CN111378323B - Ink, quantum dot film and quantum dot light-emitting diode - Google Patents
Ink, quantum dot film and quantum dot light-emitting diode Download PDFInfo
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- CN111378323B CN111378323B CN201811633301.2A CN201811633301A CN111378323B CN 111378323 B CN111378323 B CN 111378323B CN 201811633301 A CN201811633301 A CN 201811633301A CN 111378323 B CN111378323 B CN 111378323B
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
Abstract
The invention belongs to the technical field of display, and particularly relates to ink, a quantum dot film and a quantum dot light-emitting diode. The ink comprises an organic solvent, quantum dots and a block copolymer dispersed in the organic solvent, wherein the molecular general formula of the block copolymer is mercapto-polystyrene-A-R; wherein A comprises a block chain of formula I and/or formula II in the specification, and R is an aliphatic group or an aromatic group; in the formula I and the formula II, x and y are integers, and x and y are not 0 at the same time. The ink containing the special block copolymer can improve the process, film forming performance and light emitting performance of the quantum dot light emitting semiconductor by ink jet printing.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to ink, a quantum dot film and a quantum dot light-emitting diode.
Background
Quantum Dot (QD) luminescent materials have characteristics of change in emission frequency with dimensional change, narrow emission line width, relatively high luminescent quantum efficiency, and ultra-high light stability and solution processing. Due to the characteristics, quantum dot light emitting diodes (QLEDs) using quantum dot materials as light emitting layers have wide application prospects in the fields of solid-state lighting, flat panel display and the like, and are widely concerned by academia and industry.
The solution processing property of the quantum dots enables the quantum dot light-emitting layer to be prepared in various ways such as spin coating, blade coating, spraying, ink-jet printing and the like. Compared with the previous methods, the ink-jet printing technology can accurately deposit the quantum dot luminescent material at a proper position according to the required amount, so that the semiconductor material is uniformly deposited to form a thin film layer, the utilization rate of the material is very high, a manufacturer can reduce the production cost, the manufacturing process is simplified, mass production is easy to popularize, and the cost is reduced. The ink jet printing technology is an effective method which is recognized at present and can solve the manufacturing problem of the large-size QLED screen.
However, at present, quantum dots are basically directly dispersed in a solvent, and the obtained quantum dot ink has very low viscosity, so that the prepared quantum dot film has inconsistent thickness and poor uniformity, and the light efficiency is reduced due to unbalanced electron hole injection of a quantum dot light-emitting layer.
Therefore, the prior art is in need of improvement.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides ink, a quantum dot film and a quantum dot light-emitting diode, and aims to solve the technical problem of uneven film formation caused by poor dispersibility of the existing quantum dot ink.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an ink, which comprises an organic solvent, quantum dots and a block copolymer dispersed in the organic solvent, wherein the molecular general formula of the block copolymer is as follows: mercapto-polystyrene-a-R;
wherein A comprises a block chain of formula I and/or formula II, R is an aliphatic group or an aromatic group;
wherein in the formula I and the formula II, x and y are integers, and x and y are not 0 at the same time.
The invention provides ink containing a block copolymer, wherein the block copolymer is added into the ink containing quantum dots as a modifier, so that the viscosity of the ink can be adjusted, and the printing manufacturability and the film forming property can be improved; meanwhile, the block copolymer contains a unit with a hole transmission characteristic, so that the hole transmission performance of the quantum dot can be improved, and the hole injection balance of a device is facilitated after the quantum dot light-emitting layer is prepared; and the sulfydryl in the block copolymer can be matched with the quantum dots, so that the reduction of quantum efficiency caused by too close quantum dots is avoided. In short, the ink containing the special block copolymer can improve the process, the film forming performance and the light emitting performance of the quantum dot light emitting semiconductor by ink-jet printing.
The invention also provides a quantum dot film, which comprises quantum dots and a block copolymer dispersed in the quantum dots, wherein the molecular general formula of the block copolymer is mercapto-polystyrene-A-R;
wherein A comprises a block chain of formula I and/or formula II, R is an aliphatic group or an aromatic group;
wherein in the formula I and the formula II, x and y are integers, and x and y are not 0 at the same time.
According to the quantum dot film provided by the invention, the quantum dots are dispersed with the block copolymer, and the block copolymer contains a unit with a hole transmission characteristic, so that the hole transmission performance of the quantum dot film can be improved, and thus, the quantum dot film is beneficial to hole injection balance of a device after being used for a quantum dot light-emitting layer; and the sulfydryl in the block copolymer can be matched with the quantum dots, so that the reduction of quantum efficiency caused by too close quantum dots is avoided, the energy transfer loss among the quantum dots is reduced, and the luminous performance of the quantum dot film is improved.
Finally, the invention provides a quantum dot light-emitting diode, which comprises an anode, a cathode and a quantum dot light-emitting layer arranged between the anode and the cathode, wherein the quantum dot light-emitting layer is the quantum dot film.
The quantum dot light-emitting diode provided by the invention is composed of the specific quantum dot film, so that the hole injection balance of the quantum dot light-emitting layer can be improved, the quantum efficiency of the quantum dot light-emitting layer can be improved, and the light-emitting performance of the device can be improved.
Drawings
Fig. 1 is a flowchart of a method for manufacturing a quantum dot thin film according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, embodiments of the present invention provide an ink, including an organic solvent, and quantum dots and a block copolymer dispersed in the organic solvent, where the molecular formula of the block copolymer is: mercapto-polystyrene-a-R;
wherein A comprises a block chain of formula I and/or formula II, R is an aliphatic group or an aromatic group;
wherein in the formula I and the formula II, x and y are integers, and x and y are not 0 at the same time.
The embodiment of the invention provides ink containing a block copolymer, wherein the block copolymer is added into the ink containing quantum dots as a modifier, so that the viscosity of the ink can be adjusted, and the printing manufacturability and the film forming property can be improved; meanwhile, the block copolymer contains a unit with a hole transmission characteristic, so that the hole transmission performance of the quantum dot can be improved, and the hole injection balance of a device is facilitated after the quantum dot light-emitting layer is prepared; and the sulfydryl in the block copolymer can be matched with the quantum dots, so that the reduction of quantum efficiency caused by too close quantum dots is avoided. In short, the ink containing the special block copolymer can improve the process, the film forming performance and the light emitting performance of the quantum dot light emitting semiconductor by ink-jet printing.
Further, in the block copolymer, R is an aliphatic group or an aromatic group having 3 to 10 carbon atoms; the weight average molecular weight of the block copolymer is 500-10000, more preferably, the polymerization degree of the block copolymer is 1000-5000; in the block copolymer, the mass percentage of the block chain of A in the block copolymer is 10-90%, and more preferably, the mass percentage of the block chain of A in the block copolymer is 40-60%.
For this block copolymer, a diblock copolymer in which mercapto-polystyrene-a-R is a so-called terminal mercapto group is synthesized by reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) and an aminolysis method.
The specific synthesis steps of the block copolymer comprise two steps: (1) mixing a functional monomer, a free radical initiator and a RAFT reagent (dithioester) in a certain amount of solvent, heating and polymerizing for a certain time, putting the reactant into liquid nitrogen to cool for several seconds, and precipitating by using n-hexane to obtain the first-stage functional polymer chain macromolecule RAFT reagent. (2) Dissolving the first-stage functional polymer, styrene and a free radical initiator in a certain amount of solvent, heating for polymerization for a certain time, cooling by liquid nitrogen for several seconds, and precipitating by n-hexane to obtain the diblock polymer with the tail end of dithioester. The dithioester of the polymer and primary amine are subjected to aminolysis reaction to obtain a functionalized diblock polymer with a sulfydryl terminal. The block polymer can be added into quantum dot ink after being dissolved, precipitated and dried by tetrahydrofuran and n-hexane for many times to improve the performance of the ink.
The specific synthetic process is as follows:
wherein the functional monomer R1CHCH2The structure is as follows:
the free radical initiator is a free radical thermal initiator, and the free radical thermal initiator can be one or more of azo, peroxide, persulfate and redox initiator; when the addition polymer is obtained by UV crosslinking (i.e., UV light conditions), the radical initiator is a radical photoinitiator, which may be 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-dimethoxy-2-phenylacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-dimethoxy-phenyl ketone, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinyl benzyl) butanone, 2, 4-dimethylthioxanthone or 2, one or more of 4-diethylthioxanthone. Wherein the RAFT agent is dithioester.
The organic solvent is one or more of benzene, toluene, xylene or higher boiling alkylbenzene, tetrahydrofuran, dichloromethane, dichloroethane, chloroform, chlorobenzene, nitrobenzene, dioxane, cyclohexane, esters such as ethyl acetate, N-butyl acetate or 1-methoxy-2-propyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and solvents such as N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide. Toluene, chloroform or tetrahydrofuran solvents are preferred. The primary amine is ethylamine, propylamine, n-butylamine, n-hexylamine and cyclohexylamine.
The final product, mercapto-polystyrene-a-R, has the following structure: r1R is an aliphatic group or an aromatic group (namely R in the following structure, preferably an aliphatic group or an aromatic group with 3-10 carbon atoms); wherein m and n are positive integers, and x + y is m.
The polyfluorene band gap in the block chain in the block copolymer is relatively large, and the highest occupied orbital (HOMO) energy is about-5.18 eV, so that the HOMO energy level of the quantum dot light emitting layer is increased to a certain extent, the energy barrier between the quantum dot light emitting layer and the hole transport layer is reduced, and meanwhile, the polyfluorene band gap has strong hole transport capacity and is convenient for hole transport; meanwhile, the lowest front Line Unoccupied Molecular Orbital (LUMO) energy level is about-2.12 eV, the transmission of electrons can be properly blocked, the injection of holes and electrons of the quantum dot light-emitting layer is balanced, and the efficiency of the device is improved. The block chain A also contains a polyaniline structure, and the polyaniline structure has a high electronic conductivity framework and high energy density, so that the energy barrier can be reduced, and the energy loss can be reduced. Meanwhile, methyl is an electron-donating group, so that the aniline structure is more stable. Meanwhile, the polyfluorene structure is composed of stable fluorene rings, has a large conjugated system and better rigidity coplanarity, and has high glass transition temperature and good thermal stability.
Further, in the ink of the embodiment of the present invention, the viscosity at 25 to 35 ℃ is 0.5 to 60.0mPa.s, preferably in the range of 1.0 to 15.0 mPa.s; the quantum dots are used for higher luminous efficiency.
Further, in the ink of the embodiment of the present invention, in the block copolymer, the mass percentage of the block chain of a in the block copolymer is 10% to 90%, preferably 40% to 60%.
Further, in the ink of the embodiment of the present invention, the weight ratio of the total weight of the quantum dots and the block copolymer to the organic solvent is (0.01-20.0): (80-99.9); more preferably, the weight ratio of the total weight of the quantum dots and the block copolymer to the organic solvent is (4.0-15.0): (85.0-96.0). And the mass ratio of the block copolymer to the quantum dots is 1 (10-10000). In an embodiment of the present invention, the mass ratio of the block copolymer to the quantum dots is 1: (100-1000), in another embodiment of the present invention, the mass ratio of the block copolymer to the quantum dot is 1: (200-500).
In the ink, the organic solvent is removed by selecting heating, temperature rising or cooling and/or pressure reducing modes in the post-treatment process.
The quantum dots in the ink are binary or multicomponent semiconductor compounds or mixtures of compounds of groups IV, II-VI, II-V, III-VI, IV-VI, I-III-VI, II-IV-VI and II-IV-V of the periodic table of the elements. In particular, selected from CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, HgSe, HgTe, CdZnSe; alternatively, it is selected from InAs, InP, InN, GaN, InSb, InAsP, InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSe Te, ZnCdSe and any combination thereof. Alternatively, the quantum dot is a perovskite nanoparticle material, in particular a luminescent perovskite nanoparticle, or a metal nanoparticle material, or a metal oxide nanoparticle material, or a mixture thereof.
Preferably, the size of the quantum dots is 1-20 nm of average characteristic size. May be of homogeneous mixing type, gradient mixing type, core-shell type or combination type. The quantum dots may be oil-soluble quantum dots; the quantum dots are selected from doped or undoped quantum dots. The quantum dots are combined with ligands, and the ligands are one or more of acid ligands, thiol ligands, amine ligands, (oxy) phosphine ligands, phospholipids, lecithin, polyvinyl pyridine and the like. The acid ligand comprises one or more of decaacid, undecylenic acid, tetradecanoic acid, oleic acid and stearic acid; the thiol ligand comprises one or more of octaalkylthiol, dodecylthiol and octadecylthiol; the amine ligand comprises one or more of oleylamine, octadecylamine and octamine; the (oxy) phosphine ligand comprises one or more of trioctylphosphine and trioctylphosphine.
On the other hand, the embodiment of the invention also provides a quantum dot film, which comprises quantum dots and a block copolymer dispersed in the quantum dots, wherein the molecular general formula of the block copolymer is mercapto-polystyrene-A-R; wherein A comprises a block chain of formula I and/or formula II, R is an aliphatic group or an aromatic group;
wherein in the formula I and the formula II, x and y are integers, and x and y are not 0 at the same time.
According to the quantum dot film provided by the embodiment of the invention, the quantum dots are dispersed with the block copolymer, and the block copolymer contains a unit with a hole transmission characteristic, so that the hole transmission performance of the quantum dot film can be improved, and therefore, the quantum dot film is beneficial to the hole injection balance of a device after being used for a quantum dot light-emitting layer; and the sulfydryl in the block copolymer can be matched with the quantum dots, so that the reduction of quantum efficiency caused by too close quantum dots is avoided, the energy transfer loss among the quantum dots is reduced, and the luminous performance of the quantum dot film is improved.
Accordingly, an embodiment of the present invention provides a method for preparing a quantum dot thin film, as shown in fig. 1, including the following steps:
s01: providing a substrate;
s02: the printing ink provided by the embodiment of the invention is deposited on the substrate, and then drying treatment is carried out to obtain the quantum dot film.
Specifically, the method of ink configuration includes: firstly, dissolving a functional block copolymer in one or more organic solvents according to a certain proportion to obtain a solvent with proper viscosity, boiling point and surface tension; and then the quantum dots are dissolved into the modified solvent according to a preset proportion to obtain the quantum dot ink.
In particular, the method of depositing the ink on the substrate is an ink jet printing method comprising: and carrying out ink-jet printing on the quantum dot luminescent layer film by selecting a proper ink-jet printer. The ink is preferably applied by piezoelectric or thermal ink jet printing. The ink jet printing film is preferably formed so that the dry film thickness is 10 to 100 nm. Particularly, the ink coating film is preferably formed to have a thickness of 20 to 50 nm.
The drying treatment is post-treatment: factors including post-treatment temperature, treatment time, etc. are appropriately adjusted to form the desired quantum dot thin film. Under the action of heating and/or reduced pressure and vacuum, the organic solvent in the quantum dot film is removed, so that the solvent in the ink is completely volatilized, and the block copolymer and the quantum dots form a uniform and flat film. The post-treatment time is 0-30 min. The heating temperature is 60-180 ℃. Heating can be controlled by pulse heating or continuous heating, and heating time is 0-30min, and vacuum degree is 1 × 10-6And (5) carrying out the Torr to normal pressure to ensure that the solvent in the quantum dot film is completely volatilized and the quantum dots are not damaged.
The ink prepared by the embodiment of the invention has proper viscosity and surface tension, and can meet the film-forming property requirement of a printer. Depositing and forming a quantum dot film (used as a quantum dot light-emitting layer in a quantum dot light-emitting diode) with a pixel lattice by an ink-jet printing method; meanwhile, after post-treatment, the thickness of the printed quantum dot film is uniform and flat, and the segmented copolymer is uniformly distributed in the quantum dots. The electron-charge injection of the quantum dot film can be more balanced, the energy transfer loss among quantum dots is reduced, and the luminous efficiency is improved.
Finally, the embodiment of the invention provides a quantum dot light-emitting diode, which comprises an anode, a cathode and a quantum dot light-emitting layer arranged between the anode and the cathode, wherein the quantum dot light-emitting layer is the quantum dot film.
The quantum dot light-emitting diode provided by the embodiment of the invention is composed of the quantum dot film which is specific to the embodiment of the invention, so that the hole injection balance of the quantum dot light-emitting layer can be improved, the quantum efficiency of the quantum dot light-emitting layer can be improved, and the light-emitting performance of a device can be improved.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
A preparation method and a printing method of ink comprise the following steps:
(1) functional block polymer modifier: synthesis of mercapto-polystyrene-A-R
5g of functional monomer N-phenyl-N-methylphenyl-p-vinylaniline of the type I block chain, 5mg of Azodiisobutyronitrile (AIBN) serving as a free radical initiator and 60mg of phenethyl dithiobenzoate are mixed and dissolved in 50mL of tetrahydrofuran, oxygen in the mixture is removed by defoaming in vacuum-liquid nitrogen for several times, nitrogen is filled, the mixture is heated to 50 ℃, and polymerization is carried out for 48 hours. And (3) putting the reactant mixture into liquid nitrogen to cool for several seconds to terminate the chain transfer reaction, and then precipitating by using normal hexane to obtain 3.8g of the first-stage functional polymer chain macromolecular RAFT reagent.
Dissolving 3g of the polymer RAFT reagent, 2g of styrene and 2mg of AIBN in 50mL of tetrahydrofuran, defoaming the mixture by vacuum-liquid nitrogen for several times to remove oxygen in the mixture, filling nitrogen, heating to 50 ℃, and polymerizing for 48 hours. The reaction mixture was cooled in liquid nitrogen for several seconds to terminate the chain transfer reaction, and then n-hexane was precipitated to obtain 4.1g of a diblock polymer terminated with a dithioester.
4g of the diblock polymer having a terminal dithioester was reacted with 10g of cyclohexylamine in 50mL of tetrahydrofuran at room temperature for 6 hours, and then n-hexane was precipitated to obtain 3.7g of the diblock polymer having a terminal mercapto group.
The block polymer is dissolved and precipitated by tetrahydrofuran and n-hexane for many times, is dried in vacuum to constant weight, and is added into the quantum dot ink, so that the performance of the ink is improved.
(2) Preparation and printing of quantum dot ink
500mg of the polymer obtained above was mixed with 20g of dodecane and dissolved by heating to 100 ℃ for 30 minutes, followed by filtration through a 1 μ filter for use. 1.5g of oleylamine stabilized red CdSe/ZnS quantum dots and 8.5g of the above polymer solution were mixed and stirred for 30 minutes, and filtered through a 0.45 μ filter to obtain quantum dot ink.
A layer of red quantum dots of 20 × 30um, resolution 200 × 200ppi was printed by an inkjet printer. Heating to 100 ℃ on a hot plate, nitrogen flow and vacuum of 1X 10-6And volatilizing and drying for 30min under the condition of Torr to obtain the monochromatic quantum dot luminescent layer.
Example 2
A preparation method and a printing method of ink comprise the following steps:
(1) functional block polymer modifier: synthesis of mercapto-polystyrene-A-R
3g of functional monomer N-phenyl-N-methylphenyl-p-vinylaniline of the type I block chain, 3mg of Azodiisobutyronitrile (AIBN) serving as a free radical initiator and 60mg of phenethyl dithiobenzoate are mixed and dissolved in 50mL of tetrahydrofuran, oxygen in the mixture is removed by vacuum-liquid nitrogen defoaming for several times, nitrogen is filled, the mixture is heated to 50 ℃, and polymerization is carried out for 48 hours. Then 2g of II type block chain functional monomer 3-vinyl-9, 9-dimethyl fluorene is added, oxygen in the mixture is removed by vacuum-liquid nitrogen defoaming for several times, nitrogen is filled, and then the mixture is heated to 50 ℃ and polymerized for 48 hours. And (3) putting the reactant mixture into liquid nitrogen to cool for several seconds to terminate the chain transfer reaction, and then precipitating by using normal hexane to obtain 3.5g of the first-stage functional polymer chain macromolecular RAFT reagent.
Dissolving 3g of the polymer RAFT reagent, 2g of styrene and 2mg of AIBN in 50mL of tetrahydrofuran, defoaming the mixture by vacuum-liquid nitrogen for several times to remove oxygen in the mixture, filling nitrogen, heating to 50 ℃, and polymerizing for 48 hours. The reaction mixture was cooled in liquid nitrogen for several seconds to terminate the chain transfer reaction, and then n-hexane was precipitated to obtain 4g of a diblock polymer terminated with a dithioester.
4g of the diblock polymer having a terminal dithioester was reacted with 10g of cyclohexylamine in 50mL of tetrahydrofuran at room temperature for 6 hours, and then n-hexane was precipitated to obtain 3.6g of the diblock polymer having a terminal mercapto group.
The block polymer is dissolved and precipitated by tetrahydrofuran and n-hexane for many times, is dried in vacuum to constant weight, and is added into the quantum dot ink, so that the performance of the ink is improved.
(2) Preparation and printing of quantum dot ink
500mg of the polymer obtained above was mixed with 15g of tetradecane and 10g of cyclohexylbenzene, and the mixture was dissolved by heating to 100 ℃ for 30 minutes, and then filtered through a 1. mu. filter for use. 1.0g of oleylamine stabilized red CdSe/ZnS quantum dot and 9.0g of the polymer solution were mixed and stirred for 30 minutes, and filtered through a 0.45 μ filter to obtain a quantum dot ink.
A layer of red quantum dots of 20 × 30um, resolution 200 × 200ppi was printed by an inkjet printer. Heating to 120 ℃ on a hotplate, nitrogen flow and vacuum of 1X 10-6And volatilizing and drying for 30min under the condition of Torr to obtain the monochromatic quantum dot luminescent layer.
Example 3
A preparation method and a printing method of ink comprise the following steps:
(1) functional block polymer modifier: synthesis of mercapto-polystyrene-A-R
3g of the functional monomer N-phenyl-N-methylphenyl-p-vinylaniline of the I type block chain, 2g of the functional monomer 3-vinyl-9, 9-dimethyl fluorene of the II type block chain, 3mg of Azodiisobutyronitrile (AIBN) serving as a free radical initiator and 60mg of phenethyl dithiobenzoate are mixed and dissolved in 50mL of tetrahydrofuran, oxygen in the mixture is removed by vacuum-liquid nitrogen defoaming for several times, nitrogen is filled, then the mixture is heated to 50 ℃, and polymerization is carried out for 48 hours. And (3) cooling the reactant mixture in liquid nitrogen for several seconds to terminate the chain transfer reaction, and then precipitating by using normal hexane to obtain 3.3g of the first-stage functional polymer chain macromolecular RAFT reagent.
Dissolving 3g of the polymer RAFT reagent, 2g of styrene and 2mg of AIBN in 50mL of tetrahydrofuran, defoaming the mixture by vacuum-liquid nitrogen for several times to remove oxygen in the mixture, filling nitrogen, heating to 50 ℃, and polymerizing for 48 hours. The reaction mixture was cooled in liquid nitrogen for several seconds to terminate the chain transfer reaction, and then n-hexane was precipitated to obtain 3.9g of a diblock polymer having a dithioester terminal.
4g of the diblock polymer having a terminal dithioester was reacted with 10g of cyclohexylamine in 50mL of tetrahydrofuran at room temperature for 6 hours, and then n-hexane was precipitated to obtain 3.5g of the diblock polymer having a terminal mercapto group.
The block polymer is dissolved and precipitated by tetrahydrofuran and n-hexane for many times, is dried in vacuum to constant weight, and is added into the quantum dot ink, so that the performance of the ink is improved.
(2) Preparation and printing of quantum dot ink
500mg of the polymer obtained above was mixed with 20g of dodecane and 5g of decalin, and the mixture was dissolved by heating to 100 ℃ for 30 minutes, and then filtered through a 1 μ filter for use. 1.2g of oleylamine stabilized red CdSe/ZnS quantum dot and 8.8g of the above polymer solution were mixed and stirred for 30 minutes, and filtered through a 0.45 μ filter to obtain a quantum dot ink.
A layer of red quantum dots of 20 × 30um, resolution 200 × 200ppi was printed by an inkjet printer. Heating to 100 ℃ on a hot plate, nitrogen flow and vacuum of 1X 10-6And volatilizing and drying for 30min under the condition of Torr to obtain the monochromatic quantum dot luminescent layer.
Example 4
A preparation method and a printing method of ink comprise the following steps:
(1) functional block polymer modifier: synthesis of mercapto-polystyrene-A-R
6g of functional monomer 3-vinyl-9, 9-dimethyl fluorene of the type II block chain, 5mg of Azodiisobutyronitrile (AIBN) serving as a free radical initiator and 60mg of phenethyl dithiobenzoate are mixed and dissolved in 50mL of tetrahydrofuran, oxygen in the mixture is removed by vacuum-liquid nitrogen defoaming for several times, nitrogen is filled, then the mixture is heated to 50 ℃, and polymerization is carried out for 48 hours. And (3) putting the reactant mixture into liquid nitrogen to cool for several seconds to terminate the chain transfer reaction, and then precipitating by using normal hexane to obtain 4.2g of the first-stage functional polymer chain macromolecular RAFT reagent.
Dissolving 3g of the polymer RAFT reagent, 2g of styrene and 2mg of AIBN in 50mL of tetrahydrofuran, defoaming the mixture by vacuum-liquid nitrogen for several times to remove oxygen in the mixture, filling nitrogen, heating to 50 ℃, and polymerizing for 48 hours. The reaction mixture was cooled in liquid nitrogen for several seconds to terminate the chain transfer reaction, and then n-hexane was precipitated to obtain 4.3g of a diblock polymer terminated with a dithioester.
4g of the diblock polymer having a terminal dithioester was reacted with 10g of cyclohexylamine in 50mL of tetrahydrofuran at room temperature for 6 hours, and then n-hexane was precipitated to obtain 3.5g of the diblock polymer having a terminal mercapto group.
The block polymer is dissolved and precipitated by tetrahydrofuran and n-hexane for many times, is dried in vacuum to constant weight, and is added into the quantum dot ink, so that the performance of the ink is improved.
(2) Preparation and printing of quantum dot ink
500mg of the polymer obtained above was mixed with 20g of pentadecane and 5g of tetrahydronaphthalene, and the mixture was dissolved by heating to 100 ℃ for 30 minutes and then filtered through a 1 μ filter for use. 1.5g of oleylamine stabilized red CdSe/ZnS quantum dots and 8.5g of the above polymer solution were mixed and stirred for 30 minutes, and filtered through a 0.45 μ filter to obtain quantum dot ink.
A layer of red quantum dots of 20 × 30um, resolution 200 × 200ppi was printed by an inkjet printer. Heating to 100 ℃ on a hot plate, nitrogen flow and vacuum of 1X 10-6And volatilizing and drying for 30min under the condition of Torr to obtain the monochromatic quantum dot luminescent layer.
Example 5
A quantum dot light emitting diode comprising an anode, a cathode, and a quantum dot light emitting layer disposed between the anode and the cathode, wherein the quantum dot light emitting layer is obtained by any one of the preparation methods of embodiments 1-4.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. The preparation method of the ink is characterized by comprising the following steps of:
dissolving a segmented copolymer with a molecular general formula of sulfydryl-polystyrene-A-R in an organic solvent, and then adding quantum dots for mixing to obtain the ink;
wherein A comprises a block chain of the following formula I and formula II, R is an aliphatic group or an aromatic group;
wherein in the formula I and the formula II, x and y are integers, and x and y are not 0 at the same time.
2. The method for producing an ink according to claim 1, wherein R in the block copolymer is an aliphatic group or an aromatic group of 3 to 10 carbons; and/or the presence of a gas in the gas,
the weight average molecular weight of the block copolymer is 500-10000; and/or the presence of a gas in the gas,
in the block copolymer, the block chain of A accounts for 10-90% of the mass of the block copolymer.
3. The method of claim 2, wherein the block copolymer has a degree of polymerization of 1000-5000.
4. The method for producing an ink according to claim 2, wherein the block chain of a in the block copolymer accounts for 40 to 60 mass% of the block copolymer.
5. The method of preparing an ink according to any one of claims 1 to 4, wherein the weight ratio of the total weight of the quantum dot and the block copolymer to the organic solvent is (0.01-20.0): (80-99.9); and/or the presence of a gas in the gas,
the mass ratio of the block copolymer to the quantum dots is 1 (10-10000).
6. The method of claim 5, wherein the weight ratio of the total weight of the quantum dots and the block copolymer to the organic solvent is (4.0-15.0): 85.0-96.0.
7. The quantum dot film is characterized by comprising quantum dots and a block copolymer dispersed in the quantum dots, wherein the molecular general formula of the block copolymer is mercapto-polystyrene-A-R;
wherein A comprises a block chain of the following formula I and formula II, R is an aliphatic group or an aromatic group;
wherein x and y are integers in the formula I and are not 0 at the same time;
the quantum dot film is obtained by carrying out ink-jet printing on the ink prepared by the preparation method of the ink according to any one of claims 1 to 6.
8. A quantum dot light emitting diode comprising an anode, a cathode, and a quantum dot light emitting layer disposed between the anode and the cathode, wherein the quantum dot light emitting layer is the quantum dot thin film of claim 7.
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| CN108586711A (en) * | 2018-05-14 | 2018-09-28 | 华南理工大学 | A kind of side chain contains poly- spiro fluorene of cavity transmission group and the preparation method and application thereof |
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| 有机空穴传输材料在钙钛矿太阳电池中的应用;刘雪朋等;《物理化学学报》;20160615;第32卷(第6期);第1362-1363、1366页 * |
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