WO2017008442A1 - 发光复合物、发光材料、显示用基板及制备方法、显示装置 - Google Patents

发光复合物、发光材料、显示用基板及制备方法、显示装置 Download PDF

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WO2017008442A1
WO2017008442A1 PCT/CN2015/098245 CN2015098245W WO2017008442A1 WO 2017008442 A1 WO2017008442 A1 WO 2017008442A1 CN 2015098245 W CN2015098245 W CN 2015098245W WO 2017008442 A1 WO2017008442 A1 WO 2017008442A1
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group
luminescent
substrate
organic ligand
color
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PCT/CN2015/098245
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English (en)
French (fr)
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周婷婷
张斌
齐永莲
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京东方科技集团股份有限公司
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Priority to EP15892055.3A priority Critical patent/EP3255117A4/en
Priority to US15/311,718 priority patent/US10287498B2/en
Publication of WO2017008442A1 publication Critical patent/WO2017008442A1/zh

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    • 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
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • 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
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    • G02F1/133514—Colour filters
    • G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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 
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
    • G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
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    • 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
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    • G—PHYSICS
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    • 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
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    • H—ELECTRICITY
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    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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Definitions

  • the present invention relates to the field of display technologies, and in particular, to a light-emitting composite, a light-emitting material, a display substrate, a preparation method, and a display device.
  • the liquid crystal display panel is mainly composed of a color filter substrate and an array substrate of the pair of boxes, and a liquid crystal layer between the two.
  • the color film substrate is provided with red, green and blue resistance arranged in an array to realize color display.
  • the red, green, and blue dye molecules in the red, green, and blue dye molecules in the backlight emitted by the backlight module display red, green, and blue light, because the light passes through the red and green colors in the color resistance. After the blue dye molecules, brightness loss occurs (usually losing 70% of the backlight brightness), resulting in lower backlight utilization. It is necessary to further increase the backlight power consumption to reduce the effect of color resistance on backlight brightness loss.
  • One of the ways in which the prior art solves the backlight brightness loss is to replace the dye molecules in the red, green and blue resistance by using photoluminescent particles combined with common organic ligands, such as Quantum Dots (QDs). That is, a quantum dot color film is formed.
  • QDs Quantum Dots
  • the luminescent particles such as quantum dots are illuminated by the backlight
  • the electrons in the valence band are excited by the photon energy to the conduction band.
  • the electrons on the conduction band are again transitioned back to the valence band, the energy is released in the form of photons, thereby exciting
  • Corresponding red, green and blue light-emitting principles reduce the loss of color resistance to backlight brightness; and the color purity of quantum dots is better, and the color gamut is also higher.
  • the size of the luminescent particles such as quantum dots is very small, the dimensions of the three dimensions are usually below 100 nanometers (nm), and therefore, the luminescent particles are prone to agglomeration in the color resisting host material (such as resin).
  • the quantum dot color film has a problem of uneven illumination; and, since the photoluminescence property of the luminescent particles is dependent on its minute size, when the luminescent particles agglomerate in the color resisting host material, the photoluminescence thereof The performance will be greatly reduced.
  • the luminescent particles are illuminated by the backlight, the electrons on the valence band transition to the conduction band. However, the electrons on the conduction band do not jump back to the valence band, but fall into the trap level, and the energy is non-radiative. The form is quenched, resulting in a decrease in luminous efficiency.
  • embodiments of the present invention provide a light-emitting composite, a light-emitting material, a substrate for display, a preparation method, and a display device, which can improve luminescent particles such as quantum dots in a color resist material.
  • the degree of dispersion solves the problems of uneven illumination of the display substrate composed of luminescent particles and low luminous efficiency, thereby further reducing the loss of backlight brightness.
  • an embodiment of the present invention provides a light emitting composite, the light emitting composite comprising:
  • the A group is a binding group that binds to the luminescent particles
  • the E group represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a thiol group, an amine group, a formyl group, -SO 2 NH 2 , -NHNH 2 , a saturated carbon chain having 1 to 30 carbon atoms, or a carbon number of 1 ⁇ 10 unsaturated carbon chain;
  • the D group represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a thiol group, an amine group, a formyl group, -SO 2 NH 2 , -NHNH 2 , a saturated carbon chain having 1 to 30 carbon atoms, or a carbon number of 1 ⁇ 10 unsaturated carbon chain;
  • n is an integer, and 0 ⁇ n ⁇ 30
  • s is an integer, and 0 ⁇ s ⁇ 30
  • p is an integer, and 1 ⁇ p ⁇ (m+n+s) ⁇ 30
  • the carbon-carbon double bond of the structural formula of the organic ligand to the X 1 group, the X 2 group, and the X 3 group may be cross-linked with a photosensitive resin under exposure conditions.
  • the luminescent particles are quantum dots.
  • the quantum dot comprises at least one compound of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgTe, GaN, GaAs, InP, InAs;
  • the structure of the quantum dot is at least one of a core-shell type, a uniform mixture type, and a gradient mixing type.
  • the structural formula of the organic ligand comprises:
  • the embodiment of the present invention further provides a luminescent material, the luminescent material comprising: a photosensitive resin; the luminescent material further comprising: the illuminating according to any one of the above-mentioned ones dispersed in the photosensitive resin a complex; wherein a carbon-carbon double bond in the structural formula of the organic ligand in the light-emitting complex and the X 1 group, the X 2 group, and the X 3 group may be bonded to a photosensitive resin A crosslinking reaction occurs under exposure conditions.
  • the photosensitive resin comprises a negative photoresist material.
  • the mass ratio of the light-emitting composite incorporated into the photosensitive resin is 50% or less based on the mass of the photosensitive resin.
  • the mass ratio is from 3 to 20%.
  • the embodiment of the present invention further provides a substrate for display, the substrate for display includes a substrate; the substrate for display further includes: a plurality of arrays arranged on the substrate a color resisting unit of a color; wherein the color resisting unit of the at least one color comprises an exposure-cured luminescent material, the luminescent material being the luminescent material according to any one of the above; In the color resisting unit of the luminescent material, the luminescent particles in the luminescent material are excited by light to generate red light, or green light, or blue light.
  • the embodiment of the invention further provides a method for preparing the above-mentioned display substrate, the method comprising:
  • the luminescent material is coated on the base substrate; the luminescent material is sequentially heated, exposed, developed, and heated a second time to form a color resisting unit of at least one color.
  • an embodiment of the present invention further provides a display device including the above-described display substrate.
  • the display device further includes: a backlight module; the backlight module provides illumination for the display substrate.
  • the illumination is blue light.
  • the display substrate is a color filter substrate; the display device further includes: an organic electroluminescence display panel corresponding to the color filter substrate; wherein the organic electroluminescence display The panel provides white light or blue light to the color filter substrate.
  • the above-mentioned luminescent composite provided by the embodiment of the present invention is connected to the X 1 group, the X 2 group and the X 3 group in the structural formula of the organic ligand due to the combination of the luminescent particles and the organic ligand.
  • the carbon-carbon double bond can be cross-linked with the photosensitive resin as the color-blocking host material under exposure conditions, so that the luminescent particles are uniformly incorporated into the polymer system of the photosensitive resin, and the luminescent particles can achieve physical dispersion such as stirring in the photosensitive resin.
  • Unmatched molecular-level uniform dispersion effect and prevent luminescent particles from re-agglomerating during subsequent processing steps or use during the second heating, thereby improving the dispersion of luminescent particles such as quantum dots in the color resist host material.
  • the problem that the display substrate composed of the luminescent particles has uneven luminescence due to agglomeration of the luminescent particles and low luminous efficiency is further improved, and the loss of brightness of the backlight by the color film is further reduced.
  • FIG. 1 is a schematic structural view of a light emitting composite according to an embodiment of the present invention.
  • 3 is a specific structural formula 5-8 of an organic ligand in a light-emitting composite according to an embodiment of the present invention
  • FIG. 8 is a schematic diagram of a ligand exchange process according to Embodiment 4 of the present invention.
  • FIG. 10 is a schematic structural diagram of a luminescent material according to an embodiment of the present invention.
  • Figure 11 is a reaction principle of a negative photoresist during exposure
  • FIG. 12 is a comparison diagram of illuminating test results of a luminescent material and a red color resist provided by the prior art according to an embodiment of the present invention
  • FIG. 13 is a schematic cross-sectional view of a color filter substrate along a direction perpendicular to a board surface according to an embodiment of the present invention.
  • 01-luminescent complex 10-luminescent particle; 10a-luminescent core; 10b-semiconductor shell; 11-organic ligand; 11a-organic ligand backbone moiety; 11b-functional group with carbon-carbon double bond; 02-display substrate; 20-substrate substrate; 21-color resistive unit; 22-black matrix.
  • the dimensions of the structures involved in the embodiments of the present invention are generally on the order of millimeters (mm), micrometers ( ⁇ m), submicrometers (100 nm to 1.0 m), and nanometers (nm), for the sake of clarity,
  • the dimensions of the structures in the drawings of the embodiments of the present invention are enlarged, and do not represent actual dimensions and proportions.
  • the embodiment of the invention provides a luminescent composite 01, the luminescent composite 01 comprising:
  • the luminescent particles 10; the organic ligand 11 located on the surface of the luminescent particles; the structural formula of the organic ligand 11 is:
  • the A group is a binding group bonded to the luminescent particle 10;
  • the X 1 group, the X 2 group and the X 3 group each independently represent a hydrogen atom, an aryl group having 6 to 30 carbon atoms, and a halogen.
  • An atom, -CH 3 , -(CH 2 ) a -CH 3 , -COOH, -COOCH 3 , or -CH CH 2 , wherein a is an integer greater than or equal to 1, wherein preferably, the number of carbon atoms is
  • the aryl group of 6 to 30 is a phenyl group, and a is an integer of 1 or more and 30 or less;
  • the E group represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a thiol group, an amine group, a formyl group, -SO 2 NH 2 , -NHNH 2 , a saturated carbon chain having 1 to 30 carbon atoms, or a carbon number of 1 ⁇ 10 unsaturated carbon chain;
  • the D group represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a thiol group, an amine group, a formyl group, -SO 2 NH 2 , -NHNH 2 , a saturated carbon chain having 1 to 30 carbon atoms, or a carbon number of 1 ⁇ 10 unsaturated carbon chain;
  • n is an integer, and 0 ⁇ n ⁇ 30
  • s is an integer, and 0 ⁇ s ⁇ 30
  • p is an integer, and 1 ⁇ p ⁇ (m+n+s) ⁇ 30
  • the carbon-carbon double bond in the structural formula of the organic ligand 11 which is bonded to the X 1 group, the X 2 group and the X 3 group can be cross-linked with the photosensitive resin under exposure conditions.
  • the first and the above-mentioned luminescent particles 10 refer to minute particles which are irradiated with light of a specific wavelength, and may be, for example, quantum dots.
  • the organic ligand 11 in order to allow the organic ligand 11 to be stably bonded to the luminescent particles 10 and further dispersed in a photosensitive resin (a red, green, and blue resistive material in a color filter substrate), the organic ligand 11 has a structural formula A binding group A which can be combined with the luminescent particles 10.
  • the type of the A group depends on the specific material composition of the luminescent particles 10, and the combined force of the two may be a chemical bond force or an intermolecular force (such as a hydrogen bond force).
  • quantum dots are less than 100 nm in three dimensions, the appearance is like a very small dot, and the movement of internal electrons in all directions is limited, so the quantum confinement effect is particularly remarkable. . Moreover, quantum dots, as a novel semiconductor nanomaterial, have many unique nano-properties, especially in the field of photoluminescence.
  • the structure of the quantum dot is at least one of a core-shell type, a uniform hybrid type, and a gradient mixing type.
  • a core-shell type ie, the luminescent particle 10 described above
  • a uniform hybrid type ie, CdS, etc.
  • a gradient mixing type ie, the gradient mixing type.
  • the quantum dot of the core-shell structure is composed of the luminescent core 10a and the semiconductor shell 10b covering the luminescent core 10a, and the quantum dot can be coated by such a shell coating.
  • the luminous efficiency is further improved, and the structural stability thereof is increased. Therefore, in the embodiment of the present invention, it is further preferred that the structure of the quantum dot is a core-shell type.
  • the semiconductor shell 10b covering the illuminating core 10a may be, for example, a wide bandgap semiconductor material such as CdS or ZnS; correspondingly, the illuminating core 10a may be a semiconductor material such as CdSe; and the specific material types of the illuminating core 10a and the semiconductor shell 10b may be used.
  • a wide bandgap semiconductor material such as CdS or ZnS
  • the illuminating core 10a may be a semiconductor material such as CdSe
  • the specific material types of the illuminating core 10a and the semiconductor shell 10b may be used.
  • the quantum dot structure of the technique is not specifically limited.
  • a carbon-carbon double bond at the end of the chain structure is bonded to the X 1 group, the X 2 group, and the X 3 group.
  • the functional group 11b having a carbon-carbon double bond is located at the end with respect to the organic ligand main chain portion 11a, reaction is apt to occur; and the X 1 group, the X 2 group, and the X 3 group are present. They are all relatively simple carbon chain structures with lower reactivity than the linked unsaturated carbon-carbon double bonds, so that under the exposure conditions, the X 1 group and the X 2 group are attached at the end of the chain structure.
  • the carbon-carbon double bond of the X 3 group can be cross-linked with the monomer or prepolymer in the photosensitive resin, so that the luminescent particles 10 (such as the above-mentioned quantum dots having a core-shell structure) are uniformly incorporated into the photosensitive resin.
  • the luminescent particles 10 such as the above-mentioned quantum dots having a core-shell structure
  • the above-mentioned luminescent composite 01 provided by the embodiment of the present invention in combination with the organic ligand 11 in the luminescent particle 10, in the structural formula of the organic ligand 11, with the X 1 group, the X 2 group and the X 3
  • the carbon-carbon double bond to which the group is bonded can be cross-linked with the photosensitive resin as the color resisting host material under exposure conditions, so that the luminescent particles 10 are uniformly incorporated into the polymer system of the photosensitive resin, and the luminescent particles 10 are in the photosensitive resin.
  • the effect of uniform dispersion of the molecular level unmatched by physical dispersion such as stirring can be achieved, and the luminescent particles are prevented from re-agglomerating during the subsequent processing steps or during the second heating, thereby increasing the luminescent particles 10 such as quantum dots.
  • the degree of dispersion in the color resist main body improves the problem that the display substrate composed of the luminescent particles 10 has uneven luminescence due to agglomeration of luminescent particles, and low luminous efficiency, and further reduces the loss of brightness of the backlight by the color film.
  • the electron cloud is relatively asymmetrical, and can play the role of electron donating or electron withdrawing in the process of synthesizing the organic ligand 11, which is beneficial to the design and synthesis of the organic ligand 11.
  • each group coefficient m, n, s, and p respectively satisfy the following range and relationship:
  • the above-mentioned range of values and the relationship of the chain structure of the organic ligand 11 are suitable, and it is difficult to synthesize or synthesize the reaction after synthesis because the number of chain structures is too long.
  • the two groups of carbon-carbon double bonds are designed in the same molecule (ie, the above-mentioned organic ligand 11).
  • the organic ligand main chain portion 11a preferably has a carboxylic acid or an amide which is easy to synthesize. That is, as shown in FIG. 2, the structural formula of the above-described organic ligand 11 may specifically include at least one of the four structural formulae shown in the drawing.
  • the two groups of carbon-carbon double bonds are designed in the same molecule (ie, the above-mentioned organic ligand 11).
  • the organic ligand main chain portion 11a preferably has a carboxyl group or an amide beside the carbon-carbon double bond to which the X 1 group, the X 2 group and the X 3 group are bonded, and the reactivity of the obtained product carbon-carbon double bond Higher, it is more conducive to cross-linking reaction with the photosensitive resin under exposure conditions. That is, as shown in FIG. 3, the structural formula of the above-described organic ligand 11 may specifically include at least one of the four structural formulae shown in the drawing.
  • the organic ligand 11 having the above specific structural formulas 1 to 8 may be synthesized first, and then the quantum dots may be synthesized; or the organic compound carrying the luminescent particles 10 may be modified by a post-functionalization method to form the above specific The organic ligand 11 of Structural Formulas 1-8.
  • the luminescent particle 10 having a thioglycolic acid (C 2 H 4 O 2 S) as a ligand may be synthesized, and then reacted with a carboxylic acid having a hydroxyl group or an amino group by a molecule containing a hydroxyl group or an amino group, thereby synthesizing
  • the above-mentioned synthetic reaction formula of the organic ligand 11 of the above specific structural formulas 1 to 8 can be as shown in Fig. 4 or Fig. 5 .
  • the group coefficient s is an integer and 0 ⁇ s ⁇ 30; and the relationship between the above coefficients is also satisfied, namely:
  • DCC (dicyclohexylcarbodiimide, molecular formula: C 13 H 22 N 2 ) acts as a water-reducing agent to positively shift the equilibrium of the synthesis reaction and increase the reaction yield
  • DMAP 4-Dimethylaminopyridine, having the formula: C 7 H 10 N 2
  • DMAP 4-Dimethylaminopyridine, having the formula: C 7 H 10 N 2
  • the luminescent complex 01 is composed of an organic ligand 1 and luminescent particles 1.
  • the organic ligand 1 is 10-undecenoic acid (CAS No.: 112-38-9), and its structural formula is as follows:
  • the luminescent particle 1 is a CdSe@CdS core-shell type quantum dot.
  • the reaction product obtained in the above step S12 may be dispersed in toluene, and the fluorescence emission peak of the reaction product is around 540 nm by fluorescence spectrum test ( That is, light-emitting green light), the half-peak width is about 37 nm.
  • the luminescent complex 01 is composed of an organic ligand 2 and luminescent particles 2.
  • the structural formula of the organic ligand 2 is as follows:
  • the synthesis reaction raw material of the organic ligand 2 is hexamethylenediamine (CAS No.: 124-09-4, molecular formula: NH 2 (CH 2 ) 6 NH 2 ) and methacrylic acid (CAS No. 79-41-4, The molecular formula is: C 4 H 6 O 2 ), and the reaction formula is shown in Fig. 6.
  • the specific procedure is as follows.
  • SOCl 2 is thionyl chloride as a chlorinating agent
  • DMF is dimethylformamide (molecular formula: C 3 H 7 NO), which can be used as a high boiling point polarity (hydrophilic)
  • An aprotic solvent can promote the reaction mechanism of SN2
  • Et 3 N is triethylamine (molecular formula: C 6 H 15 N) as a catalyst for the above reaction
  • THF is tetrahydrofuran (molecular formula: C 4 H 8 O) In the above reaction as a moderately polar aprotic solvent.
  • the above-mentioned organic ligand 2 was subjected to mass spectrometry and nuclear magnetic resonance measurement, and its structural formula was determined as described above.
  • the data of mass spectrometry detection is: EI-MS m/z 184.2(M)+; the data of nuclear magnetic resonance detection are: 1 H-NMR (400MHz, CDCl3) ⁇ 8.26 (t, 1H), 5.99 (s, 1H) ), 5.58 (s, 1H), 3.02 (m, 2H), 2.13 (m, 2H), 2.72 (m, 2H), 2.01 (s, 3H), 1.22-1.68 (m, 8H).
  • the luminescent particles 2 are CdSe quantum dots.
  • the reaction product obtained in the above step S22 may be dispersed in toluene, and the fluorescence emission peak of the reaction product is shown to be around 525 nm by fluorescence spectrum test ( That is, light causes green light), The half peak is about 32 nm wide.
  • the luminescent complex 01 is composed of an organic ligand 3 and luminescent particles 3. Among them, the structural formula of the organic ligand 3 is as follows:
  • the synthesis reaction raw material of the organic ligand 3 is 3-buten-1-ol (CAS No.: 627-27-0, molecular formula: C 4 H 8 O) and 1,10-sebacic acid (CAS No.: 693) -23-2, the molecular formula is: C 12 H 22 O 4 ), and the reaction formula is shown in Fig. 7, and the specific procedure is as follows.
  • DPTS is pyridinium p-toluenesulfonate (molecular formula: C 7 H 8 O 3 S ⁇ C 5 H 5 N);
  • DCC is dicyclohexylcarbodiimide (molecular formula: C 13 H 22 N 2 ) acts as a water-reducing agent to positively shift the equilibrium of the synthesis reaction and increase the reaction yield.
  • the above-mentioned organic ligand 3 was subjected to mass spectrometry and nuclear magnetic resonance measurement, and its structural formula was determined as described above.
  • the data of mass spectrometry detection is: EI-MS m/z 284.23(M)+;
  • the data of nuclear magnetic resonance detection are: 1 H-NMR (400MHz, CDCl3) ⁇ 12.13(S,1H), 5.73(m,1H ), 4.97-5.15 (m, 2H), 4.32 (t, 2H), 2.23 - 2.36 (m, 6H), 1.56-1.68 (m, 4H), 1.22-1.29 (m, 12H).
  • the reaction product obtained in the above step S32 may be dispersed in toluene, and the fluorescence emission peak indicates that the fluorescence emission peak is near 540 nm (ie, light-induced Green light), the half-peak width is about 37nm.
  • the preparation methods adopted in the above embodiments 1 to 3 are all firstly synthesizing the organic ligand 11 having the above certain structural formula, and synthesizing the quantum dots to form the above-mentioned luminescent composite 01; an embodiment 4 is provided below to describe in detail
  • the functionalized method modifies the organic compound carrying the luminescent particles 10 to form the preparation process of the above luminescent composite 01.
  • the luminescent complex 01 is composed of an organic ligand 4 and luminescent particles 4.
  • the structural formula of the organic ligand 4 is as follows:
  • the luminescent particles 4 are made of the same material as the luminescent particles 1, that is, CdSe@CdS core-shell type quantum dots.
  • the reaction product obtained in the above step S42 may be dispersed in toluene, and the fluorescence emission peak indicates that the fluorescence emission peak is near 540 nm (ie, light-induced Green light), the half-peak width is about 37nm.
  • the ligand exchange reaction was carried out by a rotary evaporator at room temperature.
  • the reaction principle is shown in Fig. 8.
  • the rotation speed was 8000 r/min, thereby obtaining a CdSe@CdS quantum dot with thioglycolic acid as a ligand.
  • the above reaction product was dispersed in THF.
  • the use of rotary evaporation ensures that no oxygen is present in the reaction system, thereby avoiding oxidation of the surface of the quantum dots. Moreover, the sample in the rotary evaporation process is protected from light to prevent photodegradation of the luminescent core CdSe.
  • the quantum dot having the thioglycolic acid as the ligand in the above step S52 or the solution is prepared into a solution having a solubility of 0.5 wt% under the action of ultrasonic vibration.
  • the embodiment of the present invention further provides a luminescent material, the luminescent material comprising: a photosensitive resin; and the luminescent composite 01 dispersed in the photosensitive resin; wherein, under exposure conditions
  • the photosensitive resin may be cross-linked with a carbon-carbon double bond to the X 1 group, the X 2 group, and the X 3 group in the structural formula of the organic ligand 11 in the light-emitting complex 01.
  • the above-mentioned photosensitive resin refers to a photosensitive resin which can undergo crosslinking reaction with an unsaturated bond under exposure conditions (usually ultraviolet exposure, abbreviated as UV).
  • the photosensitive resin may be composed of a negative photoresist material, and the principle of exposure and development thereof is as shown in FIG. 11 : a developer which is insoluble in alkali after UV exposure, and a double in its molecule during exposure. The bond is opened and cross-linking occurs between the chain and the chain to form an insoluble network structure, thereby providing corrosion resistance.
  • the specific composition of the negative photoresist material can be: monomer or prepolymer (Monomer, such as acrylic acid), solvent (Solvent, improve coating uniformity, ensure uniformity of line width after exposure), photoinitiator (Photo- Initiator, photochemical reaction under UV irradiation), dye (Pigment, photochemical reaction), sensitizer (speed enhancer), and surfactant (Surfactant), radiation, water ripple after exposure, development
  • monomer or prepolymer such as acrylic acid
  • solvent solvent
  • solvent solvent
  • Photoinitiator Photo- Initiator, photochemical reaction under UV irradiation
  • dye Pigment, photochemical reaction
  • sensitizer speed enhancer
  • surfactant surfactant
  • the mass ratio of the light-emitting composite 01 incorporated into the photosensitive resin is 50% or less.
  • the ratio of the incorporation of the light-emitting composite 01 is too large, the effect of improving the crosslinking reaction with the negative photoresist is not large, and the viscosity of the light-emitting material may be lowered to affect the coating of the color resistance;
  • the ratio of incorporation is too small, the color resistance of the formed color resist is insufficient. Therefore, in the embodiment of the present invention, it is further preferred that the aforementioned mass ratio is 3 to 20%.
  • part (a) is a red color resist light-emitting effect test chart provided by the prior art; wherein the quantum dot incorporated into the photosensitive resin is combined with a common organic ligand (That is, the above-mentioned crosslinking reaction does not occur with the photosensitive resin; (b) the above-mentioned luminescent material provided by the embodiment of the present invention, that is, the luminescent effect of the luminescent particles 10 incorporated in the photosensitive resin in combination with the novel organic ligand 11 described above.
  • the illuminating intensity of the luminescent material provided by the embodiment of the invention is significantly higher than the red color resistance provided by the prior art, which proves that
  • the organic ligand 11 can be cross-linked with a photosensitive resin as a color resisting host material under exposure conditions, and the luminescent particles 10 are uniformly incorporated into the photosensitive resin, and the color film composed of the luminescent particles 10 is improved due to the presence of luminescent particles agglomerated. The problem of uneven illumination and low luminous efficiency is reflected in the higher luminous intensity.
  • an embodiment of the present invention further provides a substrate 02 for display, the substrate 02 for display includes a substrate substrate 20; and a plurality of colors arranged in an array on the substrate substrate 20 a color resisting unit 21; wherein the color resisting unit 21 of at least one color is composed of the above-mentioned light-emitting material which is cured by exposure; in the color resisting unit 21 of one color of the light-cured material which is cured by exposure, in the light-emitting material The luminescent particles 10 are excited by light to produce red light, or green light, or blue light.
  • the display substrate 02 described above may specifically be a color filter substrate.
  • the color film substrate may of course include a black matrix 22, a protective layer, and the like, and may be used in the prior art, which is not limited in the embodiment of the present invention.
  • the display substrate 02 may be an array substrate provided with a color resisting unit (ie, a COA substrate integrated with a color film and an array function, Color filter on Array); in this case, the color resist unit 21 and the base substrate Further, a structure including a TFT (Thin Film Transistor) array layer and an insulating layer is also included.
  • the COA substrate may of course also include a structure of a pixel electrode and a common electrode, and the like may be used in the prior art.
  • the display substrate 02 generally includes a red color resist, a green color resist, and a blue color resist
  • the color resist having only one color may be composed of the above-mentioned light-emitting material, and the color resist of the remaining colors may be formed by using the color resist material of the prior art.
  • the color resistance of each color in the display substrate 02 described above may also be composed of the above-described luminescent materials, that is, the color resistance of each color indicated by "R", "G", and "B" in the figure.
  • the embodiment of the present invention further provides a method for preparing the above-mentioned display substrate 02, and the method includes:
  • the base substrate 20 is coated with a luminescent material
  • a spin coating process may be employed, which is spin-coated.
  • the rate may be 150-500 rpm, spin coated for 10 s to form a film layer having a thickness of 3 ⁇ m-20 ⁇ m.
  • the first heating is a so-called "pre-baking" which is generally called by those skilled in the art, and the function is to remove the photosensitive resin.
  • the drying temperature can be 60 ⁇ 100 ° C, drying 60 ⁇ 120s; exposure process can choose i-line wavelength (365nm), the exposure parameter is 60 ⁇ 200mj / cm 2 ; development process can choose KOH (hydrogen hydroxide a potassium solution or a TMAH (tetramethylammonium hydroxide) solution; the second heating is a so-called "post-baking" which is generally referred to by those skilled in the art, and the function of further removing the solvent remaining in the photosensitive resin to further cause a crosslinking reaction.
  • the film is made denser and harder, and the adhesion to the substrate 20 is improved.
  • the drying temperature can be 100 to 200 °C.
  • an embodiment of the present invention further provides a display device including the above-mentioned display substrate 02.
  • the display device when the display device is specifically a liquid crystal display device, the display device further includes a backlight module; the backlight module provides illumination for the display panel.
  • the luminescent composite 01 in the luminescent material has photoluminescence characteristics (for example, luminescent particles 10 composed of quantum dots) ). Therefore, the illumination emitted by the backlight module provides photon energy for the illumination of the illumination composite 01.
  • the illumination emitted by the backlight module is white light
  • the light directly emitted by the light source such as an LED (Light Emitting Diode) is not white light (usually blue light)
  • the backlight provided by the backlight module preferably adopts blue light, so that the luminescent particles 10 in the luminescent composite 01 can emit red or green light under excitation of blue light; and the blue color resist portion can be incorporated with The color resistance of ordinary blue dye molecules.
  • the display device may further include an array substrate that is matched with the color filter substrate, and a liquid crystal layer between the two, specifically Technology is not described here.
  • the display device described above may specifically be a product or component having any display function such as a liquid crystal display, a liquid crystal television, a digital photo frame, a mobile phone, or a tablet computer.
  • the display substrate 02 is specifically a color filter substrate
  • the display device further includes: an organic device that is combined with the color filter substrate.
  • An organic light-emitting display panel OLED panel; wherein the OLED panel provides white light or blue light for the color film substrate described above.
  • the light-emitting layer (Emitting Layer, EL for short) in each pixel unit in the OLED panel emits white light or blue light.

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Abstract

本发明实施例提供了一种发光复合物、发光材料、显示用基板及制备方法、显示装置，涉及显示技术领域，可提高量子点等发光颗粒在色阻主体材料中的分散度，解决包含发光颗粒的显示用基板发光不均匀、发光效率低等问题，进一步降低对背光亮度的损耗。该发光复合物包含发光颗粒；附着在发光颗粒表面的有机配体；有机配体结构式中的A基团为与发光颗粒相结合的结合基团；有机配体的结构式中与所述X1基团、所述X2基团和所述X3基团相连接的碳碳双键可与感光树脂在曝光条件下发生交联反应。本发明还提供了用于发光复合物，包括该发光复合物的发光材料以及包括该发光材料的显示用基板、显示装置的制备方法。

Description

发光复合物、发光材料、显示用基板及制备方法、显示装置 技术领域
本发明涉及显示技术领域，尤其涉及一种发光复合物、发光材料、显示用基板及制备方法、显示装置。
背景技术
液晶显示面板主要由对盒的彩膜基板与阵列基板，以及位于二者之间的液晶层构成。其中，彩膜基板上设置有呈阵列排列的红、绿、蓝色阻，以实现彩色显示。
在背光模组发出的背光透过红、绿、蓝色阻中的红、绿、蓝染料分子进而显示红光、绿光、蓝光的过程中，由于光在穿过色阻中的红、绿、蓝染料分子后会发生亮度损耗(通常会损失背光亮度的70％)，从而导致背光的利用率较低，需要以进一步加大背光能耗的方式来削弱色阻对背光亮度损耗的影响。
现有技术解决背光亮度损耗的方式之一是通过用结合有普通有机配体的光致发光颗粒，如量子点(Quantum Dot，简称QDs)来替代红、绿、蓝色阻中的染料分子，即形成量子点彩膜。利用量子点等发光颗粒在背光照射下，其价带上的电子受光子能量激发跃迁至导带，当导带上的电子再次跃迁回价带时，能量以光子的形式释放出，从而激发出相应的红光、绿光、蓝光的发光原理来降低色阻对背光亮度的损耗；并且量子点发光的色纯度较好，色域也较高。
然而，由于量子点等发光颗粒的尺寸非常微小，其三个维度的尺寸通常都在100纳米(nm)以下，因此，发光颗粒在色阻的主体材料(如树脂等)内容易发生团聚现象，使得量子点彩膜存在发光不均匀的问题；并且，由于发光颗粒的光致发光特性是取决于其微小的尺寸的，当发光颗粒在色阻的主体材料内发生团聚后，其光致发光的性能会大为减小，发光颗粒在背光照射下，价带上的电子跃迁至导带，然而导带上的电子没有跃迁回价带，而是落入了陷阱能级中，能量以非辐射的形式而淬灭了，导致发光效率降低。
发明内容
鉴于此，为解决现有技术的问题，本发明的实施例提供一种发光复合物、发光材料、显示用基板及制备方法、显示装置，可提高量子点等发光颗粒在色阻主体材料中的分散度，解决由发光颗粒构成的显示用基板发光不均匀、发光效率低等问题，从而进一步降低对背光亮度的损耗。
为达到上述目的，本发明的实施例采用如下技术方案：
在第一方面中，本发明实施例提供了一种发光复合物，所述发光复合物包括：
发光颗粒；
位于所述发光颗粒表面的有机配体；
所述有机配体的结构式为：
Figure PCTCN2015098245-appb-000001
其中，A基团为与所述发光颗粒相结合的结合基团；
X1基团、X2基团以及X3基团各自独立地表示氢原子、碳原子数为6～30的芳基、卤素原子、-CH3、-(CH2)a-CH3、-COOH、-COOCH3、或-CH＝CH2，其中a为大于等于1的整数，其中，优选地，所述碳原子数为6～30的芳基为苯基，并且a为大于等于1且小于等于30的整数；
E基团表示氢原子、卤素原子、羟基、羧基、巯基、胺基、甲酰基、-SO2NH2、-NHNH2、碳原子数为1～30的饱和碳链、或碳原子数为1～10的不饱和碳链；
D基团表示氢原子、卤素原子、羟基、羧基、巯基、胺基、甲酰基、-SO2NH2、-NHNH2、碳原子数为1～30的饱和碳链、或碳原子数为1～10的不饱和碳链；
G基团表示-CH2-、-C＝C-、-C≡C-、-COO-、-CONH-、-CO-、-O-、-OCONH、-NH-、-S-、-COS-、-CH＝N-、-NHCONH-、-NHCSNH-、-NHNH-，或从苯环、环己烷、环戊烷、噻吩、吡啶、吡咯、咪唑、苯胺、呋喃或咔唑中的两个成环碳原子上分别脱去一个碳原子而形成 的二价环状基团；
其中，m为整数，且0≤m≤30；n为整数，且0≤n≤30；s为整数，且0≤s≤30；(m+n+s)≠0；p为整数，且1≤p·(m+n+s)≤30，
所述有机配体的结构式中与所述X1基团、所述X2基团和所述X3基团相连接的碳碳双键可与感光树脂在曝光条件下发生交联反应。
优选地，所述发光颗粒为量子点。
进一步优选地，所述量子点包含CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、HgS、HgTe、GaN、GaAs、InP、InAs中的至少一种化合物；所述A基团表示NC-、HOOC-、HRN-、O＝P(R)2-、POOOH-、RS-、RSS-中的任一种，所述R基团表示氢原子、碳原子数为1～10的饱和碳链、碳原子数为1～10的不饱和碳链中的任一种。
进一步优选地，若所述量子点包含两种或两种以上所述化合物，则所述量子点的结构为核-壳型、均一混合型、梯度混合型中的至少一种。
在上述基础上优选地，所述有机配体的结构式包括：
Figure PCTCN2015098245-appb-000002
Figure PCTCN2015098245-appb-000003
以及
Figure PCTCN2015098245-appb-000004
中的至少一种。
在第二方面中，本发明实施例还提供了一种发光材料，所述发光材料包括：感光树脂；所述发光材料还包括：分散在所述感光树脂中的上述任一项所述的发光复合物；其中，所述发光复合物中的有机配体结构式中与所述X1基团、所述X2基团和所述X3基团相连接的碳碳双键可与感光树脂在曝光条件下发生交联反应。
优选地，所述感光树脂包含负性光刻胶材料。
优选地，基于所述感光树脂的质量，所述发光复合物掺入所述感光树脂的质量比例小于等于50％。
进一步优选地，所述质量比例为3～20％。
在第三方面中，本发明实施例还提供了一种显示用基板，所述显示用基板包括衬底基板；所述显示用基板还包括：位于所述衬底基板上呈阵列排列的多种颜色的色阻单元；其中，至少一种颜色的色阻单元包含经曝光固化的发光材料，所述发光材料为上述任一项所述的发光材料；在一种颜色的包含经曝光固化的所述发光材料的所述色阻单元中，所述发光材料中的发光颗粒被光照激发后产生红光、或绿光、或蓝光。
本发明实施例还提供了上述的显示用基板的制备方法，所述方法包括：
在衬底基板上涂覆发光材料；对所述发光材料依次进行第一次加热、曝光、显影、第二次加热，形成至少一种颜色的色阻单元。
在第四方面中，本发明实施例还提供了一种显示装置，所述显示装置包括上述的所述的显示用基板。
作为一种可选的方式，所述显示装置还包括：背光模组；所述背光模组为所述显示用基板提供光照。
优选地，所述光照为蓝光。
作为另一种可选的方式，所述显示用基板为彩膜基板；所述显示装置还包括：与所述彩膜基板对应的有机电致发光显示面板；其中，所述有机电致发光显示面板为所述彩膜基板提供白光或蓝光。
基于此，通过本发明实施例提供的上述发光复合物，由于发光颗粒与有机配体相结合，在有机配体的结构式中与X1基团、X2基团和X3基团相连接的碳碳双键可与作为色阻主体材料的感光树脂在曝光条件下发生交联反应，使发光颗粒均匀的掺入感光树脂的聚合物体系内，发光颗粒在感光树脂中可达到搅拌等物理分散所无法比拟的分子级的均匀分散的效果，并且防止发光颗粒在第二次加热等后续处理步骤或者使用过程中发生再次团聚，从而提高了量子点等发光颗粒在色阻主体材料中的分散度，改善了由发光颗粒构成的显示用基板由于存在发光颗粒团聚而产生的发光不均匀、发光效率低等问题，进一步降低了彩膜对背光亮度的损耗。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例提供的一种发光复合物的结构示意图；
图2为本发明实施例提供的一种发光复合物中有机配体的具体结构式1～4；
图3为本发明实施例提供的一种发光复合物中有机配体的具体结构式5～8；
图4为本发明具体实施例提供的一种发光复合物中有机配体的合成反应式一；
图5为本发明具体实施例提供的一种发光复合物中有机配体的合成反应式二；
图6为本发明实施例2提供的一种合成有机配体②的合成反应式；
图7为本发明实施例3提供的一种合成有机配体③的合成反应式；
图8为本发明实施例4提供的一种配体交换过程示意图；
图9为本发明实施例4提供的一种合成有机配体④的合成反应式；
图10为本发明实施例提供的一种发光材料的结构示意图；
图11为负性光刻胶在曝光过程中的反应原理；
图12为本发明实施例提供的一种发光材料与现有技术提供的红色色阻的发光测试结果对比图；
图13为本发明实施例提供的一种彩膜基板沿垂直于板面方向的剖面结构示意图。
附图标记：
01-发光复合物；10-发光颗粒；10a-发光核；10b-半导体壳；11-有机配体；11a-有机配体主链部分；11b-带有碳碳双键的功能性基团；02-显示用基板；20-衬底基板；21-色阻单元；22-黑矩阵。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
需要指出的是，除非另有定义，本发明实施例中所使用的所有术语(包括技术和科学术语)具有与本发明所属领域的普通技术人员共同理解的相同含义。还应当理解，诸如在通常字典里定义的那些术语应当被解释为具有与它们在相关技术的上下文中的含义相一致的含义，而不应用理想化或极度形式化的意义来解释，除非这里明确地这样定义。
并且，由于本发明实施例所涉及的各结构尺寸通常在毫米(mm)、微米(μm)、亚微米(100nm～1.0m)、纳米(nm)数量级，为了清楚起见， 本发明实施例附图中各结构的尺寸均被放大，不代表实际尺寸与比例。
此外，本领域技术人员还应当理解，本发明所有附图中示意出的各结构并不构成对本发明实施例提供的以下发光复合物01和/或发光材料XX具体结构组成的限定，只为清楚描述本发明体现了与发明点相关的结构，对于其他的与发明点无关的结构是现有结构，在附图中并未体现或只体现部分。
本发明实施例提供了一种发光复合物01，该发光复合物01包括：
发光颗粒10；位于发光颗粒表面的有机配体11；有机配体11的结构式为：
Figure PCTCN2015098245-appb-000005
其中，A基团为与发光颗粒10相结合的结合基团；X1基团、X2基团以及X3基团各自独立地表示氢原子、碳原子数为6～30的芳基、卤素原子、-CH3、-(CH2)a-CH3、-COOH、-COOCH3、或-CH＝CH2，其中a为大于等于1的整数，其中，优选地，所述碳原子数为6～30的芳基为苯基，并且a为大于等于1且小于等于30的整数；
E基团表示氢原子、卤素原子、羟基、羧基、巯基、胺基、甲酰基、-SO2NH2、-NHNH2、碳原子数为1～30的饱和碳链、或碳原子数为1～10的不饱和碳链；
D基团表示氢原子、卤素原子、羟基、羧基、巯基、胺基、甲酰基、-SO2NH2、-NHNH2、碳原子数为1～30的饱和碳链、或碳原子数为1～10的不饱和碳链；
G基团表示-CH2-、-C＝C-、-C≡C-、-COO-、-CONH-、-CO-、-O-、-OCONH、-NH-、-S-、-COS-、-CH＝N-、-NHCONH-、-NHCSNH-、-NHNH-，或从苯环、环己烷、环戊烷、噻吩、吡啶、吡咯、咪唑、苯胺、呋喃或咔唑中的两个成环碳原子上分别脱去一个碳原子而形成的二价环状基团；
其中，m为整数，且0≤m≤30；n为整数，且0≤n≤30；s为整数，且0≤s≤30；(m+n+s)≠0；p为整数，且1≤p·(m+n+s)≤30，
有机配体11结构式中与X1基团、X2基团以及X3基团相连接的碳碳双键可与感光树脂在曝光条件下发生交联反应。
需要说明的是，第一、上述的发光颗粒10是指受到光照可发出特定波长光的微小颗粒，例如可以为量子点。
这里，为了使有机配体11可与发光颗粒10稳定地结合在一起，进而分散在感光树脂(作为彩膜基板中的红、绿、蓝色阻材料)中，有机配体11的结构式中具有可与发光颗粒10相结合的结合基团A。
其中，A基团的种类取决于发光颗粒10的具体材料组成，二者相结合的作用力可以为化学键作用力或分子间力(如氢键作用力)等。
考虑到量子点在三个维度的尺寸都在100nm以下，外观恰似一极小的点状物，其内部电子在各方向上的运动都受到局限，所以量子限域效应(quantum confinement effect)特别显著。并且，量子点作为一种新颖的半导体纳米材料，具有许多独特的纳米性质，尤其在光致发光领域具有良好的发光特性。
因此，如图1所示，本发明实施例优选地，上述的发光颗粒10为量子点。若量子点包含CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、HgS、HgTe、GaN、GaAs、InP、InAs中的至少一种化合物，则A基团表示NC-、HOOC-、HRN-、O＝P(R)2-、POOOH-、RS-、RSS-中的任一种，R基团表示氢原子、碳原子数为1～10的饱和碳链、碳原子数为1～10的不饱和碳链中的任一种。
进一步的，若量子点(即上述的发光颗粒10)包含两种或两种以上化合物(即CdS等)，则量子点的结构为核-壳型、均一混合型、梯度混合型中的至少一种。
其中，参考图1所示，考虑到核-壳型结构的量子点由于是由发光核10a以及包覆发光核10a的半导体壳10b构成的，通过这样一种壳层包覆可使量子点的发光效率得到进一步提高，并且增加其结构稳定性，因此，本发明实施例进一步优选地，量子点的结构为核-壳型。
示例的，包覆发光核10a的半导体壳10b例如可以采用宽带隙的半导体材料如CdS、ZnS；相应地，发光核10a可以采用CdSe等半导体材料；发光核10a与半导体壳10b的具体材料种类可沿用现有技 术的量子点结构，具体不作限定。
第二、在上述有机配体11的结构式中，位于链结构末端的碳碳双键与X1基团、X2基团以及X3基团相连接。其中，这三个基团是相互独立的，每一个基团都可以表示氢原子、芳基、卤素原子、-CH3、-(CH2)a-CH3，-COOH、-COOCH3，-CH＝CH2中的任一种，其中a为大于等于1的整数，其中，优选地，所述碳原子数为6～30的芳基为苯基，并且a为大于等于1且小于等于30的整数。
参考图1所示，由于带有碳碳双键的功能性基团11b相对于有机配体主链部分11a位于末端，易于发生反应；且X1基团、X2基团以及X3基团均为较为简单的碳链结构，其反应活性低于相连的不饱和的碳碳双键，这样一来，在曝光条件下，位于链结构末端的连接有X1基团、X2基团以及X3基团的碳碳双键可与感光树脂中的单体或者预聚物发生交联反应，使发光颗粒10(如上述的具有核-壳型结构的量子点)均匀的掺入感光树脂的聚合物体系内。
基于此，通过本发明实施例提供的上述发光复合物01，由于发光颗粒10与有机配体11相结合，在有机配体11的结构式中，与X1基团、X2基团以及X3基团相连接的碳碳双键可与作为色阻主体材料的感光树脂在曝光条件下发生交联反应，使发光颗粒10均匀的掺入感光树脂的聚合物体系内，发光颗粒10在感光树脂中可达到搅拌等物理分散所无法比拟的分子级的均匀分散的效果，并且防止发光颗粒在第二次加热等后续处理步骤或者使用过程中发生再次团聚，从而提高了量子点等发光颗粒10在色阻主体材料中的分散度，改善了由发光颗粒10构成的显示用基板由于存在发光颗粒团聚而产生的发光不均匀、发光效率低等问题，进一步降低了彩膜对背光亮度的损耗。
上述的E、D以及G基团作为有机配体主链部分11a中的连接基团，采用上述的如氢原子、卤素原子、羟基以及-C＝C-等基团时，由于这些基团的电子云较为不对称，在合成有机配体11的过程中可以起到给电子或吸电子的作用，有利于有机配体11的设计合成。
其中，在有机配体11的结构式中，各基团系数m、n、s以及p分别满足以下取值范围和关系式：
m为整数，且0≤m≤30；n为整数，且0≤n≤30；s为整数，且0≤s≤30； (m+n+s)≠0；p为整数，且1≤p·(m+n+s)≤30。
这里，满足的以上取值范围以及关系式的有机配体11的链结构数量适宜，不会由于链结构数量过长而难以合成或合成后的反应活性较差。
进一步的，为了方便将A基团、与X1基团、X2基团以及X3基团相连接的碳碳双键这两种基团设计在同一分子中(即上述的有机配体11)，有机配体主链部分11a优选地具有易于合成的羧酸或酰胺。即，如图2所示，上述的有机配体11的结构式具体可包括图中所示的4种结构式中的至少一种。
其中，当上述有机配体11的结构式中，E基团＝D基团＝氢原子、G基团＝-COO-；系数n＝p＝1即可得到以上的具体结构式1。
当上述有机配体11的结构式中，E基团＝D基团＝氢原子、G基团＝-OOC-；系数n＝p＝1即可得到以上的具体结构式2。
当上述有机配体11的结构式中，E基团＝D基团＝氢原子、G基团＝-CONH-；系数n＝p＝1即可得到以上的具体结构式3。
当上述有机配体11的结构式中，E基团＝D基团＝氢原子、G基团＝-HNOC-；系数n＝p＝1即可得到以上的具体结构式4。
进一步的，为了方便将A基团、与X1基团、X2基团以及X3基团相连接的碳碳双键这两种基团设计在同一分子中(即上述的有机配体11)，有机配体主链部分11a优选地在连接有X1基团、X2基团以及X3基团的碳碳双键旁具有羧基或酰胺，以及得到的产物碳碳双键的反应活性更高，更有利于与感光树脂在曝光条件下发生交联反应。即，如图3所示，上述的有机配体11的结构式具体可包括图中所示的4种结构式中的至少一种。
其中，当上述有机配体11的结构式中，E基团＝氢原子、G基团＝-OOC-；系数n＝1、s＝0即可得到以上的具体结构式5。
当上述有机配体11的结构式中，E基团＝氢原子、G基团＝-COO-；系数n＝1、s＝0即可得到以上的具体结构式6。
当上述有机配体11的结构式中，E基团＝氢原子、G基团＝-NHCO-；系数n＝1、s＝0即可得到以上的具体结构式7。
当上述有机配体11的结构式中，E基团＝氢原子、G基团＝-CONH-；系数n＝1、s＝0即可得到以上的具体结构式8。
这里，可以先合成具有上述具体结构式1～8的有机配体11，再合成量子点；或者，也可以采用后功能化的方法对携带有发光颗粒10的有机化合物进行修饰，以形成具有上述具体结构式1～8的有机配体11。
示例的，可以先合成以巯基乙酸(分子式为：C2H4O2S)为配体的发光颗粒10，再通过含有羟基或氨基的分子与发光颗粒10上的羧酸反应，从而合成具有上述具体结构式1～8的有机配体11，上述的合成反应式可如图4或图5所示。
需要说明的是，第一、在上述图4和图5中，基团系数s为整数，且0≤s≤30；并且同样满足上述的各系数之间的关系式，即：
(m+n+s)≠0，且1≤p·(m+n+s)≤30。
第二、在上述合成反应式中，DCC(二环己基碳二亚胺，分子式为：C13H22N2)作为失水剂，使合成反应平衡正向移动，提高反应产率；DMAP(4-二甲氨基吡啶，分子式为：C7H10N2)是一种超强亲核的酰化作用催化剂，可提高酰化反应产率。
第三、在上述有机配体11的具体结构式1中，进一步当A基团＝HS-、系数m＝1，即可得到图4中所示的反应产物结构式；在上述有机配体11的具体结构式3中，进一步当A基团＝HS-、系数m＝1，即可得到图5中所示的反应产物结构式。
下面给出四个具体实施例，用于详细描述上述的发光复合物01的制备方法：
实施例1
1、发光复合物01由有机配体①和发光颗粒①构成。其中，有机配体①为10-十一烯酸(CAS号为：112-38-9)，其结构式如下所示：
Figure PCTCN2015098245-appb-000006
这里，在上述有机配体11的结构式：
Figure PCTCN2015098245-appb-000007
中：
当X1基团＝X2基团＝X3基团＝氢原子、A基团＝HOOC-、G基团＝-CH2-；系数m＝s＝0、p＝1、n＝8即可得到上述的有机配体①的结构式；此外，有机配体①的具体合成过程可沿用现有技术，在此不作赘述。
发光颗粒①为CdSe@CdS核-壳型结构量子点。
2、发光颗粒①前驱体溶液的制备
硫前驱体溶液的制备：
称取0.033g硫粉，量取10mL液体石蜡，将上述两种原料加入到第一个三口烧瓶中，持续搅拌加热至120℃至完全溶解，形成浅黄色澄清溶液，即为硫前驱体溶液。
硒前驱体溶液的制备：
称取0.078g硒粉，量取50mL液体石蜡，将上述两种原料加入到第二个三口烧瓶中，持续搅拌加热至220℃至完全溶解，形成酒红色澄清溶液，即为硒前驱体溶液。
镉前驱体溶液的制备：
称取1.28g氧化镉，量取40mL液体石蜡和9.8mL有机配体①(即10-十一烯酸)，将上述三种原料加入到第三个三口烧瓶中，持续搅拌加热至180℃，以使氧化镉完全溶解，形成棕红色澄清溶液，即为镉前驱体溶液。
3、有机配体①+发光颗粒①的制备：
S11、取出5mL镉前驱体溶液，注入到硒前驱体溶液中，此时溶液温度会降低到210℃左右，待溶液温度回升至220℃后，反应1分钟后，注入硫前驱体溶液，反应40分钟后停止加热，将反应产物静置至室温。
S12、在上述的反应产物中加入一定量的无水甲醇，促进产物的沉淀，溶液中产生明显的浑浊，通过离心分离，去掉溶液中的上清液， 再加入环己烷或甲苯以分散产物，之后对产物进行离心。重复以上操作三次以上，将产物中绝大部分的有机反应物洗涤去除，即获得上述的发光复合物01。
这里，为了检测制备出的发光颗粒①的受光照激发出的光的波长，可以将上述步骤S12获得的反应产物分散到甲苯中，经荧光光谱测试表明，反应产物的荧光发射峰在540nm附近(即光致发绿光)，半高峰宽约37nm。
实施例2
1、发光复合物01由有机配体②和发光颗粒②构成。其中，有机配体②的结构式如下所示：
Figure PCTCN2015098245-appb-000008
这里，在上述有机配体11的具体结构式4中，进一步当X1基团＝-CH3、X2基团＝X3基团＝氢原子、A基团＝-NH2；系数s＝0、m＝3即可得到上述的有机配体②的结构式。
有机配体②的合成反应原料为己二胺(CAS号为：124-09-4，分子式为：NH2(CH2)6NH2)与甲基丙烯酸(CAS号为79-41-4，分子式为：C4H6O2)，反应式如图6所示，具体过程如下所述。
将8.6g甲基丙烯酸、100mL甲苯以及13.1g的SOCl2加入三口烧瓶中，加入适量的DMF，加热回流2h，减压回收甲苯、冷却。在残液中加入100mL的THF，持续搅拌溶解。加入11.1g的Et3N和12.8g己二胺，加热回流1.5h，冷却。过滤除去三乙胺盐酸盐，将滤液减压蒸馏除去滤液中残留的THF，得到有机配体②的粗品。将粗品用异丙醇/环己烷重结晶，得到13.8g有机配体②，产率为75％。
其中，在上述反应式中，SOCl2为亚硫酰氯，作为氯化剂；DMF为二甲基甲酰胺(分子式为：C3H7NO)，可作为高沸点的极性(亲水性)非质子性溶剂，能促进SN2反应机理的进行；Et3N为三乙胺(分子式为：C6H15N)，作为上述反应的催化剂；THF为四氢呋喃(分子式为：C4H8O)，在上述反应中作为一种中等极性的非质子溶 剂。
对上述的有机配体②进行质谱和核磁共振的测试，可确定其结构式如上所述。其中，质谱检测的数据为：EI-MS m/z 184.2(M)+；核磁共振检测的数据为：1H-NMR(400MHz，CDCl3)δ8.26(t，1H)，5.99(s，1H)，5.58(s，1H)，3.02(m，2H)，2.13(m，2H)，2.72(m，2H)，2.01(s，3H)，1.22-1.68(m，8H)。
发光颗粒②为CdSe量子点。
2、发光颗粒②前驱体溶液的制备
镉前驱体溶液的制备：
称取1.28g氧化镉，量取17mL液体石蜡和8mL油酸2，将上述三种原料加入到三角烧瓶中，持续搅拌缓慢加热至150℃，以使氧化镉完全溶解，形成暗红色透明溶液，即为镉前驱体溶液。
硒前驱体溶液的制备：
称取0.08g硒粉，量取50mL液体石蜡，将上述两种原料加入到三口烧瓶中，持续搅拌缓慢加热至220℃，形成亮黄色透明溶液，即为硒前驱体溶液。
3、有机配体②+发光颗粒②的制备：
S21、取出5mL镉前驱体溶液，迅速注入到硒前驱体溶液中，加入2mL有机配体②，并快速搅拌，溶液迅速变至橙色。维持溶液反应温度在220℃，使量子点逐步生长。继续反应5min后，将溶液加至50mL冷甲苯中，阻止量子点生长(避免量子点发生团聚现象)。
S22、在上述的反应产物中加入一定量的无水甲醇，促进产物的沉淀，溶液中产生明显的浑浊，通过离心分离，去掉溶液中的上清液，再加入环己烷或甲苯以分散产物，之后对产物进行离心。重复以上操作三次以上，将产物中绝大部分的有机反应物洗涤去除，即获得上述的发光复合物01。
这里，为了检测制备出的发光颗粒②的受光照激发出的光的波长，可以将上述步骤S22获得的反应产物分散到甲苯中，经荧光光谱测试表明，反应产物的荧光发射峰在525nm附近(即光致发绿光)， 半高峰宽约32nm。
实施例3
1、发光复合物01由有机配体③和发光颗粒③构成。其中，有机配体③的结构式如下所示：
Figure PCTCN2015098245-appb-000009
这里，在上述有机配体11的具体结构式1中，进一步当X1基团＝X2基团＝X3基团＝氢原子、A基团＝COOH-；系数s＝2、m＝10即可得到上述的有机配体③的结构式。
有机配体③的合成反应原料为3-丁烯-1-醇(CAS号为：627-27-0，分子式为：C4H8O)和1，10-癸二酸(CAS号：693-23-2，分子式为：C12H22O4)，反应式如图7所示，具体过程如下所述。
将10g的3-丁烯-1-醇10g溶于50mL无水二氯甲烷中，加入0.46g的DPTS和0.95g的DCC。再将23.0g的1，10-癸二酸溶于100mL无水二氯甲烷中，在氮气氛围中滴入到上述的含有3-丁烯-1-醇的溶液中，室温条件下搅拌反应48h，过滤去除沉淀，将滤液以旋转蒸发的方式除去溶剂，得到有机配体③的粗品。将粗品用石油醚和丙酮重结晶，得到19.3g有机配体③，产率为68％。
其中，在上述反应式中，DPTS为对甲苯磺酸吡啶盐(分子式为：C7H8O3S·C5H5N)；DCC为二环己基碳二亚胺(分子式为：C13H22N2)作为失水剂，使合成反应平衡正向移动，提高反应产率。
对上述的有机配体③进行质谱和核磁共振的测试，可确定其结构式如上所述。其中，质谱检测的数据为：EI-MS m/z 284.23(M)+；核磁共振检测的数据为：1H-NMR(400MHz，CDCl3)δ12.13(S，1H)，5.73(m，1H)，4.97-5.15(m，2H)，4.32(t，2H)，2.23-2.36(m，6H)，1.56-1.68(m，4H)，1.22-1.29(m，12H)。
2、发光颗粒③前驱体溶液的制备
硫前驱体溶液的制备：
称取0.033g硫粉，量取10mL液体石蜡，将上述两种原料加入到第一个三口烧瓶中，持续搅拌缓慢加热至120℃至完全溶解，形成浅黄色澄清溶液，即为硫前驱体溶液。
硒前驱体溶液的制备：
称取0.078g硒粉，量取50mL液体石蜡，将上述两种原料加入到第二个三口烧瓶中，持续搅拌缓慢加热至220℃至完全溶解，形成酒红色澄清溶液，即为硒前驱体溶液。
镉前驱体溶液的制备：
称取1.28g氧化镉，量取40mL液体石蜡以及9.8ml有机配体③，将上述三种原料加入到第三个三口烧瓶中，持续搅拌加热到180℃，以使氧化镉完全溶解，形成棕红色澄清溶液，即为镉前驱体溶液。
3、有机配体③+发光颗粒③的制备：
S31、取出5mL镉前驱体溶液，注入到硒前驱体溶液中，此时温度会降低到210℃左右，待温度回升至220℃后，反应1分钟后，注入硫前驱体溶液，反应40分钟后停止加热，将反应产物静置至室温。
S32、在上述的反应产物中加入一定量的无水甲醇，促进产物的沉淀，溶液中产生明显的浑浊，通过离心分离，去掉溶液中的上清液，再加入环己烷或甲苯分散产物，之后对产物进行离心。重复以上操作三次以上，将产物中绝大部分的有机反应物洗涤去除，即获得上述的发光复合物01。
这里，为了检测制备出的发光颗粒③的受光照激发出的光的波长，可以将上述步骤S32获得的反应产物分散到甲苯中，经荧光光谱测试表明，荧光发射峰在540nm附近(即光致发绿光)，半高峰宽大约是37nm。
上述实施例1～3采用的制备方式均为先合成具有上述一定结构式的有机配体11，再合成量子点，以形成上述的发光复合物01；下面提供一个实施例4，以详细描述采用后功能化的方法对携带有发光颗粒10的有机化合物进行修饰，以形成上述发光复合物01的制备过程。
实施例4
1、发光复合物01由有机配体④和发光颗粒④构成。其中，有机配体④的结构式如下所示：
Figure PCTCN2015098245-appb-000010
这里，在上述有机配体11的具体结构式3中，进一步当X1基团＝CH3-、X2基团＝X3基团＝氢原子、A基团＝HS-；系数s＝m＝1即可得到上述的有机配体④的结构式。
发光颗粒④采用与发光颗粒①相同的材料，即CdSe@CdS核-壳型结构量子点。
2、以油酸为配体的CdSe@CdS核-壳结构量子点的制备
2.1、CdSe@CdS前驱体溶液的制备
硫前驱体溶液的制备：
称取0.033g硫粉，量取10mL液体石蜡，将上述两种原料加入到第一个三口烧瓶中，持续搅拌缓慢加热至120℃至完全溶解，形成浅黄色澄清溶液，即为硫前驱体溶液。
硒前驱体溶液的制备：
称取0.078g硒粉，量取50mL液体石蜡，将上述两种原料加入到第二个三口烧瓶中，持续搅拌缓慢加热至220℃至完全溶解，形成酒红色澄清溶液，即为硒前驱体溶液。
镉前驱体溶液的制备：
称取1.28g氧化镉，量取40mL液体石蜡以及10mL油酸，将上述三种原料加入到第三个三口烧瓶中，持续搅拌加热到180℃，以使氧化镉完全溶解，形成棕红色澄清溶液，即为镉前驱体溶液。
2.2、油酸+CdSe@CdS的制备：
S41、取出5ml镉前驱体溶液，注入到硒前驱体溶液中，此时温度会降低到210℃左右，待温度回升至220℃后，反应1分钟后，注入硫前驱体溶液，反应40分钟后停止加热，将反应产物静置至室温。
S42、在上述的反应产物中加入一定量的无水甲醇，促进产物的沉淀，溶液中产生明显的浑浊，通过离心分离，去掉溶液中的上清液，再加入环己烷或甲苯分散产物。重复以上操作三次以上，将产物中绝大部分的有机反应物洗涤去除，即获得上述的发光复合物01。
这里，为了检测制备出的发光颗粒④的受光照激发出的光的波长，可以将上述步骤S42获得的反应产物分散到甲苯中，经荧光光谱测试表明，荧光发射峰在540nm附近(即光致发绿光)，半高峰宽大约是37nm。
3、巯基乙酸与油酸的配体交换反应：
S51、称取上述步骤S42获得的离心提纯的产物20g，分散在THF(即四氢呋喃)中，在超声波振荡的作用下滴入15mL浓度为3mol/L的巯基乙酸水溶液，上述的滴加过程在5min内完成。
S52、在室温条件下，用旋转蒸发仪进行配体交换反应，反应原理如图8所示，旋转速度为8000r/min，从而获得巯基乙酸为配体的CdSe@CdS量子点。为了防止量子点在进行之后的反应处理前产生团聚现象，将上述的反应产物分散在THF中。
这里，采用旋转蒸发可以保证反应体系中没有氧气的存在，从而避免了量子点表面发生氧化。并且，对旋转蒸发过程的中的样品采取避光处理，以防止发光核CdSe发生光降解。
4、巯基乙酸+CdSe@CdS的后功能化修饰反应：
S61、在超声波振荡的作用下，将上述步骤S52或的巯基乙酸为配体的量子点配制成溶度为0.5wt％的溶液。
S62、称取上述溶液5g、100mg的DCC以及10mg的DMAP，将上述三种原料加入到三角烧瓶中，搅拌均匀；将称量好的0.46g(即6.5mmol)2-甲基烯丙基胺(CAS号为2878-14-0)滴加到前述的5g溶液中，搅拌反应2h，反应结束后过滤除去不溶物；在上述溶液中加入甲醇，在8000r/min的离心条件下进行离心分离处理，从而得到具有有机配体④的量子点。其中，配体巯基乙酸与2-甲基烯丙基胺反应如图9所示。
在上述基础上，如图10所示，本发明实施例还提供了一种发光 材料，该发光材料包括：感光树脂；以及分散在感光树脂中的上述发光复合物01；其中，在曝光条件下，感光树脂可与发光复合物01中的有机配体11结构式中与X1基团、X2基团以及X3基团相连接的碳碳双键发生交联反应。
需要说明的是，第一、上述感光树脂是指在曝光条件(通常为紫外曝光，缩写为UV)下可与不饱和键发生交联反应的感光树脂。
具体的，上述感光树脂可以由负性光刻胶材料构成，其曝光显影的原理如图11所示：在UV曝光后不溶于碱性的显影液，在曝光的过程中，其分子中的双键被打开，链与链之间发生交联，形成一种不溶于碱性的网状结构，从而起到抗蚀作用。
负性光刻胶材料的具体组成可以由：单体或预聚物(Monomer，如丙烯酸)、溶剂(Solvent，提高涂布均一性，保证曝光后的线幅均一)、光引发剂(Photo-initiator，在UV照射下引发光化学反应)、染料(Pigment，促进光化学反应)、增感剂(Speed enhancer，提高曝光感度)以及界面活性剂(Surfactant，防止曝光、显影后出现放射线状水波纹，改善涂布特性)等，具体组分可沿用现有技术，本发明实施例对此不作限定。
第二、发光复合物01掺入感光树脂的质量比例小于等于50％。这里，考虑到发光复合物01掺入的比例过大时，对提高与负性光刻胶的交联反应效果不大，可能还会降低发光材料的粘滞性，影响色阻的涂布；而掺入的比例过小时，会导致形成的色阻发光强度不足。因此，本发明实施例进一步优选地，前述的质量比例为3～20％。
这里，掺入到感光树脂中的发光复合物01的具体制备过程可参见前述的实施例1～4，在此不再赘述。
示例的，如图12所示，其中(a)部分为现有技术提供的一种红色色阻的发光效果测试图；其中，掺入到感光树脂中为结合有普通有机配体的量子点(即不与感光树脂发生上述交联反应)；(b)部分为本发明实施例提供的上述发光材料，即掺入到感光树脂中为结合有上述新型的有机配体11的发光颗粒10发光效果测试图；可以看出，在同样为光致发红光的情况下，采用本发明实施例提供的发光材料的发光强度明显高于现有技术提供的红色色阻，证明了由于上述的新型 有机配体11可与作为色阻主体材料的感光树脂在曝光条件下发生交联反应，使发光颗粒10均匀的掺入感光树脂内，改善了由发光颗粒10构成的彩膜由于存在发光颗粒团聚而产生的发光不均匀、发光效率低等问题，即体现出了更高的发光强度。
在上述基础上，如图13所示，本发明实施例还提供了一种显示用基板02，该显示用基板02包括衬底基板20；位于衬底基板20上呈阵列排列的多种颜色的色阻单元21；其中，至少一种颜色的色阻单元21由经曝光固化的上述发光材料构成；在一种颜色的由经曝光固化的发光材料构成的色阻单元21中，发光材料中的发光颗粒10被光照激发后产生红光、或绿光、或蓝光。
需要说明的是，上述的显示用基板02具体可以为彩膜基板。该彩膜基板当然还可包括黑矩阵22、保护层等结构，具体可沿用现有技术，本发明实施例对此不作限定。
或者，上述的显示用基板02也可以为设置有色阻单元的阵列基板(即集成有彩膜与阵列功能的COA基板，Color filter on Array)；在此情况下，色阻单元21与衬底基板20之间还包括有TFT(Thin Film Transistor，薄膜晶体管)阵列层、绝缘层等结构。该COA基板当然还可以包括像素电极和公共电极等结构，具体可沿用现有技术，本发明实施例对此不作限定。
由于显示用基板02通常包括红色色阻、绿色色阻以及蓝色色阻，可以是仅有一种颜色的色阻由上述的发光材料构成，其余颜色的色阻可沿用现有技术的色阻材料构成。当然，上述的显示用基板02中各个颜色的色阻也可均由上述的发光材料构成，即图中以“R”、“G”以及“B”示意出的各个颜色的色阻。
进一步的，本发明实施例还提供了一种上述显示用基板02的制备方法，该方法包括：
S01、衬底基板20上涂覆发光材料；
S02、对发光材料依次进行第一次加热、曝光、显影、第二次加热，形成至少一种颜色的色阻单元21。
这里，示例的，在上述步骤S01中，可以采用旋涂工艺，旋涂的 速率可以为150-500rpm，旋涂10s以形成3μm-20μm厚度的膜层。
由于发光材料是由感光树脂以及分散在其内的发光复合物01构成的，因此在上述步骤S02中，第一次加热即本领域技术人员通常所谓的“前烘”，其作用是去除感光树脂中的溶剂，烘干温度可为60～100℃，烘干60～120s；曝光工艺可选用i-line波长(365nm)，曝光参数为60～200mj/cm2；显影工艺可选用KOH(氢氧化钾)溶液或TMAH(四甲基氢氧化铵)溶液；第二次加热即本领域技术人员通常所谓的“后烘”，其作用是进一步去除感光树脂中残留的溶剂，进一步发生交联反应，使胶膜更为致密坚硬，提高与衬底基板20的附着力烘干温度可为100～200℃。
进一步的，本发明实施例还提供了一种显示装置，该显示装置包括上述的显示用基板02。
作为一种可选的方式，当上述显示装置具体为液晶显示装置时，该显示装置还包括背光模组；背光模组为显示面板提供光照。
由于上述的显示用基板02中的至少一个色阻单元是由前述实施例提供的发光材料构成，而发光材料中的发光复合物01具有光致发光特性(例如，由量子点构成的发光颗粒10)。因此，背光模组发出的光照即为上述发光复合物01的发光提供光子能量。
这里，考虑到当背光模组发出的光照为白光时，由于LED(Light Emitting Diode，发光二极管)等光源直接发出的光并非为白光(通常为蓝光)，还需要使得非白光经过荧光粉才可转化为白光，从而降低了光源的发光效率。
因此，进一步的，上述背光模组提供的光照优选为采用蓝光，使得发光复合物01中的发光颗粒10可在蓝光的激发下发出红光或绿光；而蓝色色阻部分可沿用掺入有普通蓝色染料分子的色阻。
其中，当上述的显示用基板02具体为彩膜基板时，该显示装置具体还可包括与上述的彩膜基板对合的阵列基板，以及位于二者之间的液晶层，具体可沿用现有技术，在此不作赘述。
上述的显示装置具体可以为液晶显示器、液晶电视、数码相框、手机、平板电脑等具有任何显示功能的产品或者部件。
作为另一种可选的方式，当上述显示装置具体为有机电致发光显示装置时，上述的显示用基板02具体为彩膜基板，该显示装置还包括：与彩膜基板对合的有机电致发光显示面板(Organic Light-Emitting Display，OLED面板)；其中，该OLED面板为上述的彩膜基板提供白光或蓝光。
即，OLED面板中各个像素单元内的发光层(Emitting Layer，简称EL)发白光或蓝光。
需要说明的是，本发明所有附图是上述的发光复合物、发光材料、彩膜基板的简略的示意图，只为清楚描述本方案体现了与发明点相关的结构，对于其他的与发明点无关的结构是现有结构，在附图中并未体现或只体现部分。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。

Claims (15)

  1. 一种发光复合物，其特征在于，所述发光复合物包括：
    发光颗粒；
    位于所述发光颗粒表面的有机配体；
    所述有机配体的结构式为：
    Figure PCTCN2015098245-appb-100001
    其中，A基团为与所述发光颗粒相结合的结合基团；
    X1基团、X2基团以及X3基团各自独立地表示氢原子、碳原子数为6～30的芳基、卤素原子、-CH3、-(CH2)a-CH3、-COOH、-COOCH3、或-CH＝CH2，其中a为大于等于1的整数；
    E基团表示氢原子、卤素原子、羟基、羧基、巯基、胺基、甲酰基、-SO2NH2、-NHNH2、碳原子数为1～30的饱和碳链、或碳原子数为1～10的不饱和碳链；
    D基团表示氢原子、卤素原子、羟基、羧基、巯基、胺基、甲酰基、-SO2NH2、-NHNH2、碳原子数为1～30的饱和碳链、或碳原子数为1～10的不饱和碳链；
    G基团表示-CH2-、-C＝C-、-C≡C-、-COO-、-CONH-、-CO-、-O-、-OCONH、-NH-、-S-、-COS-、-CH＝N-、-NHCONH-、-NHCSNH-、-NHNH-，或从苯环、环己烷、环戊烷、噻吩、吡啶、吡咯、咪唑、苯胺、呋喃或咔唑中的两个成环碳原子上分别脱去一个碳原子而形成的二价环状基团；
    其中，m为整数，且0≤m≤30；n为整数，且0≤n≤30；s为整数，且0≤s≤30；(m+n+s)≠0；p为整数，且1≤p·(m+n+s)≤30，
    所述有机配体的结构式中与所述X1基团、所述X2基团和所述X3基团相连接的碳碳双键可与感光树脂在曝光条件下发生交联反应。
  2. 根据权利要求1所述的发光复合物，其特征在于，所述发光颗粒为量子点。
  3. 根据权利要求2所述的发光复合物，其特征在于，
    所述量子点包含CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、HgS、HgTe、GaN、GaAs、InP、InAs中的至少一种化合物；
    所述A基团表示NC-、HOOC-、HRN-、O＝P(R)2-、POOOH-、RS-、RSS-中的任一种，所述R基团表示氢原子、碳原子数为1～10的饱和碳链、碳原子数为1～10的不饱和碳链中的任一种。
  4. 根据权利要求3所述的发光复合物，其特征在于，若所述量子点包含两种或两种以上所述化合物，则所述量子点的结构为核-壳型、均一混合型、梯度混合型中的至少一种。
  5. 根据权利要求1所述的发光复合物，其特征在于，所述有机配体的结构式包括：
    Figure PCTCN2015098245-appb-100002
    Figure PCTCN2015098245-appb-100003
    以及
    Figure PCTCN2015098245-appb-100004
    和的至少一种。
  6. 一种发光材料，所述发光材料包括：感光树脂；其特征在于，所述发光材料还包括：分散在所述感光树脂中的如权利要求1至5任 一项所述的发光复合物；
    其中，所述发光复合物中的有机配体结构式中与所述X1基团、所述X2基团和所述X3基团相连接的碳碳双键可与感光树脂在曝光条件下发生交联反应。
  7. 根据权利要求6所述的发光材料，其特征在于，所述感光树脂包含负性光刻胶材料。
  8. 根据权利要求6或7所述的发光材料，其特征在于，基于所述感光树脂的质量，所述发光复合物掺入所述感光树脂的质量比例小于等于50％。
  9. 根据权利要求8所述的发光材料，其特征在于，所述质量比例为3～20％。
  10. 一种显示用基板，所述显示用基板包括衬底基板；其特征在于，所述显示用基板还包括：
    位于所述衬底基板上呈阵列排列的多种颜色的色阻单元；
    其中，至少一种颜色的色阻单元包含经曝光固化的发光材料，所述发光材料为上述权利要求6至9任一项所述的发光材料；
    在一利颜色的包含经曝光固化的所述发光材料的所述色阻单元中，所述发光材料中的发光颗粒被光照激发后产生红光、或绿光、或蓝光。
  11. 一种如权利要求10所述的显示用基板的制备方法，其特征在于，所述方法包括：
    在衬底基板上涂覆发光材料；
    对所述发光材料依次进行第一次加热、曝光、显影、第二次加热，形成至少一种颜色的色阻单元。
  12. 一种显示装置，其特征在于，所述显示装置包括如权利要求10所述的显示用基板。
  13. 根据权利要求12所示的显示装置，其特征在于，所述显示装置还包括：背光模组；
    所述背光模组为所述显示用基板提供光照。
  14. 根据权利要求13所示的显示装置，其特征在于，所述光照为蓝光。
  15. 根据权利要求12所示的显示装置，其特征在于，所述显示用基板为彩膜基板；
    所述显示装置还包括：与所述彩膜基板对应的有机电致发光显示面板；
    其中，所述有机电致发光显示面板为所述彩膜基板提供白光或蓝光。
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