CN109980127B - Substrate, preparation method thereof, light-emitting device and display screen - Google Patents
Substrate, preparation method thereof, light-emitting device and display screen Download PDFInfo
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Abstract
The invention discloses a substrate and a preparation method thereof, a light-emitting device and a display screen, wherein the method comprises the following steps: providing hexagonal boron nitride, and carrying out alcoholization treatment on the hexagonal boron nitride to obtain hydroxylated hexagonal boron nitride; providing an organic ligand, wherein the organic ligand is provided with amino and an active group, and the surface of hydroxylated hexagonal boron nitride is modified through the organic ligand; providing cellulose, and crosslinking the cellulose and the hexagonal boron nitride subjected to surface modification to prepare a hexagonal boron nitride/cellulose aerogel skeleton with a three-dimensional network structure; providing an organic polymer base material, and filling the organic polymer base material in a hexagonal boron nitride/cellulose aerogel skeleton to prepare the base. The invention solves the problem of poor heat conduction of the substrate in the existing light-emitting device.
Description
Technical Field
The invention relates to the technical field of quantum dot light-emitting diodes, in particular to a substrate, a preparation method of the substrate, a light-emitting device and a display screen.
Background
With the continuous development of display technology, people have higher and higher requirements on the display quality of display devices. Quantum dot Light-Emitting Diodes (QLEDs) and Organic Light-Emitting Diodes (OLEDs) are two new types of Light-Emitting devices with similar structures. The QLED adopts Quantum dot materials (QDs) as a light emitting layer, and has incomparable advantages compared with other light emitting materials, such as controllable small-size effect, ultrahigh internal Quantum efficiency, excellent color purity, and the like; the OLED adopts organic matters as a light emitting layer, and has the advantages of low driving voltage, high light emitting efficiency, short response time, high definition and contrast, nearly 180-degree visual angle, wide use temperature range, large-area full-color display and the like. Therefore, the two display devices have great application prospects in the future display technical field.
Because the service life of the display device is easily affected by the factors of water vapor, oxygen and the like in the surrounding environment, the device generally needs to be sealed in an environment without water and oxygen to prolong the service life of the device, however, although the device is packaged in a closed environment, the device can block the water and oxygen in the air from entering, the heat emitted by the device in the using process cannot be diffused out in time, the temperature of the whole display is increased, and the efficiency and the service life of the device are affected. The substrate with good heat conduction performance is beneficial to timely dissipation of heat generated by the device, so that the efficiency of the device is improved, and the service life of the device is prolonged.
Therefore, the prior art has yet to be improved.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, the present invention aims to provide a substrate, a method for manufacturing the substrate, and a light emitting device, and aims to solve the problem of poor heat conduction of the substrate in the prior light emitting device.
The technical scheme of the invention is as follows:
a method of preparing a substrate, comprising the steps of:
providing hexagonal boron nitride, and carrying out alcoholization treatment on the hexagonal boron nitride to obtain hydroxylated hexagonal boron nitride;
providing an organic ligand, wherein the organic ligand is provided with amino and an active group, and the surface of hydroxylated hexagonal boron nitride is modified through the organic ligand;
providing cellulose, and crosslinking the cellulose and the hexagonal boron nitride subjected to surface modification to prepare a hexagonal boron nitride/cellulose aerogel skeleton with a three-dimensional network structure;
providing an organic polymer base material, and filling the organic polymer base material in a hexagonal boron nitride/cellulose aerogel skeleton to prepare the base.
The preparation method of the substrate comprises the step of preparing the substrate, wherein the active group is one or more of hydroxyl, carboxyl, ester group, sulfydryl, aldehyde group and halogen.
The preparation method of the substrate comprises the step of preparing the hexagonal boron nitride, wherein the size of the hexagonal boron nitride is 5-8000 nm.
The preparation method of the substrate, wherein the step of crosslinking the cellulose and the hexagonal boron nitride after surface modification to prepare the hexagonal boron nitride/cellulose aerogel skeleton of the three-dimensional network structure, comprises the following steps:
mixing cellulose, strong base and urea in deionized water to obtain a mixed solution;
adding the surface-modified hexagonal boron nitride and a cross-linking agent into the mixed solution to perform a cross-linking reaction between the cellulose and the hexagonal boron nitride to obtain a cross-linked product;
and (3) freeze-drying the cross-linked product to obtain the hexagonal boron nitride/cellulose aerogel skeleton with a three-dimensional network structure.
The preparation method of the substrate comprises the following steps of (1) preparing a mixed solution, wherein the concentration of cellulose in the mixed solution is 3-97 mg/mL; and/or the concentration of strong base is 13-174 mg/mL; and/or the concentration of urea is 65-380 mg/mL.
The preparation method of the substrate comprises the following steps of adding the surface-modified hexagonal boron nitride and a cross-linking agent into the mixed solution, wherein the volume percentage of the surface-modified hexagonal boron nitride is 0.2-36 vol%; and/or the volume percentage of the cross-linking agent is 0.008-0.16 vol%.
The preparation method of the substrate comprises the following steps of (1) freeze drying at-62 to-44 ℃; and/or the freeze drying time is 12-96 h.
The preparation method of the substrate comprises the step of preparing a cross-linking agent by using epoxy chloropropane.
The preparation method of the substrate comprises the step of preparing the organic polymer substrate material, wherein the organic polymer substrate material is one or more of polyethylene terephthalate, polyethylene naphthalate, polyether ether ketone, polystyrene, polyether sulfone, polycarbonate, polyarylate, polyimide, polyvinyl chloride, polyethylene, polyvinylpyrrolidone and textile fibers.
A substrate, wherein the substrate is prepared by the method for preparing a substrate as described above, and the substrate comprises a hexagonal boron nitride/cellulose aerogel skeleton and an organic polymer substrate material filled in the hexagonal boron nitride/cellulose aerogel skeleton.
A light-emitting device comprising a substrate as described above.
The light emitting device is an OLED device or a QLED device.
A display screen comprising a substrate as described above.
Has the advantages that: the invention utilizes the characteristics of the hexagonal boron nitride material that the hexagonal boron nitride material has higher thermal conductivity, excellent electrical insulation, good corrosion resistance and lower thermal expansion coefficient, the hexagonal boron nitride after surface modification and cellulose are crosslinked to prepare the hexagonal boron nitride/cellulose aerogel skeleton with a three-dimensional net structure, then the organic polymer substrate material is filled in the skeleton and wraps the skeleton, because the skeleton is provided with a plurality of regular hexagonal boron nitrides after surface modification, the substrate also has excellent thermal conductivity and electrical insulation performance, and the skeleton is in the three-dimensional net structure, thus being capable of providing a multi-dimensional and multi-directional heat flow transmission mode, leading the heat to be effectively transmitted from points to lines and surfaces in time, and the cellulose with good thermal conductivity is arranged between each hexagonal boron nitride unit as a heat conduction bridge, and the heat is not separated by a non-heat-conducting insulating material, so that the heat can be more effectively dissipated, and meanwhile, the structure of the cellulose long-chain cross-linked network can effectively disperse and eliminate various stresses generated by the original substrate or due to the introduction of hexagonal boron nitride, so that the flexibility of the substrate is further improved on the basis of certain flexibility caused by the original organic polymer substrate material, and the bending performance is better.
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FIG. 1 is a schematic flow chart of a preferred embodiment of a method for preparing a substrate according to the present invention;
fig. 2 is a schematic structural view of the substrate of the present invention.
Detailed Description
The invention provides a substrate, a preparation method thereof, a light-emitting device and a display screen, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Because the structure of the hexagonal boron nitride (h-BN) is similar to that of graphite and has a hexagonal layered structure, the h-BN is a stable phase in a normal pressure environment, atoms in a layer are combined together by strong covalent bonds, and layers are combined by Van der Waals force, so that the bonding force is weak, and the layers can easily slide. In the conventional substrate using the hexagonal boron nitride material, boron nitride (and not necessarily hexagonal boron nitride having better heat transfer performance) is often directly mixed with the substrate material, because each heat-conducting filler is not associated, and the heat-conducting filler in the substrate is not in direct contact with a functional layer (mainly referred to as an electrode) of the device at all, so that heat generated by the device reaches the heat-conducting filler after passing through the non-heat-conducting substrate material, and the heat in the heat-conducting filler is transferred out and also needs to be transferred to the non-heat-conducting substrate material, so that the heat-conducting effect of the structure is very limited.
The preparation method of the substrate of the invention, as shown in fig. 1, comprises the steps of:
100. providing hexagonal boron nitride, and carrying out alcoholization treatment on the hexagonal boron nitride to obtain hydroxylated hexagonal boron nitride;
200. providing an organic ligand, wherein the organic ligand is provided with amino and an active group, and the surface of hydroxylated hexagonal boron nitride is modified through the organic ligand;
300. providing cellulose, and crosslinking the cellulose and the hexagonal boron nitride subjected to surface modification to prepare a hexagonal boron nitride/cellulose aerogel skeleton with a three-dimensional network structure;
400. providing an organic polymer base material, and filling the organic polymer base material in a hexagonal boron nitride/cellulose aerogel skeleton to prepare the base.
It is known that Interface Thermal Resistance (ITR) is one of the most important factors that cause a decrease in Thermal Transfer Efficiency (TTE). In substrates containing internal fillers, the Total Interfacial Area (TIA) decreases with increasing dimensions (Ds) of the internal Filler, and thus the TTE per unit mass of Filler in the substrate follows the rule: thermal conductivity of the three-dimensional structure > thermal conductivity of the two-dimensional structure > thermal conductivity of the one-dimensional structure > thermal conductivity of the zero-dimensional structure. Therefore, when the heat conductive filler is disposed in a three-dimensional structure inside the substrate, the heat transfer efficiency is the highest.
The invention carries out alcoholization and surface modification on hexagonal boron nitride, and then carries out crosslinking with cellulose to prepare a three-dimensional network structure taking the hexagonal boron nitride/the cellulose as a framework, then filling the organic polymer substrate material in the framework and wrapping the three-dimensional reticular structure, wherein the hexagonal boron nitride with the modified surface is uniformly, continuously and stably distributed on the three-dimensional reticular structure, thus being capable of providing a multi-dimensional and multi-directional heat flow transmission mode, leading the heat to be effectively transmitted from point to line and surface in time, meanwhile, the structure of the cellulose long-chain cross-linked network can effectively disperse and eliminate various stresses generated by the original inside of the substrate or due to the introduction of hexagonal boron nitride, on the basis of certain original flexibility, the flexibility and the performance of the substrate are further improved, the bending performance is better, and the flexible substrate with excellent heat-conducting performance is formed.
The above steps are described in detail below with reference to specific embodiments.
In the step 100, hexagonal boron nitride is provided, and the hexagonal boron nitride is subjected to alcoholization treatment to obtain hydroxylated hexagonal boron nitride, so that the hexagonal boron nitride is further subjected to surface modification through the hydroxyl groups. Specifically, the boron nitride hydroxide is obtained by mixing hexagonal boron nitride, alcohol amine and organic alcohol, adjusting the pH value and carrying out soaking reaction.
Preferably, the alkanolamine is ethanolamine, the organic alcohol is ethanol, the hexagonal boron nitride nanosheets are mixed with the ethanolamine and ethanol solvent, the pH is adjusted to 8.5, the mixture is stirred at normal temperature for 24 hours, and then the mixture is washed and dried by deionized water, so that the hexagonal boron nitride nanosheets subjected to surface alcoholization are obtained.
Preferably, the hexagonal boron nitride is nanometer hexagonal boron nitride with the particle size of 5-8000 nm.
In the step 200, an organic ligand is provided, where the organic ligand has an amine group and other active groups capable of promoting the crosslinking of hexagonal boron nitride and cellulose, and then the hydroxylated hexagonal boron nitride is subjected to surface modification by the organic ligand, where the organic ligand has a structure: X-R-NH2Wherein amino group-NH2And forming chemical bonding through reaction with hydroxyl on the surface of the hexagonal boron nitride after alcoholization treatment, so as to graft the organic ligand on the hexagonal boron nitride. Wherein the X groups include, but are not limited to: one or more of hydroxyl, carboxyl, ester group, sulfydryl, aldehyde group and halogen, X group is an optional surface modification group, R is a connection modification group-X and-NH2An organic group of (2).
In the step 300, the cellulose and the hexagonal boron nitride after surface modification are crosslinked to form a hexagonal boron nitride/cellulose aerogel skeleton of a three-dimensional network structure, and a plurality of surface-modified hexagonal boron nitrides are uniformly distributed on the three-dimensional network structure. The surface-modified hexagonal boron nitride has a large number of functional groups on the surface, so that hexagonal boron nitride nanosheets can be tightly and effectively anchored on the long chain of cellulose, heat can be effectively conducted along the long chain with the hexagonal boron nitride anchored, in addition, the cellulose has toughness, and the three-dimensional network structure can further improve the flexibility.
Specifically, the step of crosslinking the cellulose and the surface-modified hexagonal boron nitride to form a hexagonal boron nitride/cellulose aerogel skeleton of a three-dimensional network structure includes:
mixing cellulose, strong base and urea in deionized water to obtain a mixed solution; placing the mixed solution at a temperature of-21-38 ℃ and continuously stirring for 0.15-18 h, adding the surface-modified hexagonal boron nitride and a cross-linking agent into the mixed solution in the stirring process, wherein the surface of the surface-modified hexagonal boron nitride has a large number of amino groups and other active groups, so that the surface-modified hexagonal boron nitride can be cross-linked on cellulose under the action of the cross-linking agent, and meanwhile, cross-linking bonds (namely bridge bonds) are also generated between cellulose macromolecules under the action of the cross-linking agent and molecules of the active groups to form a network structure, so that the hydrogel with the hexagonal boron nitride-cellulose cross-linking network structure, namely a cross-linking product, is obtained; and washing the crosslinked product with deionized water for 3-5 times, removing impurities, and then carrying out freeze drying treatment to remove water, so as to obtain the hexagonal boron nitride/cellulose aerogel skeleton with the three-dimensional network structure. Preferably, the temperature of the freeze drying is-62 to-44 ℃, and the time of the freeze drying is 12 to 96 hours.
Wherein the concentration of the cellulose in the mixed solution is 3-97 mg/mL. Preferably, the concentration of the cellulose is 25-84 mg/mL, and the cellulose can be better contacted with strong alkali and urea for activation under the concentration, and can be fully and freely contacted with the hexagonal boron nitride after surface modification and a cross-linking agent for cross-linking reaction.
Wherein the concentration of the strong base in the mixed solution is 13-174 mg/mL. Preferably, the concentration of the strong base is 47-111 mg/mL, so that the cellulose can be sufficiently activated and etched to facilitate the crosslinking reaction, and excessive loss and even dissolution of the cellulose can not be caused.
Wherein the concentration of urea in the mixed solution is 65-380 mg/mL. Preferably, the concentration of the urea is 92-173 mg/mL.
Preferably, after the surface-modified hexagonal boron nitride and the cross-linking agent are added into the mixed solution, the volume percentage of the surface-modified hexagonal boron nitride is 0.2-36 vol%, and the volume percentage of the cross-linking agent is 0.008-0.16 vol%.
In the step 400, an organic polymer base material serving as a matrix skeleton is provided, the organic polymer base material is filled in the hexagonal boron nitride/cellulose aerogel skeleton, specifically, the organic polymer base material is infiltrated into the inside and the periphery of the three-dimensional reticular hexagonal boron nitride/cellulose aerogel skeleton in a molten state, the whole skeleton is wrapped, and then the substrate is prepared by curing and molding. In the substrate, because the three-dimensional net-shaped hexagonal boron nitride/cellulose skeleton is distributed all over, a multi-dimensional and multi-directional heat flow transfer mode can be provided, heat can be timely and effectively transferred from points to lines and surfaces, meanwhile, the structure of the cellulose long-chain cross-linked network can effectively disperse and eliminate various stresses generated by the original inside of the substrate or due to the introduction of the hexagonal boron nitride, so that the flexibility of the substrate is not reduced or increased, and the flexible substrate with excellent heat conductivity is formed. Therefore, when the inside of the light emitting device is connected with the outside through the substrate, the substrate can directly and effectively dissipate heat in time, and dense multipoint heat conduction contact can be realized no matter how the device is bent due to good flexibility of the substrate, so that heat transfer is more efficient.
Preferably, the organic polymer base material is one or more of polyethylene terephthalate, polyethylene naphthalate, polyetheretherketone, polystyrene, polyethersulfone, polycarbonate, polyarylate, polyimide, polyvinyl chloride, polyethylene, polyvinylpyrrolidone, and textile fibers.
The invention also provides a substrate, wherein the substrate is prepared by the preparation method of the substrate. The structure is shown in fig. 2, wherein 10 is hexagonal boron nitride, 20 is an organic ligand, 30 is cellulose, and 40 is an organic polymer matrix material. In the invention, the substrate with the required heat conduction effect, flexibility and light transmittance can be obtained by reasonably controlling appropriate parameters.
The invention also provides a light-emitting device, which comprises the substrate, wherein the light-emitting device is an OLED device or a QLED device.
The OLED device comprises a substrate, a bottom electrode, a first functional layer, an organic light emitting layer, a second functional layer and a top electrode which are sequentially arranged. Wherein the organic light emitting diode may be a positive type OLED device or an inverted type OLED device. For a positive-type OLED device, the bottom electrode is an anode, the top electrode is a cathode, the first functional layer is a hole injection layer and a hole transport layer which are sequentially laminated and combined on the anode, and the second functional layer is an electron injection/transport layer which is laminated and combined on the organic light-emitting layer; for an inverted OLED device, the bottom electrode is a cathode, the top electrode is an anode, the first functional layer is an electron injection/transport layer, and the second functional layer is a hole injection layer and a hole transport layer which are sequentially laminated and combined on the organic light-emitting layer.
The bottom and top electrode materials include, but are not limited to, doped or undoped metal oxides, metals, and/or conductive non-metallic materials. Wherein the doped metal oxide includes, but is not limited to, one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), and aluminum-doped magnesium oxide (AMO); the metal includes but is not limited to Al, Ag, Mg, Cu, Mo, Au, or their alloy; the conductive non-metallic material includes but is not limited to one or more of graphene, graphite, carbon nano tube, fullerene and carbon fiber. In addition, the bottom electrode and the top electrode can be made of doped or undoped transparent metal oxides with metal sandwiched therebetween, including but not limited to AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO/Al/ZnO, or composite electrodes2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2、TiO2/Al/TiO2One or more of (a).
The hole injection layer is selected from one or more of PEDOT, PSS, CuPc, F4-TCNQ, HATCN, transition metal oxide and transition metal chalcogenide compound; wherein the transition metal oxide comprises one or more of MoOx, VOx, WOx, CrOx and CuO; the metal chalcogenide compound comprises MoS2、MoSe2、WS2、WSe2And CuS.
The hole transport layer is selected from poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N ' -bis (4-butylphenyl) -N, N ' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4', 4' ' -tris (carbazol-9-yl) triphenylamine, 4' -bis (9-carbazol) biphenyl, N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1 ' -biphenyl-4, 4' -diamine, 15N, N ' -diphenyl-N, at least one of N ' - (1-naphthyl) -1,1 ' -biphenyl-4, 4' -diamine, graphene and C60. As another embodiment, the hole transport layer is selected from inorganic materials having hole transport capabilities including, but not limited to, NiOx, MoOx, WOx, CrOx, CuO, MoS2、MoSe2、WS2、WSe2And CuS.
The organic luminescent material is selected from 9, 10-di-2-zeitylanthracene (ADN), 2,3,6, 7-tetramethyl-9, 10-dinaphthylanthracene (TMADN), PPV, Alq3, DCM, C540, Rubene, Bebq2, OXD-7 and the like.
The electron transport layer is selected from ZnO and TiO2、SnO2、Ta2O3、AlZnO、ZnSnO、InSnO、Alq3、Ca、Ba、CsF、LiF、CsCO3One or more of (a).
The OLED device may be of a positive or negative configuration.
The QLED device comprises the substrate, a bottom electrode, a first functional layer, a quantum dot light-emitting layer, a second functional layer and a top electrode which are sequentially arranged. Wherein the quantum dot light emitting diode may be a positive type QLED device or an inverse type QLED device. For a positive type QLED device, the bottom electrode is an anode, the top electrode is a cathode, the first functional layer is a hole injection layer and a hole transport layer which are sequentially stacked and combined on the anode, and the second functional layer is an electron injection/transport layer which is stacked and combined on the quantum dot light-emitting layer; for the inversion type QLED device, the bottom electrode is a cathode, the top electrode is an anode, the first functional layer is an electron injection/transport layer, and the second functional layer is a hole injection layer and a hole transport layer which are sequentially laminated and combined on the quantum dot light-emitting layer.
The bottom and top electrode materials include, but are not limited to, doped or undoped metal oxides, metals, and/or conductive non-metallic materials. Wherein the doped metal oxide includes, but is not limited to, one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), and aluminum-doped magnesium oxide (AMO); the metal includes but is not limited to Al, Ag, Mg, Cu, Mo, Au, or their alloy; the conductive non-metallic material includes but is not limited to one or more of graphene, graphite, carbon nano tube, fullerene and carbon fiber. In addition, the top electrode and the bottom electrode can be made of doped or undoped transparent metal oxides with metal sandwiched therebetween, including but not limited to AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO/Al/ZnO, or composite electrodes2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2、TiO2/Al/TiO2One or more of (a).
The hole injection layer is selected from one or more of PEDOT, PSS, CuPc, F4-TCNQ, HATCN, transition metal oxide and transition metal chalcogenide compound; wherein the transition metal oxide comprises one or more of MoOx, VOx, WOx, CrOx and CuO; the metal chalcogenide compound comprises MoS2、MoSe2、WS2、WSe2And CuS.
The hole transport layer is selected from poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N ' -bis (4-butylphenyl) -N, N ' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4', 4' ' -tris (carbazol-9-yl) triphenylamine, 4' -bis (9-carbazol) biphenyl, N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1 ' -biphenyl-4, 4' -diamine, 15N, N ' -diphenyl-N, n' - (A)1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, graphene and C60. As another embodiment, the hole transport layer is selected from inorganic materials having hole transport capabilities including, but not limited to, NiOx, MoOx, WOx, CrOx, CuO, MoS2、MoSe2、WS2、WSe2And CuS.
The material of the quantum dot light-emitting layer is one or more of II-VI compound, III-V compound, II-V compound, III-VI compound, IV-VI compound, I-III-VI compound, II-IV-VI compound or IV elementary substance. Specifically, the semiconductor materials used for the quantum dot light emitting layer include, but are not limited to, nanocrystals of II-VI semiconductors such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe and other binary, ternary, quaternary II-VI compounds; nanocrystals of group III-V semiconductors such as GaP, GaAs, InP, InAs and other binary, ternary, quaternary III-V compounds; the semiconductor material for electroluminescence is not limited to group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds, group IV simple substance, and the like;
the quantum dots comprise doped or undoped inorganic perovskite type semiconductors and/or organic-inorganic hybrid perovskite type semiconductors; specifically, the structural general formula of the inorganic perovskite type semiconductor is AMX3Wherein A is Cs+Ion, M is a divalent metal cation, including but not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+X is a halide anion, including but not limited to Cl-、Br-、I-(ii) a The structural general formula of the organic-inorganic hybrid perovskite type semiconductor is BMX3Wherein B is an organic amine cation including but not limited to CH3(CH2)n-2NH3 +(n.gtoreq.2) or NH3(CH2)nNH3 2+(n.gtoreq.2). When n =2, inorganicMetal halide octahedron MX6 4-The metal cations M are positioned in the center of a halogen octahedron through connection in a roof sharing mode, and the organic amine cations B are filled in gaps among the octahedrons to form an infinitely extending three-dimensional structure; inorganic metal halide octahedra MX linked in a coterminous manner when n > 26 4-The organic amine cation bilayer (protonated monoamine) or the organic amine cation monolayer (protonated diamine) is inserted between the layers, and the organic layer and the inorganic layer are overlapped with each other to form a stable two-dimensional layered structure; m is a divalent metal cation including, but not limited to, Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+(ii) a X is a halide anion, including but not limited to Cl-、Br-、I-；
The electron transport layer is selected from ZnO and TiO2、SnO2、Ta2O3One or more of AlZnO, ZnSnO, InSnO, Alq3, Ca, Ba, CsF, LiF and CsCO 3.
The QLED device may be of a positive or negative type.
The invention also provides a display screen, which comprises the substrate, wherein the display screen can be a flexible display screen, and the substrate has good thermal conductivity and flexibility, so that the flexibility of the display screen is particularly good.
The present invention will be described in detail below with reference to examples.
Example 1
(1) And carrying out ball milling on the hexagonal boron nitride particles for 48 hours, and then carrying out ultrasonic treatment for 5 hours to prepare the nano-sheets.
(2) Mixing the hexagonal boron nitride nanosheets with an ethanolamine and ethanol solvent, adjusting the pH to 8.5, stirring at normal temperature for 24 hours, and then washing and drying with deionized water to obtain the hexagonal boron nitride nanosheets subjected to surface alcoholization. Wherein, after alcoholization, the-H hydroxylation of the surface of the hexagonal boron nitride forms hydroxyl boron nitride.
(3) Adding cellulose, sodium hydroxide and urea into deionized water, and uniformly mixing to obtain a mixed solution, wherein the concentration of the cellulose is 45 mg/ml, the concentration of the sodium hydroxide is 53 mg/ml, and the concentration of the urea is 115 mg/ml. After the mixed solution is obtained, the mixed solution is placed at the temperature of minus 17 ℃ and is continuously stirred for 12 hours, and in the stirring process, 33vol% of hexagonal boron nitride lamella subjected to surface modification is added, and 0.08vol% of epoxy chloropropane is added as a cross-linking agent.
(4) And after stirring, taking out the solid from the mixed solution, standing for 4 hours at 60 ℃, and then washing for 5 times by using deionized water to obtain the hexagonal boron nitride-cellulose crosslinked network structure hydrogel.
(5) And (3) treating the hexagonal boron nitride-cellulose cross-linked network structure hydrogel obtained in the step (4) in a freeze drying mode, controlling the temperature within the range of-54 ℃, controlling the freeze drying time within 52h, and freeze drying to obtain the cross-linked hexagonal boron nitride-cellulose aerogel skeleton with the three-dimensional network structure.
(6) And (3) taking the hexagonal boron nitride-cellulose aerogel framework which is prepared in the step (5) and has the three-dimensional network structure and is crosslinked with each other as a frame, penetrating the PET material in a molten liquid state into and around the frame, and then curing and forming to obtain the novel high-thermal-conductivity flexible substrate.
Example 2
Preparing a flexible QLED device, comprising the steps of:
(1) depositing an ITO electrode on the substrate in the embodiment 1;
(2) and sequentially printing a PEDOT hole injection layer, a TFB hole transmission layer, a CdSe quantum dot light emitting layer and a ZnO electron transmission layer on the ITO anode, and finally evaporating an Al cathode to form the flexible QLED device.
In summary, the invention provides a substrate, a preparation method thereof, a light emitting device and a display screen, the substrate provided by the invention utilizes the characteristics of a hexagonal boron nitride material with higher thermal conductivity, excellent electrical insulation property, good corrosion resistance and lower thermal expansion coefficient to cross-link the hexagonal boron nitride subjected to surface modification and cellulose to prepare a hexagonal boron nitride/cellulose aerogel skeleton with a three-dimensional network structure, and then an organic polymer substrate material is filled in the skeleton and wraps the skeleton, because the skeleton is provided with a plurality of regular hexagonal boron nitrides subjected to surface modification, the substrate also has excellent thermal conductivity and electrical insulation property, and the skeleton is in a three-dimensional network structure, a multi-dimensional and multi-directional heat flow transfer mode can be provided, and heat can be timely and effectively transferred from points to lines and planes, and the cellulose with good thermal conductivity is arranged between each hexagonal boron nitride unit and is used as a thermal conductive bridge, but not separated by a non-thermal conductive insulating material, so that heat can be effectively dissipated, and meanwhile, the structure of the cellulose long-chain cross-linked network can effectively disperse and eliminate various stresses in the substrate or generated by the introduction of the hexagonal boron nitride, so that the flexibility of the substrate is further improved on the basis of certain flexibility caused by the original organic polymer substrate material, and the bending performance is better. The invention solves the problem of poor heat conduction of the substrate in the existing light-emitting device.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (12)
1. A method of preparing a substrate, comprising the steps of:
providing hexagonal boron nitride, and carrying out alcoholization treatment on the hexagonal boron nitride to obtain hydroxylated hexagonal boron nitride;
providing an organic ligand, wherein the organic ligand is provided with amino and an active group, and the surface of hydroxylated hexagonal boron nitride is modified through the organic ligand;
providing cellulose, and crosslinking the cellulose and the hexagonal boron nitride subjected to surface modification through the action of the active group and the cellulose to prepare a hexagonal boron nitride/cellulose aerogel skeleton with a three-dimensional network structure;
providing an organic polymer base material, and filling the organic polymer base material in a hexagonal boron nitride/cellulose aerogel skeleton to prepare a base;
wherein the active group is one or more of hydroxyl, carboxyl, ester group, sulfhydryl, aldehyde group and halogen;
the organic ligand has the structure as follows: X-R-NH2Wherein X is an active group and R is a linkage of-X and-NH2by-NH in said organic ligand2Reacting with hydroxyl on the surface of the hydroxylated hexagonal boron nitride to form chemical bonding, and grafting the organic ligand on the hexagonal boron nitride.
2. The method of manufacturing a substrate according to claim 1, wherein the hexagonal boron nitride has a size of 5 to 8000 nm.
3. The method for preparing a substrate according to claim 1, wherein the step of crosslinking the cellulose with the surface-modified hexagonal boron nitride and forming a hexagonal boron nitride/cellulose aerogel skeleton of a three-dimensional network structure comprises:
mixing cellulose, strong base and urea in deionized water to obtain a mixed solution;
adding the surface-modified hexagonal boron nitride and a cross-linking agent into the mixed solution to perform a cross-linking reaction between the cellulose and the hexagonal boron nitride to obtain a cross-linked product;
and (3) freeze-drying the cross-linked product to obtain the hexagonal boron nitride/cellulose aerogel skeleton with a three-dimensional network structure.
4. The method for preparing a substrate according to claim 3, wherein the concentration of cellulose in the mixed solution is 3 to 97 mg/mL; and/or the concentration of strong base is 13-174 mg/mL; and/or the concentration of urea is 65-380 mg/mL.
5. The method for preparing a substrate according to claim 4, wherein the volume percentage of the hexagonal boron nitride after surface modification is 0.2-36 vol% after the hexagonal boron nitride after surface modification and the cross-linking agent are added into the mixed solution; and/or the volume percentage of the cross-linking agent is 0.008-0.16 vol%.
6. The method for preparing a substrate according to claim 3, wherein the temperature of the freeze-drying is-62 to-44 ℃; and/or the freeze drying time is 12-96 h.
7. Process for the preparation of a substrate according to claim 3, characterized in that the crosslinking agent is epichlorohydrin.
8. The method of claim 1, wherein the organic polymer substrate material is one or more of polyethylene terephthalate, polyethylene naphthalate, polyetheretherketone, polystyrene, polyethersulfone, polycarbonate, polyarylate, polyimide, polyvinyl chloride, polyethylene, polyvinylpyrrolidone, and textile fibers.
9. A substrate prepared by the method of any one of claims 1 to 8, comprising a hexagonal boron nitride/cellulose aerogel framework and an organic polymeric substrate material filled in the hexagonal boron nitride/cellulose aerogel framework.
10. A light-emitting device comprising the substrate according to claim 9.
11. The light-emitting device according to claim 10, wherein the light-emitting device is an OLED device or a QLED device.
12. A display screen comprising the substrate of claim 9.
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