–600nm波段内SiAlON:Eu2+绿色荧光粉所发出的黄绿色光。当不采用本发明的技术方案，只加入SiAlON:Eu2+绿色荧光粉、K2SiF6:Mn4+红色荧光粉时，LED器件的激发发射光谱图为图11-13中501线所示，所制得的LED发光器件的色域为95％NTSC。而采用本发明当前实施例的技术方案，按照上述比例加入光调制剂时，本实施例的LED发光器件色域最高可达110％NTSC，以DCI-P3色域标准来看，其色域覆盖率可从104％提升至116％左右。所制得的LED发光器件加入光调制剂前后的激发发射光谱图如图12中602所示，其中，为了比对方便，同时示出了不加入调制剂时的光谱501。
实际上，当以蓝光Led为发光芯片、目标光的波长位于470nm-500nm、560nm-610nm范围内时，本发明的效果尤佳，这是因为，当采用这种组合时，光调制剂能够将基色光之间的光转化到非蓝色的基色光内(若转化到蓝光范围内，则色温会升高)，可以实现增强亮度、增广色域、降低色温三方面的效果。
实施例6
本实施例与实施例1大体相同，主要区别在于使用的光调制剂为铜配位的紫菜碱衍生物(ii)和钌配位的紫菜碱衍生物(iii)。其中光调制剂(ii)可以有效吸收第一预定波长570nm–590nm范围内的橙黄色光，并转化为第二预定波长610nm-660nm范围内的光和以热能的形式散发；光调制剂(iii)可以有效吸收第一预定波长590–610nm波段范围内的橙色光，并转化为第二预定波长610nm-660nm范围内的光和以热能的形式散发，两者的搭配使用可以显著提高红、绿两基色光的纯度。本实施例制备的LED器件其色坐标点为(0.28，0.28)，荧光转换层中所需光调制剂(ii)、光调制剂(iii)、 SiAlON:Eu2+绿色荧光粉与K2SiF6:Mn4+红色荧光粉占封装胶的质量比例为0.01％、0.012％、20％、20％、荧光转换层的基质或载体为硅胶。如图13所示，当不采用本发明的技术方案，只加入荧光粉，不加入光调制剂时，LED发光器件的激发发射光谱图为501所示，所制得的LED发光器件的NTSC为95％，以DCI-P3色域标准来看，其色域覆盖率可从104％提升至116％左右。当采用本发明当前实施例的技术方案，按照上述比例加入光调制剂时，所制得的LED发光器件的激发发射光谱图为702所示。本实施例的LED发光器件色域最高也可达110％NTSC。
实施例7
本实施例的LED封装结构与实施例5类似，不同的是本实施例使用的荧光粉为Sr3SiO5:Ce3+绿色荧光粉和CaAlSiN3:Eu2+红色荧光粉。绿色荧光粉采用硅酸盐荧光粉，其对蓝光具有显著吸收，光转换效率高，红色荧光粉采用氮化物荧光粉，具有丰富的发光颜色，且物化性能十分稳定。虽然硅酸盐绿色荧光粉与氮化物红色荧光粉的色域覆盖率不如SiAlON:Eu2+绿色荧光粉与K2SiF6:Mn4+红色荧光粉，但由于其物理化学性能也能满足LED发光器件的基本要求，且其价格更为适中，使得其使用范围远比后者广泛。蓝光LED芯片搭配该氮化物红色荧光粉和硅酸盐绿色荧光粉，其色域可达85％NTSC，其白光谱如图14中的801线所示。将该红、绿荧光粉搭配光调制剂钌配位的紫菜碱衍生物(iii)以一定质量比例混合到封装胶中，均匀分散后覆到LED的封装杯中，最后加热进行固化，可以得到100％NTSC色域的LED发光器件。本实施例中使用的红色荧光粉、绿色荧光粉、光调制剂(iii)占封装胶质量比例为3％、10％、0.02％，荧光转换层的基质为硅胶树脂。其中，光调制剂(iii)在第一预定波长590-610nm波段范围内具有较强吸收，并转化为第二预定波长630nm-660nm范围内的光和以热能的形式散发。光调制剂(iii)有效吸收了红光和绿光之间的橙色光，可将红、绿荧光粉的发射峰调制变窄，红、绿光的色纯度提高，得以将LED发光器件的色域值提升至100％NTSC以上，以DCI-P3色域标准来看，其色域覆盖率可从94％提升至105％左右，将此高色域白光LED发光器件用于显示器背光中，可使显示器的色彩还原能力大幅提升。该实施例中经光调制前后的白光光谱对比图如图15所示。图9中示出了不加入调制剂时的光谱线801，以及加入光调制剂(iii)后的光谱线902。光谱线902在 590-610nm波段的光强度明显低于光谱线801，即该波段的橙色光被吸收转换，使得红光和绿光的半峰宽变窄，实现LED发光器件色域增广的目标。
实施例8
本实施例所用的荧光粉与实施例7相同，使用的荧光粉为CaAlSiN3:Eu2+红色荧光粉和Sr3SiO5:Ce3+绿色荧光粉，不同的是使用的光调制剂为镍配位的紫菜碱衍生物(i)、三芳基甲烷衍生物(iv)，将红色荧光粉、绿色荧光粉、光调制剂(i)、光调制剂(iv)以占封装胶质量比例的3％、10％、0.01％、0.01％、混合到封装硅胶中，使之均匀分散后固化。光调制剂(iv)在第一预定波长480nm–500nm波段范围内具有较强吸收，有效吸收了蓝光和绿光之间的青色光，并转化为第二预定波长500nm-530nm、610nm-660nm范围内的光和以热能的形式散发；光调制剂(i)在第一预定波长590nm–610nm波段范围内具有较强吸收，有效吸收了红光和绿光之间的橙色光，并转化为第二预定波长610nm-660nm范围内的光和以热能的形式散发。两种光调制剂的搭配使用，可同时将红、绿、蓝三种基色光的光谱波形调制变窄，提高了三基色光的色彩纯度。按照上述比例加入光调制剂(i)、光调制剂(iv)时，所制得的LED器件的激发发射光谱图如图14中1002所示，图14中的谱线801与图9相同为在发光器件采用上述荧光材料情况下不加入调制剂时的光谱线。本实施例的LED色域最高可达105％NTSC，其DCI-P3的色域覆盖率可达115％。
实施例9
本实施例的LED封装结构与实施例5类似，不同的是本实施例使用的荧光粉为YAG：Ce3+的黄色荧光粉，YAG：Ce3+的石榴石结构决定了其具有优良的光学特性，其半波宽可以达到110-120nm，仅用这一种荧光粉即可实现白光，是白光LED中使用最广泛的一种荧光材料。但也由于该荧光粉本身的光谱分布单一，故存在显示色域不高的问题，YAG：Ce3+的黄色荧光粉的色域为65％-75％。YAG：Ce3+荧光粉与合适的光调制材料搭配使用，即可显著提升色域。
本实施例中将光调制剂镍配位的紫菜碱衍生物(i)、钌配位的紫菜碱衍生物(iii)和YAG：Ce3+黄色荧光粉以一定质量比例混合到封装胶中，均匀分散后覆到LED的封 装杯中，最后加热进行固化。其中，光调制剂(i)在第一预定波长580nm–600nm范围内具有较强吸收，并转换为第二预定波长620nm-660nm范围内的光和以热能的形式散发；光调制剂(iii)可以有效吸收第一预定波长590–610nm波段范围内的橙色光，并转化为第二预定波长610nm-660nm范围内的光和以热能的形式散发，光调制剂(i)和光调制剂(iii)两者的搭配使用可将YAG：Ce3+荧光粉发出的一整个黄光波谱调制成红、绿两个峰的波谱，其实质也是提高红色和绿色基色光的纯度。本实施例中使用的YAG：Ce3+黄色荧光粉、光调制剂(i)、光调制剂(iii)占封装胶的质量比例为10％、0.005％、0.005％，荧光转换层的基质为硅胶树脂。当不采用本发明的技术方案，荧光转换层中只加入YAG：Ce3+黄色荧光粉时，LED器件的激发发射光谱图为图11中1101线所示，所制得的LED器件的NTSC为68％。而采用本发明当前实施例的技术方案，按照上述最佳比例加入光调制剂(i)和光调制剂(iii)时，所制得的LED器件的激发发射光谱图如图18中1202线所示，为了方便对比，图18中同样绘出了不加入光调制剂时的光谱图线1101。本实施例的LED发光器件色域最高可达85％NTSC，其DCI-P3的色域覆盖率可达94％。
本实施例中，由于采用了光调制剂，利用单一的黄色荧光粉就实现了85％NTSC的色域，达到了普通的添加红、绿两种荧光粉的发光器件所达到的色域。对于一般产品而言，采用本实施例中的技术方案，在同等条件下，可以显著降低成本，简化工艺的复杂度。
实施例10
在本实施例中，本申请的发明人在实施例5的基础上对其结构进行了改进。本实施例中所用的光调制剂与实施例5类似，在此不再进行赘述。
具体而言，发明人注意到LED发光器件中，如果通过在荧光材料中掺杂的方式加入光调制剂，则光调制剂与芯片的距离很近，芯片工作过程中释放的热量容易被光调制剂吸收，长期的热辐射会影响光调制剂的使用寿命。为对这一问题进行改善，本发明人将光调制剂与红色、绿色荧光粉分离，将荧光转换材料制成荧光转换层，将光调制剂制成光调制剂层设置在包含红色、绿色荧光粉的荧光转换层的上一层，以降低光调制剂的工作环境温度，提升其稳定性，进一步改善LED光源的光效和色域。图19 示出了本发明实施例10的LED发光器件结构示意图，图中1301为光调制层，1302为荧光转换层。
该实施例中通过将荧光转换层(荧光粉胶层)与光吸收层(光调制层)分离开来，可以减少荧光粉与光调制剂之间的相互影响，提升光转换效率与光吸收效率，以提升LED发光器件整体的发光效率和色域。
本实施例中荧光粉胶层内光调制剂镍配位的紫菜碱衍生物(i)、K2SiF6:Mn4+红色荧光粉、SiAlON:Eu2+绿色荧光粉占封装胶的质量比例为0.01％、15％、15％，得到的LED发光器件色域也可达110％NTSC,其DCI-P3的色域覆盖率可达116％。
实施例11
在本实施例中，本申请的发明人在实施例10的基础上进行了进一步改进。
硅胶等有机类的树脂在LED发光器件中一方面可以起到隔水隔氧的效果，避免荧光粉与外界接触，另一方面还起到光学透镜的作用，透镜的形貌对于封装的光强分布和空间颜色均匀性具有重要影响。本实施例类似于实施例10，将光调制剂与红色、绿色荧光粉分离，不同的是本实施例将最上面一层的光调制层制成了椭球曲面形，其结构示意图如图20所示，与图19类似地，1301为光调制层，1302为荧光转换层，不同的是光调制层为椭球曲面型。当光线通过曲面时，会发生折射而起到聚光的效果，该椭球曲面结构由于具有水平和垂直两个方向的弧度，可以实现均匀、高效的光分布。
本实施例中荧光粉胶层内光调制剂镍配位的紫菜碱衍生物(i)、K2SiF6:Mn4+红色荧光粉、SiAlON:Eu2+绿色荧光粉占封装胶的质量比例为0.01％、15％、15％，得到的LED发光器件的色域也可达110％NTSC,其DCI-P3的色域覆盖率可达116％。
需要说明的是，虽然上面实施例中，以LED发光芯片为例对本发明进行了说明，但是本领域技术人员应该理解，本发明的发光器件不限于使用LED作为发光光源，还可以使用其他单色发光光源。
虽然上面结合本发明的优选实施例对本发明的原理进行了详细的描述，本领域技术人员应该理解，上述实施例仅仅是对本发明的示意性实现方式的解释，并非对本发明包含范围的限定。实施例中的细节并不构成对本发明范围的限制，在不背离本发明的精神和范围的情况下，任何基于本发明技术方案的等效变换、简单替换等显而易见 的改变，均落在本发明保护范围之内。

Claims (20)

  1. 一种用于增广色域的复合光学材料，其特征在于，所述复合光学材料包括透明基质和光波长转化材料，所述光波长转化材料离散地分布在所述透明基质内，所述光波长转化材料用于将第一预定波长范围内的光中的至少部分转化为第二预定波长范围内的光。
  2. 根据权利要求1所述的复合光学材料，其特征在于，所述第一预定波长范围包括：0-430nm、470nm-500nm、560nm-610nm、660nm-750nm以及上述波长范围内的任意一个或多个波段；所述第二预定波长范围包括：430nm-470nm、500nm-560nm、610nm-660nm以及上述波长范围内的任意一个或多个波段。
  3. 根据权利要求2所述的复合光学材料，其特征在于，所述光波长转化材料为有机分子荧光染料，所述有机分子荧光染料为Sulforhodamine101、Rhodamine101以及HR101中的一种或多种的混合物。
  4. 根据权利要求2所述的复合光学材料，其特征在于，所述光波长转化材料为稀土离子掺杂的上转换晶体粉末。
  5. 根据权利要求1所述的复合光学材料，其特征在于，所述复合光学材料还包括散射粒子，所述散射粒子离散地分布在所述透明基质中。
  6. 根据权利要求1或5所述的复合光学材料，其特征在于，所述复合光学材料还包括白平衡补偿材料。
  7. 根据权利要求5所述的复合光学材料，其特征在于，所述散射粒子为无机粒子和有机聚合物微球中的一种或两种。
  8. 一种复合光学材料的制备方法，其特征在于，所述制备方法包括：
    步骤A)、准备液态基质材料和光波长转化材料；
    步骤B)、将光波长转化材料按预定比例加入到所述液态基质材料中，并混合均匀；
    步骤C)、将混合溶液布置成预定形状或限制在预定形状内；
    步骤D)、对混合溶液进行固化，
    所述光波长转化材料能够将第一预定波长范围内的光中的至少部分转化为第二预定波长范围内的光，优选地，所述第一预定波长范围包括：0-430nm、470nm-500nm、 560nm-610nm、660nm-750nm以及上述波长范围内的任意一个或多个波段；所述第二预定波长范围包括：430nm-470nm、500nm-560nm、610nm-660nm以及上述波长范围内的任意一个或多个波段，优选地，所述光波长转化材料为有机分子荧光染料，所述有机分子荧光染料为Sulforhodamine101、Rhodamine101以及HR101中的一种或多种的混合物。
  9. 根据权利要求8所述的方法，其特征在于，所述制备方法用于制备复合光学材料薄膜，所述步骤C)包括将所述混合溶液涂覆在预定基膜上。
  10. 一种高色域显示设备，其特征在于，所述高色域显示设备包括显示屏，所述显示屏包含由权利要求1-7中任意一项所述的复合光学材料制成的膜片或者所述显示屏的至少一层由权利要求1-7中任意一项所述的复合光学材料制成。
  11. 一种广色域的发光器件，其特征在于，所述广色域的发光器件包括：发光芯片、封装器件和光谱转换层，所述发光器件置于所述封装器件内，所述光谱转换层设置于在所述封装器件内、所述发光芯片的前方，所述发光芯片用于发出第一基色光，所述光谱转换层中包括荧光转换材料和光调制材料，所述荧光转换材料用于对所述第一基色光中的至少部分进行荧光转换，所述荧光转换的目标光至少包括第二基色光，所述光调制材料用于将第一预定波长范围内的光中的至少部分转化为第二预定波长范围内的光，或者将吸收的第一预定波长范围内的光转换成热能。
  12. 根据权利要求11所述的广色域的发光器件，其特征在于，所述第一预定波长范围包括：0-430nm、470nm-500nm、560nm-610nm、660nm-750nm以及上述波长范围内的任意一个或多个波段；所述第二预定波长范围包括：430nm-470nm、500nm-560nm、610nm-660nm及上述波长范围内的任意一个或多个波段，优选地，所述第二预定波长范围还包括750nm-1mm及该范围内的任意一个或多个波段。
  13. 根据权利要求12所述的广色域的发光器件，其特征在于，所述发光芯片为蓝光发光芯片，所述第一基色光为蓝光，优选地，所述荧光转换的目标光包括波长在610nm-660nm和500nm-560nm范围内的光，所述光调制材料用于将所述第一预定波长范围内的光的至少部分转换到500nm-560nm、610nm-660nm范围内的一个或多个波段。
  14. 根据权利要求12或13所述的广色域的发光器件，其特征在于，所述发光芯片为LED发光芯片，所述封装器件为封装杯。
  15. 根据权利要求14所述的广色域的发光器件，其特征在于，所述光谱转换层包括荧光转换层和光调制剂层，所述荧光转换层内具有荧光转换材料，所述光调制层内具有光调制材料，其中，所述荧光转换层设置于所述发光芯片上方，所述光调制层设置于所述荧光转换层上方。
  16. 根据权利要求11或15所述的广色域的发光器件，其特征在于，所述荧光转换材料包括红色荧光粉和绿色荧光粉，所述光调制材料包括：蒽吡啶酮及其衍生物、蒽醌及其衍生物、氧杂蒽及其衍生物、三芳基甲烷及其衍生物、酞菁及其衍生物、四氮杂紫菜碱及其衍生物、香豆素及其衍生物中的一种或多种的混合物。
  17. 根据权利要求15或16所述的广色域的发光器件，其特征在于，
    所述荧光转换材料包括宽谱带黄色荧光粉，所述光调制材料包括蒽吡啶酮及其衍生物、蒽醌及其衍生物、氧杂蒽及其衍生物、酞菁及其衍生物、四氮杂紫菜碱及其衍生物、香豆素及其衍生物中的一种或多种的混合物。
  18. 根据权利要求17所述的广色域的发光器件，其特征在于，所述光调制层的一侧表面为平面或者曲面构造，所述曲面优选为球面、椭球面或抛物面。
  19. 一种制备广色域的发光器件的方法，其特征在于，所述方法包括下述步骤：
    (1)按预定比例准备基质、荧光转换材料、光调制材料；
    (2)将所述基质、荧光转换材料、光调制材料混合均匀制成荧光粉胶；
    (3)准备发光芯片和封装器件，将所述发光芯片设置于所述封装器件底部；
    (4)将所述荧光粉胶注入到所述封装器件中所述发光芯片上方；
    (5)对所述封装器件内的荧光粉胶进行固化，
    其中，所述发光芯片用于发出第一基色光，所述荧光转换材料用于对所述第一基色光中的至少部分进行荧光转换，所述荧光转换的目标光至少包括第二基色光，所述光调制材料用于将第一预定波长范围内的光中的至少部分转化为第二预定波长范围内的光，所述第一预定波长范围包括：0-430nm、470nm-500nm、560nm-610nm、660nm-750nm以及上述波长范围内的任意一个或多个波段；所述第二预定波长范围包括：430nm-470nm、500nm-560nm、610nm-660nm及上述波长范围内的任意一个或多个波段，优选地，所述第二预定波长范围还包括750nm-1mm及该范围内的任意一个或多个波段。
  20. 一种制备广色域发光器件的方法，其特征在于，所述方法包括下述步骤：
    (1)按预定比例准备荧光转换层基质、荧光转换材料，将该荧光转换层基质、荧光转换材料混合均匀制成荧光粉胶；
    (2)按预定比例准备光调制层基质、光调制材料，将该荧光转换层基质、光调制材料混合制成光调制剂；
    (3)准备发光芯片和封装器件，将所述发光芯片设置于所述封装器件底部；
    (4)将所述荧光粉胶注入到所述封装器件中所述发光芯片上方形成荧光粉层；
    (5)将所述光调制剂注入到所述封装器件中所述荧光粉层的上方，形成光调制层；
    (6)对所述封装器件内的荧光粉层和光调制层进行固化，其中，所述发光芯片用于发出第一基色光，所述荧光转换材料用于对所述第一基色光中的至少部分进行荧光转换，所述荧光转换的目标光至少包括第二基色光，所述光调制材料用于将第一预定波长范围内的光中的至少部分转化为第二预定波长范围内的光，所述第一预定波长范围包括：0-430nm、470nm-500nm、560nm-610nm、660nm-750nm以及上述波长范围内的任意一个或多个波段；所述第二预定波长范围包括：430nm-470nm、500nm-560nm、610nm-660nm及上述波长范围内的任意一个或多个波段，优选地，所述第二预定波长范围还包括750nm-1mm及该范围内的任意一个或多个波段。
PCT/CN2016/105761 2016-05-24 2016-11-14 一种用于增广色域的复合光学材料及其制备方法与应用 WO2017201982A1 (zh)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201610347549.7A CN106019638A (zh) 2016-05-24 2016-05-24 一种用于增广色域的复合光学材料及其制备方法与应用
CN201610347549.7 2016-05-24
CN201610693659.9A CN106328635A (zh) 2016-08-18 2016-08-18 一种广色域的发光器件及其制备方法
CN201610693659.9 2016-08-18

Publications (1)

Publication Number Publication Date
WO2017201982A1 true WO2017201982A1 (zh) 2017-11-30

Family

ID=60412107

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/105761 WO2017201982A1 (zh) 2016-05-24 2016-11-14 一种用于增广色域的复合光学材料及其制备方法与应用

Country Status (1)

Country Link
WO (1) WO2017201982A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113437052A (zh) * 2021-05-06 2021-09-24 福州大学 改善微小型led背光或显示均匀性的色转换层及其制备方法
CN114035251A (zh) * 2021-11-26 2022-02-11 常州智文光电科技有限公司 含微气泡量子点扩散膜及其制备方法
US11322707B2 (en) 2019-01-29 2022-05-03 Sharp Kabushiki Kaisha Cadmium-free quantum dot LED with improved emission color

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101008736A (zh) * 2006-01-25 2007-08-01 启萌科技有限公司 液晶显示装置
CN101169487A (zh) * 2006-10-24 2008-04-30 住友化学株式会社 光漫射树脂组合物
CN102148320A (zh) * 2010-09-29 2011-08-10 友达光电股份有限公司 白光发光二极管装置、发光装置及液晶显示器
US20120256163A1 (en) * 2011-04-11 2012-10-11 Sanghyuck Yoon Light emitting unit and display device including the same
CN105572962A (zh) * 2014-10-31 2016-05-11 爱思开哈斯显示用薄膜有限公司 色纯度增强及亮度补偿膜以及包括该膜的液晶显示装置
CN106019638A (zh) * 2016-05-24 2016-10-12 武汉保丽量彩科技有限公司 一种用于增广色域的复合光学材料及其制备方法与应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101008736A (zh) * 2006-01-25 2007-08-01 启萌科技有限公司 液晶显示装置
CN101169487A (zh) * 2006-10-24 2008-04-30 住友化学株式会社 光漫射树脂组合物
CN102148320A (zh) * 2010-09-29 2011-08-10 友达光电股份有限公司 白光发光二极管装置、发光装置及液晶显示器
US20120256163A1 (en) * 2011-04-11 2012-10-11 Sanghyuck Yoon Light emitting unit and display device including the same
CN105572962A (zh) * 2014-10-31 2016-05-11 爱思开哈斯显示用薄膜有限公司 色纯度增强及亮度补偿膜以及包括该膜的液晶显示装置
CN106019638A (zh) * 2016-05-24 2016-10-12 武汉保丽量彩科技有限公司 一种用于增广色域的复合光学材料及其制备方法与应用

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11322707B2 (en) 2019-01-29 2022-05-03 Sharp Kabushiki Kaisha Cadmium-free quantum dot LED with improved emission color
CN113437052A (zh) * 2021-05-06 2021-09-24 福州大学 改善微小型led背光或显示均匀性的色转换层及其制备方法
CN113437052B (zh) * 2021-05-06 2024-01-30 福州大学 改善微小型led背光或显示均匀性的色转换层及其制备方法
CN114035251A (zh) * 2021-11-26 2022-02-11 常州智文光电科技有限公司 含微气泡量子点扩散膜及其制备方法

Similar Documents

Publication Publication Date Title
JP4767243B2 (ja) 白色光源、バックライトユニットおよびｌｃｄディスプレイ
CN100578781C (zh) 发光装置
CN103222077B (zh) 发光装置
US20160141465A1 (en) Light emitting device and fabricating method thereof
CN208284498U (zh) 一种led器件、背光灯条和背光模组
US20220231201A1 (en) Devices including green-emitting phosphors
JP2008517091A (ja) 蛍光体及びその蛍光体を利用した発光素子｛Ｐｈｏｓｐｈｏｒａｎｄｌｉｇｈｔｅｍｉｔｔｉｎｇｄｅｖｉｃｅｕｓｉｎｇｔｈｅｓａｍｅ｝
WO2011129429A1 (ja) Ｌｅｄ発光装置
CN102782891A (zh) 发光装置
WO2017201982A1 (zh) 一种用于增广色域的复合光学材料及其制备方法与应用
CN106449943A (zh) 一种倒装型量子点led灯珠的成型封装方法
CN107331753A (zh) 高色域白光led及背光模组
CN106019638A (zh) 一种用于增广色域的复合光学材料及其制备方法与应用
CN105485573B (zh) 一种高色域直下式led背光模组
CN208284497U (zh) 一种led器件、背光灯条和背光模组
CN102282687B (zh) 均匀颜色发光的led封装
CN101840987A (zh) 白光发射装置以及使用该白光发射装置的白光源模块
KR20040088418A (ko) 삼파장 백색 발광다이오드
WO2021164103A1 (zh) 一种显示用宽色域背光源
CN109524392A (zh) 一种近紫外激发白光的led装置
CN208888407U (zh) 一种导光板
CN207165565U (zh) 一种cob光源结构
CN101937963A (zh) Led发光单元及其封装方法
KR100855556B1 (ko) 발광다이오드
KR101778864B1 (ko) 광 변환 부재 및 이를 포함하는 표시장치 및 발광소자 패키지

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16902966

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 16902966

Country of ref document: EP

Kind code of ref document: A1