CN114686231A - Particle, preparation method thereof and quantum dot light-emitting diode - Google Patents
Particle, preparation method thereof and quantum dot light-emitting diode Download PDFInfo
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- CN114686231A CN114686231A CN202011613541.3A CN202011613541A CN114686231A CN 114686231 A CN114686231 A CN 114686231A CN 202011613541 A CN202011613541 A CN 202011613541A CN 114686231 A CN114686231 A CN 114686231A
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Abstract
The invention discloses a particle and a preparation method thereof, and a quantum dot light-emitting diode, wherein the particle comprises: quantum dots, and boron-oxygen-ring halide compound ligands bound to the surfaces of the quantum dots. The invention adopts the boron-oxygen-halide ring compound ligand modified quantum dots to form a quantum dot layer, and uses boron-oxygen ring compounds as the quantum dot ligands to form high-mobility network structure ligands on the surfaces of the quantum dots to provide high charge mobility, thereby promoting the injection of holes into the quantum dot light-emitting layer and improving the light-emitting efficiency.
Description
Technical Field
The invention relates to the field of quantum dot light-emitting devices, in particular to particles, a preparation method of the particles and a quantum dot light-emitting diode.
Background
Quantum Dots (QDs) are generally composed of dozens to millions of atoms, have a geometric size close to that of excitons, partially inherit the characteristics of bulk semiconductors, show unique photoelectric properties, are widely applied to the field of light emission, and can be used as a light emitting layer to be made into quantum dot light emitting diodes (QLEDs). Compared with an organic electroluminescent diode, the quantum dot light-emitting diode has the advantages of narrow light-emitting spectrum, wide color gamut, good stability, low manufacturing cost and the like.
At present, the transmission and injection of electrons and holes in a QLED device are unbalanced, the hole mobility is generally lower than the electron mobility due to the mechanism problem of hole generation and the material limitation, and the light emitting efficiency of the device is low due to insufficient hole transmission in most cases.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the present invention aims to provide a particle, a preparation method thereof, and a quantum dot light emitting diode, and aims to solve the problem that the current electron and hole transport and injection are not balanced, which results in the reduction of the light emitting efficiency of the quantum dot light emitting diode.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a particle comprising a quantum dot, and a boron halide oxygen ring type compound ligand bound to the surface of the quantum dot. In a second aspect of the present invention, there is provided a method for preparing particles, comprising the steps of:
dispersing boron-oxygen ring compounds and halides in a solvent to obtain a mixed solution containing boron-oxygen ring halide compounds;
under the condition of a preset temperature, quantum dots are added into a mixed solution containing boron halide oxygen-ring compounds, so that the boron halide oxygen-ring compounds are combined with the surfaces of the quantum dots to obtain particles.
In a third aspect, a quantum dot light emitting diode comprises a quantum dot layer, wherein the quantum dot layer comprises the particles as described above.
Has the advantages that: the invention adopts the quantum dots combined with boron-oxygen-halogenated ring compounds to form a quantum dot layer, and uses the boron-oxygen-halogenated ring compounds as ligands of the quantum dots to form the net-shaped ligand on the surface of the quantum dots, the net-shaped ligand can improve the charge mobility, and meanwhile, the ligand has negative charges to greatly improve the attraction of the quantum dots to holes, thereby promoting the injection of the holes to the quantum dot light-emitting layer, improving the transmission and injection balance of electrons and holes, and improving the luminous efficiency.
Drawings
Fig. 1 is a schematic structural diagram of a quantum dot light emitting diode provided in an embodiment of the present invention;
fig. 2 is a schematic flow chart of a method for manufacturing a quantum dot light emitting diode provided in an embodiment of the present invention.
Detailed Description
The invention provides a quantum dot light-emitting diode and a preparation method thereof, 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.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The embodiment of the invention provides a particle, which comprises quantum dots and boron halide oxygen ring compound ligands combined with the surfaces of the quantum dots.
In the embodiment, the quantum dots are modified, that is, the surfaces of the quantum dots are modified by adopting boron-oxygen halide ring compound ligands, and the boron-oxygen ring ligands containing halogen ions form high-mobility network-structure ligands with negative charges on the surfaces of the quantum dots, so that the attraction of the quantum dots to holes can be greatly improved by the negative charges carried by the ligands while the high-charge mobility is provided, the injection of the holes into a quantum dot light-emitting layer is promoted, and the light-emitting efficiency is improved.
In this embodiment, the quantum dots are oil soluble quantum dots selected from the group consisting of group II-VI CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, znsses, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, cdhgznte, CdZnSeTe, CdHgSTe, hgzneses, HgZnSeTe, HgTe; or group III-V GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaGaAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InInInAlN, InLNAs, InAsInNSb, InAlGaAs, InLPSb; or group IV-VI SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; or a combination of any one or more of the above.
In this embodiment, the surface of the oil-soluble quantum dot is linked with a ligand that is easily soluble in a less polar solvent, including but not limited to acid ligands, thiol ligands, amine ligands, (oxy) phosphine ligands, phospholipids, lecithin, polyvinylpyridine, and the like. By way of example, the acid ligand is at least one of deca acid, undecenoic acid, tetradecanoic acid, oleic acid, stearic acid; the mercaptan ligand is at least one of octaalkylmercaptan, dodecyl mercaptan and octadecyl mercaptan; the amine ligand comprises at least one of oleylamine, octadecylamine and octaamine; the (oxy) phosphine ligand is at least one of trioctylphosphine and trioctylphosphine oxide.
In this embodiment, the boron-oxygen ring-based compound in the boron halide-oxygen ring-based compound ligand refers to a cyclic compound formed of a boron atom and an oxygen atom, the cyclic compound having a plurality of oxygen atoms and a plurality of boron atoms, and the electron-rich oxygen atom and the electron-poor boron atom being capable of forming a chelate ring having a certain binding power naturally. The boron-oxygen ring compound comprises: boron-oxygen polycyclic compounds and boron-oxygen Covalent Organic Frameworks (COFs) materials. Among them, the boroxopolycyclic compounds include, but are not limited to, boroxohexacyclic compounds, boroxooctacyclic compounds, boroxododecacyclic compounds, boroxotetradecylcompounds, boroxohexadecylcyclic compounds, and the like.
In one embodiment, the mass ratio of the quantum dots to the boron oxide oxygen ring-based compound (ligand) may be 10:1,40:1, 60:1,80:1,100:1, etc. By controlling the mass ratio of the quantum dots to the ligand within the above range, quantum dots with good modification effect can be obtained, i.e., the modified quantum dots have high charge mobility.
In one embodiment, the boron-oxygen hexacyclic compound has the formula:
wherein R is1To R3At least one of which is an electron donating group.
In this embodiment, R1、R2、R3Can be mercapto-SH, carboxyl-COOH, amino-NH2Phosphine group-PxOyAnd the like, wherein x and y are natural numbers. And forming a coordination bond between the electron-donating group and Zn or Cd on the surface of the quantum dot to form a ligand of the quantum dot. When R is1To R3In R1When it is an electron-donating group, R2、R3And may be an alkyl group of 4 to 18 carbon atoms.
In the present embodiment, the boron halide oxygen ring compound refers to a ring compound formed of a boron atom and an oxygen atom modified with a halide. The halide refers to a simple halogen substance, a halogen inorganic compound, or a halogen organic compound having ionization potential; by way of example, halides are compounds such as hydrogen halides that have a certain ionization capacity. A cyclic compound comprising a boron atom and an oxygen atom, the cyclic compound having a plurality of oxygen atoms and a plurality of boron atoms, wherein an electron-rich oxygen atom and an electron-poor boron atom are capable of forming a chelate ring having a certain binding power naturally.
By way of example, boron-oxygen-six ring and hydrogen chloride are used as raw materials, halogen ions are introduced through a solution method, the halogen ions are limited in the boron-oxygen-six ring in a chelate form, and a boron-oxygen-six ring material with negative electricity is formed and serves as a ligand of a quantum dot. The structural formula of the halogen modified boron-oxygen hexacyclic compound is as follows:
In this embodiment, when the boron-oxygen ring compound is used as a ligand, the negative charge of the ligand can greatly increase the attraction of the quantum dot to the hole by introducing a halogen ion into the boron-oxygen ring compound, thereby promoting the injection of the hole into the quantum dot light-emitting layer and improving the light-emitting efficiency.
It should be noted that the quantum dot light emitting diode can be divided into a positive type structure and an inversion type structure. The structure and material selection of the quantum dot light emitting diode of this embodiment will be described below by taking the quantum dot light emitting diode of the positive type structure shown in fig. 1 as an example. As shown in fig. 1, the quantum dot light emitting diode includes, from bottom to top, a substrate 1, an anode 2, a hole transport layer 3, a quantum dot layer 4, an electron transport layer 5, and a cathode 6; wherein the quantum dot layer is formed by quantum dots of which the surfaces are combined with boron halide oxygen ring compound ligands.
In the present embodiment, the surface of the quantum dot layer refers to a surface that is in contact with other functional layers. It is easily understood that the quantum dot light emitting diode may further include: and functional layers such as a hole injection layer, a hole transport layer, and an electron transport layer. The quantum dot layer is formed between the hole transport layer and the electron transport layer, and the surface of the quantum dot layer, which is in contact with the hole transport layer and the electron transport layer, is the surface of the quantum dot layer.
In one embodiment, the substrate may be a rigid substrate or a flexible substrate, and the substrate is selected from glass, a silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyether sulfone, a combination thereof, or the like.
In one embodiment, the material of the anode may be selected from nickel, platinum, vanadium, chromium, copper, zinc, gold, or alloys thereof; the material of the anode can also be selected from one or more of zinc oxide, indium oxide, tin oxide, indium zinc oxide, indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide and the like; the material of the anode may be any two or a combination of two or more of the above.
In one embodiment, the material of the hole injection layer may be selected from materials having good hole injection properties, such as but not limited to one or more of poly (3, 4-ethylenedioxythiophene) -polystyrenesulfonic acid (PEDOT: PSS), copper phthalocyanine (CuPc), 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane (F4-TCNQ), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazatriphenylene (HATCN), doped or undoped transition metal oxides, doped or undoped metal chalcogenide compounds; wherein the transition metal oxide includes, but is not limited to, MoO3、VO2、WO3One or more of CuO and CuO; metal chalcogenide compounds including but not limited to MoS2、MoSe2、WS2、WSe2And CuS. In one embodiment, the hole injection layer has a thickness of 10 to 150 nm.
In one embodiment, the material of the hole transport layer may be selected from organic materials having good hole transport ability, such as but not limited to Poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB), Polyvinylcarbazole (PVK), Poly (N, N 'bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) (Poly-TPD), Poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-Phenylenediamine) (PFB), 4', 4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 4' -bis (9-Carbazole) Biphenyl (CBP), N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), doped graphene, undoped graphene, C60. In one embodiment, the hole transport layer has a thickness of 10 to 150 nm.
In one embodiment, the electron transport layer may be selected from ZnO, TiO2、Alq3、SnO、ZrO、 AlZnO、ZnSnO、BCP、TAZ、PBD、TPBI、Bphen、CsCO3One or more of (a). In one embodiment, the electron transport layer has a thickness of 5 to 100 nm.
In one embodiment, the cathode may be selected from metals or alloys thereof, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or alloys thereof; the cathode may also be composed of a multi-layered structure of materials, such as a first layer of an alkali metal halide, an alkaline earth metal halide, an alkali metal oxide, or a combination thereof, and a second layer of an alkaline earth metal, a group 13 metal, or a combination thereof, on the first layer. For example, the cathode is LiF/Al, LiO2Al, LiF/Ca, Liq/Al, and BaF2But not limited thereto,/Ca.
Based on the same inventive concept, the embodiment of the present invention provides a method for preparing particles, as shown in fig. 2, including the steps of:
s10, dispersing the boron-oxygen ring compound and the halide in a solvent to obtain a mixed solution containing the boron-oxygen ring halide compound.
Specifically, the boron-oxygen cyclic compound and the halide may be dispersed in a nonpolar solvent or the boron-oxygen cyclic compound and the halide may be dispersed in the ink in an inert atmosphere to obtain a mixed solution; and then raising the temperature to 50-80 ℃, for example, raising the temperature to 50 ℃, uniformly stirring, and adding quantum dots into the mixed solution to obtain a quantum dot solution of the boron-oxygen-ring halide compound ligand.
In the present embodiment, the non-polar solvent may be, but is not limited to, one or more of chloroform, toluene, chlorobenzene, n-hexane, n-octane, decalin, tridecane, n-octylbenzene, Trioctylphosphine (TOP), Tributylphosphine (TBP), Octadecene (ODE), Oleic Acid (OA), Octadecylamine (ODA), Trioctylamine (TOA), oleylamine (OAm), and the like. It is readily understood that the ink refers to quantum dot ink. The quantum dot ink contains a large amount of solvent and thus can serve as a dispersion solvent. In the quantum dot ink, the concentration of the quantum dots can be 1mg/mL to 20mg/mL, 20mg/mL to 50mg/mL, 50mg/mL to 70mg/mL, 70mg/mL to 100mg/mL, 100mg/mL to 150mg/mL, 150mg/mL to 200 mg/mL. The quantum dots with the concentration range have the characteristics of good solution processing performance and good dispersibility.
In one embodiment of this embodiment, under an inert atmosphere, the boron-oxygen ring compound may be dispersed in a nonpolar solvent or ink to obtain a boron-oxygen ring compound solution with a certain concentration, a halide with a certain concentration may be added to the boron-oxygen ring compound solution, the mixture may be heated and stirred uniformly, and quantum dots may be added to obtain a quantum dot solution of a boron-oxygen ring halide ligand. Wherein the molar ratio of the boron-oxygen ring compound to the halide is 1-2: 1. By way of example, the molar ratio of boron oxygen ring compound to halide is 1: 1. If the halide ratio is too high, the conductivity of the final boroxine compound is lowered, and if the halide ratio is too low, the ionization is too low, resulting in insignificant modification effect.
S20, adding quantum dots into the mixed solution containing the boron halide oxygen-ring compounds under the condition of preset temperature, and bonding the boron halide oxygen-ring compounds with the surfaces of the quantum dots to obtain the particles.
In this example, the boron-oxygen ring-based compound was modified with a halide, and the obtained boron-oxygen ring-based halide compound contained a halogen ion, so that the boron-oxygen ring-based compound could be negatively charged. When the boron-oxygen ring compound with negative charges is used as the quantum dots of the quantum dot ligand to form the quantum dot layer, the high-mobility net-shaped ligand with negative charges is formed on the surface of the quantum dots, so that the attraction of the quantum dots to holes can be greatly improved by the negative charges carried by the ligand while the high-charge mobility is provided, the injection of the holes to the quantum dot light-emitting layer is promoted, and the light-emitting efficiency is improved.
It should be noted that the specific steps for preparing the quantum dot layer, the selection of the process parameters, and the like are not limited herein.
The present invention will be described in detail below with reference to examples.
EXAMPLE 1
1. Hydrogen chloride is utilized to modify 1-mercapto boron-oxygen hexacyclic ring, wherein the quantum dots are CdSeS/ZnS green quantum dots with the particle size of 5-10 nm.
1-mercapto boron-oxygen-hexacyclic compound is dispersed in n-octane under the argon atmosphere, the concentration is 3mmol/mL, then HCl and hydrogen chloride are added according to the proportion of 3mmol/mL, the temperature is raised to 50 ℃, and the mixture is stirred for 30min at the rotating speed of 3000 rpm. Then, CdSeS/ZnS green quantum dots are added into the solution at the concentration of 30mg/mL to prepare a quantum dot solution for later use.
2. Preparing a quantum dot light-emitting diode:
firstly, spin-coating a material of a hole injection layer on a substrate, then spin-coating a hole transport layer on the hole injection layer, and then spin-coating the quantum dot solution prepared in the step 1 on the hole transport layer to prepare the quantum dot light-emitting layer.
And placing the substrate on which the quantum dot light emitting layer is spin-coated on a spin coater, and spin-coating the prepared precursor solution with a certain concentration to form a film. And then, placing the substrate on which the functional layers are deposited in an evaporation bin, and thermally evaporating a layer of aluminum as a cathode through a mask plate.
This embodiment quantum dot light emitting diode includes from bottom to top in proper order: an anode, a hole injection layer, a hole transport layer, a quantum dot layer, an electron transport layer and a cathode are sequentially deposited on the substrate. Wherein the substrate is a glass substrate; the anode is ITO with the thickness of 120 nm; PSS, the thickness of the hole injection layer is 80 nm; the hole transport layer was TFB and was 70nm thick. The quantum dot layer is formed by depositing the quantum dot solution prepared in the step 1, and the thickness of the quantum dot layer is 70 nm. The electron transmission layer is ZnO with the thickness of 50 nm; the cathode is Al and has a thickness of 60 nm.
Comparative example 1
Consistent with example 1, except that the quantum dot layer was formed of CdSeS/ZnS green quantum dots without modification.
EXAMPLE 2
1. Hydrogen bromide is used for modifying 1-octylamino boron-oxygen hexacyclic ring, wherein the quantum dots are CdSeS/ZnS green quantum dots with the particle size of 5-10 nm.
1-octylamino boron-oxygen hexacyclic compound is dispersed in n-octane at the concentration of 4mmol/mL, HBr hydrogen bromide is added at the ratio of 2mmol/mL, the temperature is raised to 55 ℃, and the mixture is stirred at 3500rpm for 30 min. Then, CdSeS/ZnS green quantum dots are added into the solution at the concentration of 30mg/mL to prepare a quantum dot solution for later use.
2. Preparing a quantum dot light-emitting diode:
firstly, spin-coating a material of a hole injection layer on a substrate, then spin-coating a hole transport layer on the hole injection layer, and then spin-coating the quantum dot solution prepared in the step 1 on the hole transport layer to prepare the quantum dot light-emitting layer.
And placing the substrate on which the quantum dot light emitting layer is spin-coated on a spin coater, and spin-coating the prepared precursor solution with a certain concentration to form a film. And then, placing the substrate on which the functional layers are deposited in an evaporation bin, and thermally evaporating a layer of aluminum as a cathode through a mask plate.
This embodiment quantum dot light emitting diode includes from bottom to top in proper order: an anode, a hole injection layer, a hole transport layer, a quantum dot layer, an electron transport layer and a cathode are sequentially deposited on the substrate. Wherein the substrate is a glass substrate; the anode is ITO with the thickness of 110 nm; PSS, the thickness of the hole injection layer is 60 nm; the hole transport layer was TFB and was 60nm thick. The quantum dot layer is formed by depositing the quantum dot solution prepared in the step 1, and the thickness of the quantum dot layer is 80 nm. The electron transmission layer is ZnO with the thickness of 60 nm; the cathode was Al and had a thickness of 65 nm.
EXAMPLE 3
1. The 1, 3-dioctylamino boron-oxygen-hexacyclic is modified by hydrogen bromide, wherein the quantum dot is CdSeS/ZnS green quantum dot with particle size of 5-10 nm.
1-octylamino boron-oxygen hexacyclic compound is dispersed in n-octane, the concentration is 3mmol/mL, HBr hydrogen bromide is added in the proportion of 3mmol/mL, the temperature is raised to 50 ℃, and the mixture is stirred for 30min at the rotating speed of 3500 rpm. Then, CdSeS/ZnS green quantum dots are added into the solution at the concentration of 30mg/mL to prepare a quantum dot solution for later use.
2. Preparing a quantum dot light-emitting diode:
firstly, spin-coating the material of the electron injection layer on the substrate, then spin-coating the electron transport layer on the electron injection layer, and then spin-coating the quantum dot solution prepared in the step 1 on the electron transport layer to prepare the quantum dot light-emitting layer. And depositing a hole transport layer and a hole injection layer on the quantum dot light emitting layer in sequence. And then, placing the substrate on which the functional layers are deposited in an evaporation bin, and thermally evaporating a layer of copper as an anode through a mask plate.
This embodiment quantum dot light emitting diode includes from bottom to top in proper order: a cathode, an electron injection layer, an electron transport layer, a quantum dot layer, a hole transport layer, a hole injection layer and an anode which are sequentially deposited on the substrate. Wherein the substrate is a glass substrate; the anode is Cu, and the thickness is 110 nm; the electron injection layer is PEDOT, PSS, the thickness is 60 nm; the electron transport layer was TFB and had a thickness of 60 nm. The quantum dot layer is formed by depositing the quantum dot solution prepared in the step 1, and the thickness of the quantum dot layer is 80 nm. The electron transmission layer is ZnO with the thickness of 60 nm; the cathode was Al and had a thickness of 65 nm.
Example 4
1. Hydrogen chloride is utilized to modify 1-octyl boron-oxygen phosphate hexacyclic ring, wherein the quantum dots adopt CdSeS/ZnS green quantum dots with the particle size of 5-10 nm.
1-octyl boron-oxygen phosphate hexacyclic oxide is dispersed in n-octane under the argon atmosphere, the concentration is 3mmol/mL, then HCl and hydrogen chloride are added according to the proportion of 3mmol/mL, the temperature is raised to 50 ℃, and the stirring is carried out for 30min at the rotating speed of 3000 rpm. Then, CdSeS/ZnS green quantum dots are added into the solution at the concentration of 30mg/mL to prepare a quantum dot solution for later use.
2. Preparing a quantum dot light-emitting diode:
firstly, spin-coating a material of a hole injection layer on a substrate, then spin-coating a hole transport layer on the hole injection layer, and then spin-coating the quantum dot solution prepared in the step 1 on the hole transport layer to prepare the quantum dot light-emitting layer.
And placing the substrate on which the quantum dot light emitting layer is spin-coated on a spin coater, and spin-coating the prepared precursor solution with a certain concentration to form a film. And then, placing the substrate on which the functional layers are deposited in an evaporation bin, and thermally evaporating a layer of aluminum as a cathode through a mask plate.
This embodiment quantum dot light emitting diode includes from bottom to top in proper order: an anode, a hole injection layer, a hole transport layer, a quantum dot layer, an electron transport layer and a cathode deposited on the substrate in sequence. Wherein the substrate is a glass substrate; the anode is ITO with the thickness of 120 nm; PSS, the thickness of the hole injection layer is 80 nm; the hole transport layer was TFB and was 70nm thick. The quantum dot layer is formed by depositing the quantum dot solution prepared in the step 1, and the thickness of the quantum dot layer is 70 nm. The electron transmission layer is ZnO with the thickness of 50 nm; the cathode is Al and has a thickness of 60 nm.
The quantum dot layers and quantum dot light emitting diodes prepared in comparative example 1 and examples 1 to 4 were subjected to the following performance tests, the test methods being as follows:
hole mobility:
the current density (J) -voltage (V) of the QLED devices fabricated using the quantum dots of examples 1-4 were tested, a plot was drawn, the Space Charge Limited Current (SCLC) region in the plot was fitted, and then the hole mobility was calculated according to the well-known Child, s law formula as follows:
J＝(9/8)εrε0μeV2/d3，
wherein J represents current density in mAcm-2；εrDenotes the relative dielectric constant,. epsilon0Represents the vacuum dielectric constant; mu.seDenotes hole mobility in cm2V-1s-1(ii) a V represents the drive voltage, in units of V; d represents the film thickness in m, and the test results are shown in table 1 below:
TABLE 1 device hole mobility and EQE prepared in comparative example 1 and examples 1-4
As can be seen from the test results in table 1 above, the hole mobility of the QLED devices made of the quantum dots prepared in examples 1 to 4 of the present invention is significantly higher than that of comparative example 1 using the conventional hole transport material, and the EQE of the QLED devices is also significantly higher.
In summary, the present invention provides a quantum dot light emitting diode and a method for manufacturing the same, including: and a quantum dot layer, wherein the quantum dot layer comprises quantum dots with boron-oxygen-halide ring compounds bonded on the surfaces. The quantum dots modified by the boron-oxygen-halogenated ring compound ligand are used for forming a quantum dot layer, the boron-oxygen-halogenated ring compound is used as the quantum dot ligand, the high-mobility net-shaped ligand is formed on the surface of the quantum dot, and the ligand has negative charges, so that the attraction of the quantum dot to a hole can be greatly improved, the injection of the hole into a quantum dot light emitting layer is promoted, and the light emitting efficiency is further improved.
It will be understood that the invention is not limited to the examples described above, but that modifications and variations will occur to those skilled in the art in light of the above teachings, and that all such modifications and variations are considered to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A particle comprising a quantum dot, a boron-oxygen-ring halide ligand bound to the surface of the quantum dot.
2. The particle of claim 1, wherein the boron-oxygen ring-type compound of the boron halide-oxygen ring-type compound ligand comprises: one or more of a boroxine polycyclic compound and a boroxine covalent organic framework material.
3. The particle of claim 2, wherein the boroxine compound is selected from one or more of boroxine compounds, and boroxine compounds.
4. The particle according to claim 3, wherein the boron-oxygen polycyclic compound is a boron-oxygen-hexacyclic compound having a structural formula shown below:
wherein R is1To R3At least one of themAre electron donating groups.
5. The particle of claim 4, wherein the electron donating group is selected from one or more of a thiol group, a carboxyl group, an amino group, and a phosphine group.
6. The particle of claim 1, wherein the mass ratio of the quantum dots to the boron oxide oxygen ring-based compound is 10-100: 1.
7. A method of making a particle, comprising the steps of:
dispersing the boron-oxygen ring compound and halide in a solvent to obtain a mixed solution containing a boron-oxygen ring halide compound;
under the condition of a preset temperature, quantum dots are added into the mixed solution containing the boron halide oxygen-ring compounds, and the boron halide oxygen-ring compounds are combined with the surfaces of the quantum dots to obtain the particles.
8. The method according to claim 7, wherein the quantum dot is an oil-soluble quantum dot.
9. The method of claim 8, wherein the step of dispersing the boron-oxygen ring-type compound and the halide in a solvent to obtain a mixed solution containing the boron-oxygen ring-type halide compound comprises:
dispersing the boron-oxygen ring compound in a solvent to obtain a boron-oxygen ring compound solution;
dispersing halide in the boron-oxygen ring compound solution to obtain a mixed solution containing boron-oxygen ring halide compounds;
the molar ratio of the boron-oxygen ring compound to the halide is 1: 1-2.
10. A quantum dot light emitting diode comprising a quantum dot layer, wherein the quantum dot layer comprises the particle of any one of claims 1-6.
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