CN110890467A - Quantum dot light-emitting diode - Google Patents
Quantum dot light-emitting diode Download PDFInfo
- Publication number
- CN110890467A CN110890467A CN201811044363.XA CN201811044363A CN110890467A CN 110890467 A CN110890467 A CN 110890467A CN 201811044363 A CN201811044363 A CN 201811044363A CN 110890467 A CN110890467 A CN 110890467A
- Authority
- CN
- China
- Prior art keywords
- electron transport
- transport layer
- particles
- quantum dot
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 153
- 239000002245 particle Substances 0.000 claims abstract description 184
- 239000013110 organic ligand Substances 0.000 claims abstract description 152
- 239000004054 semiconductor nanocrystal Substances 0.000 claims abstract description 142
- 239000000463 material Substances 0.000 claims abstract description 137
- 239000003446 ligand Substances 0.000 claims abstract description 124
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 95
- 150000002367 halogens Chemical class 0.000 claims abstract description 84
- 239000004065 semiconductor Substances 0.000 claims abstract description 33
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 75
- 125000004432 carbon atom Chemical group C* 0.000 claims description 64
- 150000003573 thiols Chemical class 0.000 claims description 52
- -1 halogen ion Chemical class 0.000 claims description 44
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 36
- 229910044991 metal oxide Inorganic materials 0.000 claims description 31
- 150000004706 metal oxides Chemical class 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 20
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 150000001721 carbon Chemical group 0.000 claims description 14
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
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- 229910052727 yttrium Inorganic materials 0.000 claims description 11
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 10
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 10
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- SMOJNZMNQIIIPK-UHFFFAOYSA-N silylphosphane Chemical class P[SiH3] SMOJNZMNQIIIPK-UHFFFAOYSA-N 0.000 claims description 9
- 150000003512 tertiary amines Chemical class 0.000 claims description 9
- 150000003141 primary amines Chemical class 0.000 claims description 7
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 10
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- 229910021380 Manganese Chloride Inorganic materials 0.000 description 8
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 8
- 229910021574 Manganese(II) iodide Inorganic materials 0.000 description 8
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- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 8
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- 229910052794 bromium Inorganic materials 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
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- 238000001704 evaporation Methods 0.000 description 8
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- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 8
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 8
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- 239000011565 manganese chloride Substances 0.000 description 8
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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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- 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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/165—Electron transporting layers comprising dopants
-
- 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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/166—Electron transporting layers comprising a multilayered structure
-
- 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
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a quantum dot light-emitting diode, comprising: the anode, the cathode and the lamination arranged between the anode and the cathode comprise a quantum dot light-emitting layer and an electron transport layer which are arranged in a lamination mode, the quantum dot light-emitting layer is arranged close to one side of the anode, the electron transport layer is arranged close to one side of the cathode, the electron transport layer comprises at least one first electron transport layer, and the first electron transport layer comprises: the organic semiconductor nano-particle comprises a particle, a halogen ligand and an oil-soluble organic ligand, wherein the halogen ligand and the oil-soluble organic ligand are combined on the surface of the particle, and the particle is an inorganic semiconductor nano-crystal. According to the oil-soluble first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of a luminous layer can be improved.
Description
Technical Field
The invention relates to the field of quantum dot light-emitting devices, in particular to a quantum dot light-emitting diode.
Background
In recent years, colloidal quantum dots have the characteristics of high quantum efficiency, high optical purity, adjustable emission wavelength and the like, and become novel display materials with the greatest development prospect. Researchers can mature and prepare quantum dot materials with photoluminescence efficiency as high as 100%, and the quantum dot materials can be widely applied to biomarkers, sensing devices and Light Emitting Diodes (LEDs).
In the preparation process of the quantum dot light-emitting diode, the external quantum efficiency of the device is very low, and the reported red, green and blue device efficiencies are all less than 20%. The reason why the photoluminescence efficiency and electroluminescence efficiency of quantum dot materials are so different is mainly because quantum dot materials use optical excitation, while devices use electrical excitation. In the device structure, the quantum dot light emitting layer has higher requirements on other functional layers such as an electron transport layer and a hole transport layer, and higher device efficiency and service life can be obtained only when the other functional layers achieve more ideal conditions in the aspects of work function, transport performance, stability and the like. An important factor determining the efficiency of a quantum dot device is that the electron transport rate and the hole transport rate are balanced, and in the current device structure, the electron transport rate is generally greater than the hole transport rate, and the electron transport rate and the hole transport rate are difficult to be balanced, so that the device efficiency and the service life are low.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, the present invention aims to provide a quantum dot light emitting diode, which aims to solve the problem that the electron transport rate is generally higher than the hole transport rate, and the balance between the electron transport rate and the hole transport rate is difficult to achieve in the conventional device structure, resulting in lower device efficiency and shorter service life.
The technical scheme of the invention is as follows:
a quantum dot light emitting diode comprising: the anode, the cathode and the lamination arranged between the anode and the cathode comprise a quantum dot light-emitting layer and an electron transport layer which are arranged in a lamination mode, the quantum dot light-emitting layer is arranged close to one side of the anode, the electron transport layer is arranged close to one side of the cathode, the electron transport layer comprises at least one first electron transport layer, and the first electron transport layer comprises: the organic semiconductor nano-particle comprises a particle, a halogen ligand and an oil-soluble organic ligand, wherein the halogen ligand and the oil-soluble organic ligand are combined on the surface of the particle, and the particle is an inorganic semiconductor nano-crystal.
Has the advantages that: in the first electron transport layer material of the present invention, the surface of the particle has a mixed ligand: a halogen ligand and an oil-soluble organic ligand which renders the first electron transport layer material oil-soluble. According to the oil-soluble first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of a luminous layer can be improved.
Drawings
Fig. 1 is a schematic structural diagram of a quantum dot light emitting diode according to an embodiment of the present invention.
FIG. 2 is a schematic structural diagram of the electron transport layer in FIG. 1.
FIG. 3 is another structural diagram of the electron transport layer in FIG. 1.
Detailed Description
The present invention provides a quantum dot light emitting diode, and the present invention will be described in further detail below in order to make the objects, technical solutions, and effects of the present 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.
The embodiment of the invention provides a quantum dot light-emitting diode, which comprises: the anode, the cathode and the lamination arranged between the anode and the cathode comprise a quantum dot light-emitting layer and an electron transport layer which are arranged in a lamination mode, the quantum dot light-emitting layer is arranged close to one side of the anode, the electron transport layer is arranged close to one side of the cathode, the electron transport layer comprises at least one first electron transport layer, and the first electron transport layer comprises: the organic semiconductor nano-particle comprises a particle, a halogen ligand and an oil-soluble organic ligand, wherein the halogen ligand and the oil-soluble organic ligand are combined on the surface of the particle, and the particle is an inorganic semiconductor nano-crystal.
In the first electron transport layer material of the present invention, the surface of the particle has a mixed ligand: a halogen ligand and an oil-soluble organic ligand which renders the first electron transport layer material oil-soluble. According to the oil-soluble first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of a luminous layer can be improved.
In this embodiment, the quantum dot light emitting diode has various forms, and the quantum dot light emitting diode is divided into a formal structure and a trans-structure, and this embodiment will be mainly described with the quantum dot light emitting diode of the formal structure as shown in fig. 1. Specifically, as shown in fig. 1, the quantum dot light emitting diode includes a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a quantum dot light emitting layer 5, an electron transport layer 6, and a cathode 7, which are stacked from bottom to top; wherein the electron transport layer 6 comprises at least one first electron transport layer comprising: the organic semiconductor nano-particle comprises a particle, a halogen ligand and an oil-soluble organic ligand, wherein the halogen ligand and the oil-soluble organic ligand are combined on the surface of the particle, and the particle is an inorganic semiconductor nano-crystal. The structure of the electron transport layer 6 will be described in detail below.
In a preferred embodiment, the material of the quantum dot light emitting layer is water-soluble quantum dot, and the electron transport layer 6 is a first electron transport layer 61, as shown in structure 1 in fig. 2. In the first electron transport layer material, the surface of the particle has mixed ligand: a halogen ligand and an oil-soluble organic ligand which renders the first electron transport layer material oil-soluble. According to the oil-soluble first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of the luminous layer can be improved.
In a preferred embodiment, the material of the quantum dot light-emitting layer is a water-soluble quantum dot, and the electron transport layer further comprises at least one second electron transport layer, and the material of the second electron transport layer is a water-soluble electron transport material, wherein a first electron transport layer is disposed on the quantum dot light-emitting layer, a first electron transport layer is disposed on the first electron transport layer, and a second electron transport layer is disposed on the first electron transport layer, and each subsequent electron transport layer is disposed on each preceding different kind of electron transport layer. Preferably, the total number of the first electron transport layer and the second electron transport layer is 3 to 6 layers in order to maintain a suitable electron transport distance and not to make the device too thick. In a device, different functional layers need to be adjacent to each other, either water soluble or oil soluble. In addition, because the surface of the water-soluble electron transport material is free of organic ligands, the water-soluble layer and the oil-soluble layer are alternately arranged in a laminated manner in the same functional layer, so that the electron transport distance can be further reduced, and the electron transport efficiency can be improved. The following describes a case where the total number of the first electron transport layer and the second electron transport layer is 2 to 6 with reference to fig. 2. It should be noted that the total number of the first electron transport layers and the total number of the second electron transport layers may be the same or different.
In a preferred embodiment, the electron transport layer 6 is composed of a first electron transport layer 621 and a second electron transport layer 622 that are stacked, where the first electron transport layer 621 is attached to the quantum dot light emitting layer, and the material of the quantum dot light emitting layer is a water-soluble quantum dot, as shown in structure 2 in fig. 2.
In a preferred embodiment, the electron transport layer 6 is composed of a first electron transport layer 631, a second electron transport layer 632, and a first electron transport layer 633, which are sequentially stacked, wherein the first electron transport layer 631 is disposed in close contact with the quantum dot light emitting layer, the quantum dot light emitting layer is made of water-soluble quantum dots, as shown in structure 3 in fig. 2.
In a preferred embodiment, the electron transport layer 6 is composed of a first electron transport layer 641, a second electron transport layer 642, a first electron transport layer 643, and a second electron transport layer 644, which are sequentially stacked, wherein the first electron transport layer 641 is attached to the quantum dot light emitting layer, and the material of the quantum dot light emitting layer is a water-soluble quantum dot, as shown in structure 4 in fig. 2.
In a preferred embodiment, the electron transport layer 6 is composed of a first electron transport layer 651, a second electron transport layer 652, a first electron transport layer 653, a second electron transport layer 654, and a first electron transport layer 655, which are sequentially stacked, wherein the first electron transport layer 651 is attached to the quantum dot light emitting layer, and the material of the quantum dot light emitting layer is a water-soluble quantum dot, as shown in structure 5 in fig. 2.
In a preferred embodiment, the electron transport layer 6 is composed of a first electron transport layer 661, a second electron transport layer 662, a first electron transport layer 663, a second electron transport layer 664, a first electron transport layer 665, and a second electron transport layer 666, which are sequentially stacked, wherein the first electron transport layer 661 is disposed to be attached to the quantum dot light emitting layer, and the quantum dot light emitting layer is made of water-soluble quantum dots, as shown in structure 6 in fig. 2.
In a preferred embodiment, the quantum dot light emitting layer material is an oil-soluble quantum dot, and the electron transport layer further comprises at least one second electron transport layer, and the second electron transport layer material is a water-soluble electron transport material, wherein a first electron transport layer and a second electron transport layer are stacked on the quantum dot light emitting layer, a first electron transport layer and a first electron transport layer are stacked on the first electron transport layer and the second electron transport layer, and each subsequent electron transport layer is stacked on each preceding different kind of electron transport layer. Preferably, the total number of the first electron transport layer and the second electron transport layer is 3 to 6 layers in order to maintain a suitable electron transport distance and not to make the device too thick. In a device, different functional layers need to be adjacent to each other, either water soluble or oil soluble. In addition, because the surface of the water-soluble electron transport material is free of organic ligands, the water-soluble layer and the oil-soluble layer are alternately stacked in the same functional layer, so that the electron transport distance can be further reduced, and the electron transport efficiency can be improved. The following describes a case where the total number of the first electron transport layer and the second electron transport layer is 2 to 6 with reference to fig. 3. It should be noted that the total number of the first electron transport layers and the total number of the second electron transport layers may be the same or different.
In a preferred embodiment, the electron transport layer 6 is composed of a second electron transport layer 621 ' and a first electron transport layer 622 ' which are stacked, wherein the second electron transport layer 621 ' is attached to the quantum dot light emitting layer, and the quantum dot light emitting layer is made of oil-soluble quantum dots, as shown in structure 1 in fig. 3.
In a preferred embodiment, the electron transport layer 6 is composed of a second electron transport layer 631 ', a first electron transport layer 632', and a second electron transport layer 633 'which are stacked, wherein the second electron transport layer 631' is disposed in close contact with the quantum dot light emitting layer, and the quantum dot light emitting layer is made of oil-soluble quantum dots, as shown in structure 2 in fig. 3.
In a preferred embodiment, the electron transport layer 6 is composed of a second electron transport layer 641 ', a first electron transport layer 642 ', a second electron transport layer 643 ' and a first electron transport layer 644 ' which are stacked, wherein the second electron transport layer 641 ' is attached to the quantum dot light emitting layer, and the quantum dot light emitting layer is made of oil-soluble quantum dots, as shown in structure 3 in fig. 3.
In a preferred embodiment, the electron transport layer 6 is composed of a second electron transport layer 651 ', a first electron transport layer 652', a second electron transport layer 653 ', a first electron transport layer 654' and a second electron transport layer 655 'which are stacked, wherein the second electron transport layer 651' is attached to the quantum dot light emitting layer, and the quantum dot light emitting layer is made of oil-soluble quantum dots, as shown in structure 4 in fig. 3.
In a preferred embodiment, the electron transport layer 6 is composed of a second electron transport layer 661 ', a first electron transport layer 662 ', a second electron transport layer 663 ', a first electron transport layer 664 ', a second electron transport layer 665 ', and a first electron transport layer 666 ' which are stacked, wherein the second electron transport layer 661 ' is disposed in close contact with the quantum dot, and the quantum dot light emitting layer is made of an oil-soluble quantum dot, as shown in structure 5 in fig. 3.
Further in a preferred embodiment, the second electron transport layer material may be selected from materials with good electron transport properties, such as but not limited to n-type ZnO particles, TiO2Particles, Ca particles, Ba particles, ZrO2Particles, CsF particles, LiF particles, CsCO3Particles and Alq3 particles, and the like. The water-soluble electron transport materials can be dispersed in water, methanol, ethanol, propanol, acetone and other solutions in an ionic form, the size of the nano-particles is 5-15 nm, and surface ligands are not available.
Further in a preferred embodiment, the water-soluble quantum dot is a quantum dot having a water-soluble ligand bound to the surface thereof.
Still further in a preferred embodiment, the water-soluble ligand is selected from one or more of the group consisting of a halogen ion ligand, a mercapto alcohol having less than 8 carbon atoms, a mercaptoamine having less than 8 carbon atoms, and a mercaptoacid having less than 8 carbon atoms. By way of example, the halide ion ligand is selected from one or more of chloride, bromide and iodide. By way of example, the mercaptoalcohol having a carbon number of less than 8 is selected from one or more of 2-mercaptoethanol, 3-mercapto-1-propanol, 4-mercapto-1-butanol, 5-mercapto-1-pentanol, 6-mercapto-1-hexanol, and the like. By way of example, the mercaptoamine having less than 8 carbon atoms is selected from one or more of 2-mercaptoethylamine, 3-mercaptopropylamine, 4-mercaptobutylamine, 5-mercaptopentylamine, 6-mercaptohexylamine, 2-amino-3-mercaptopropionic acid, and the like. By way of example, the mercapto acid having less than 8 carbon atoms is selected from one or more of 2-mercaptoacetic acid, 3-mercaptopropionic acid, 4-mercaptobutyric acid, mercaptosuccinic acid, 6-mercaptohexanoic acid, 4-mercaptobenzoic acid, cysteine, and the like.
Still further in a preferred embodiment, the quantum dots are selected from Au, Ag, Cu, Pt, C, CdSe, CdS, CdTe, CdS, CdZnSe, CdSeS, PbSeS, ZnCdTe, CdS/ZnS, CdZnS/ZnS, CdZnSe/ZnSe, CdSeS/CdSeS/CdS, CdSe/CdZnSe/CdZnSe/ZnSe, CdS/CdZnS/CdZnS/ZnS, NaYF4、NaCdF4One or more of, CdZnSeS, CdSe/ZnS, CdZnSe/ZnS, CdSe/CdS/ZnS, CdSe/ZnSe/ZnS, CdZnSe/CdZnS/ZnS, InP/ZnS, etc.
Further in a preferred embodiment, the oil-soluble quantum dot is a quantum dot having an oil-soluble organic ligand bound to the surface thereof. The types of the quantum dots are described above, and are not described in detail herein.
Still further in a preferred embodiment, the oil-soluble organic ligand is selected from one or more of a linear organic ligand having 8 or more carbon atoms, a secondary or tertiary amine having 4 or more branched carbon atoms, a substituted or unsubstituted alkylaminophosphine, a substituted or unsubstituted alkoxyphosphine, a substituted or unsubstituted silylphosphine, and an alkylphosphine having 4 or more branched carbon atoms. The specific types of oil-soluble organic ligands selected from the above classes are given below and will not be described in further detail herein.
In a preferred embodiment, the thickness of the electron transport layer is 20 to 60 nm.
In a preferred embodiment, the substrate may be a rigid substrate, such as glass, or a flexible substrate, such as one of PET or PI.
In a preferred embodiment, the anode may be selected from one or more of indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO), aluminum doped zinc oxide (AZO), and the like.
In a preferred embodiment, the hole transport layer material may be selected from one or more of NiO, CuO, CuS, TFB, PVK, Poly-TPD, TCTA, CBP, and the like. More preferably, the thickness of the hole transport layer is 20 to 40 nm.
In a preferred embodiment, the thickness of the quantum dot light emitting layer is 20 to 60 nm.
In a preferred embodiment, the cathode may be selected from one of an aluminum (Al) electrode, a silver (Ag) electrode, a gold (Au) electrode, and the like. More preferably, the thickness of the cathode is 60 to 100 nm.
It should be noted that the quantum dot light emitting diode of the present invention may further include one or more of the following functional layers: the electron blocking layer is arranged between the quantum dot light emitting layer and the electron transmission layer, and the electron injection layer is arranged between the electron transmission layer and the cathode.
The first electron transport layer material of this embodiment will be described in detail below.
The first electron transport layer material comprises: the organic semiconductor nano-particle comprises a particle, a halogen ligand and an oil-soluble organic ligand, wherein the halogen ligand and the oil-soluble organic ligand are combined on the surface of the particle, and the particle is an inorganic semiconductor nano-crystal.
In the first electron transport layer material described in this embodiment, the mixed ligand is provided on the surface of the particle: a halogen ligand and an oil-soluble organic ligand which renders the first electron transport layer material oil-soluble. According to the oil-soluble first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of the luminous layer can be improved. The oil-soluble organic ligand connected to the surface of the particle plays a role in surface passivation, and the surface defects are few.
In a preferred embodiment, the first electron transport layer material is non-emissive in the visible wavelength band, thereby ensuring that the first electron transport layer material can act as an electron transport material.
In a preferred embodiment, the inorganic semiconductor nanocrystal has a particle size of 2 to 7 nm. The inorganic semiconductor nano-crystal has small size and uniform particles, has better dispersibility when being dispersed in a solvent, and ensures that a solution formed by dispersing in the solvent is clear and has no precipitate.
In a preferred embodiment, the inorganic semiconductor nanocrystals are metal oxide particles selected from the group consisting of ZnO particles, CdO particles, SnO particles, and GeO particles, but not limited thereto. In another preferred embodiment, the inorganic semiconductor nanocrystal is a metal sulfide particle selected from ZnS particles, SnS particles or GeS particles, but is not limited thereto. In the embodiment of the invention, the inorganic semiconductor nanocrystal formed by the material has no emission in a visible waveband, can be used as an electron transport material, and does not influence the emission color of a luminescent layer of a quantum dot device.
In a preferred embodiment, the halogen ligand is selected from one or more of chloride, bromide and iodide.
Further in a preferred embodiment, the halogen ligand is chloride. Since chlorine has a small atomic radius relative to bromine and iodine, the distance over which electrons need to travel when the surface of the particle is used as a surface ligand is short, and thus the electron transport property can be improved.
In a preferred embodiment, the oil-soluble organic ligand is selected from one or more of a linear organic ligand having 8 or more carbon atoms, a secondary or tertiary amine having 4 or more branched carbon atoms, a substituted or unsubstituted alkylaminophosphine, a substituted or unsubstituted alkoxyphosphine, a substituted or unsubstituted silylphosphine, and an alkylphosphine having 4 or more branched carbon atoms, but is not limited thereto.
In a further preferred embodiment, the linear organic ligand having 8 or more carbon atoms is selected from one or more of an organic carboxylic acid having 8 or more carbon atoms, a thiol having 8 or more carbon atoms, an organic phosphoric acid having 8 or more carbon atoms, and a primary amine having 8 or more carbon atoms, but is not limited thereto. The organic carboxylic acid having 8 or more carbon atoms is selected from one or more of octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, hexadecanoic acid, and octadecanoic acid. By way of example, the thiol having 8 or more carbon atoms is one or more selected from octyl thiol, nonyl thiol, decyl thiol, dodecyl thiol, tetradecyl thiol, hexadecyl thiol, and octadecyl thiol. For example, the organic phosphoric acid having 8 or more carbon atoms is one or more selected from dodecyl phosphonic acid, tetradecyl phosphoric acid, hexadecyl phosphoric acid, and octadecyl phosphoric acid. For example, the primary amine having 8 or more carbon atoms is one or more selected from octylamine, nonylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, and the like.
In a further preferred embodiment, the secondary or tertiary amine having 4 or more carbon atoms as a branched chain is one or more selected from the group consisting of dibutylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, tributylamine, trihexylamine, triheptylamine, trioctylamine, trinonyl amine, tridecylamine, and the like.
Further in a preferred embodiment, the substituted or unsubstituted alkylaminophosphine is selected from one or more of tris (dimethylamino) phosphine, tris (diethylamino) phosphine, tris (dipropylamino) phosphine, tris (dibutylamino) phosphine, tris (dipentylamino) phosphine, tris (dihexylamino) phosphine, tris (diheptylamino) phosphine, tris (dioctylamino) phosphine, and dibenzyldiethylamino phosphine, but is not limited thereto.
Further in a preferred embodiment, the substituted or unsubstituted alkoxy phosphine is selected from one or more of tributyl phosphine oxide, tripentyl phosphine oxide, trihexyl phosphine oxide, triheptyl phosphine oxide, trioctyl phosphine oxide, trinonyl phosphine oxide, tridecyl phosphine oxide, diphenyl methoxy phosphine, diphenyl ethoxy phosphine oxide, diphenyl propoxy phosphine oxide, diphenyl butoxy phosphine oxide, dimethyl phenyl phosphine oxide, diethyl phenyl phosphine oxide, dipropyl phenyl phosphine oxide, dibutyl phenyl phosphine oxide, methyl diphenyl phosphine oxide, ethyl diphenyl phosphine oxide, propyl diphenyl phosphine oxide, butyl diphenyl phosphine oxide and chloro (diisopropylamino) methoxy phosphine oxide, but is not limited thereto.
Further in a preferred embodiment, the substituted or unsubstituted silyl phosphine is selected from one or more of tris (trimethylsilyl) phosphine, tris (triethylsilyl) phosphine, tris (tripropylsilyl) phosphine, tris (tributylsilyl) phosphine, tris (tripentylsilyl) phosphine, tris (trihexyl) phosphine, tris (triheptylsilyl) phosphine, and tris (trioctylsilyl) phosphine, but is not limited thereto.
Further in a preferred embodiment, the alkyl phosphine having 4 or more branched carbon atoms is selected from one or more of tributyl phosphine, triheptyl phosphine, and trioctyl phosphine, but is not limited thereto.
In a specific embodiment, the oil-soluble organic ligand is one or more of thiol with the carbon number of 8 or more, organic phosphoric acid with the carbon number of 8 or more and substituted or unsubstituted alkylamino phosphine. Because the organic phosphoric acid and the thiol ligand are respectively combined with the cations on the surface of the inorganic semiconductor nanocrystal by ionic bonds and hydrogen bonds, the alkylamino phosphine and the cations on the surface of the inorganic semiconductor nanocrystal can simultaneously adopt P lone electron pair or-NH2The first electron transport layer material has strong binding capacity and is not easy to fall off, the solubility and the transport property of the first electron transport layer material can be ensured, and the ligands and the inorganic semiconductor nanocrystalline surface ions can not be bound by-OH and can not be hydrolyzed.
In a specific embodiment, the oil-soluble organic ligand is a substituted or unsubstituted alkylaminophosphine and the particles are metal sulfide particles. Wherein the substituted or unsubstituted alkylaminophosphine and the cation on the surface of the particle can simultaneously adopt P lone electron pair or-NH2The halogen ligand has strong ionic bond, strong combination with the particle surface and difficult shedding. In addition, when the alkylamino phosphine and iodine ligands are combined with the metal sulfide particles, no-OH is combined with the surfaces of the metal sulfide particles, and the metal sulfide particles are not hydrolyzed or oxidized.
In a specific embodiment, the oil-soluble organic ligand is an organic phosphoric acid having 8 or more carbon atoms, and the particles are metal oxide particles. Wherein, the organic phosphoric acid is combined with the metal oxide particles by ionic bonds, and the combination ability is stronger. The metal oxide particles can not be directly combined with-OH and are not easy to be hydrolyzed and deteriorated.
In a specific embodiment, the oil-soluble organic ligand is a thiol having 8 or more carbon atoms, and the particles are metal sulfide particles. The mercaptan is combined with the cations on the surfaces of the metal sulfide particles through hydrogen bonds, and the metal sulfide particles are high in combining capacity and not easy to fall off. In addition, when the mercaptan is combined with the metal sulfide particles, no-OH is combined with the surfaces of the metal sulfide particles, and the metal sulfide particles cannot be hydrolyzed or oxidized.
In a preferred embodiment, the inorganic semiconductor nanocrystal contains a metal doping element. Due to the existence of the oil-soluble organic ligand, the electron transport performance of the organic ligand can be greatly reduced, the injection barrier of the electron transport layer to the luminescent layer can be reduced or redundant free electrons can be formed by further doping metal elements, and the electron transport performance can be properly improved, so that the electron transport rate and the hole transport rate in the device can be further adjusted, and the luminous efficiency of the luminescent layer can be further improved. Preferably, the metal doping element accounts for 0.5-10% of the inorganic semiconductor nanocrystal by mass percentage.
In a preferred embodiment, the metal doping element is selected from one or more of Mg, Mn, Al, Y, V and Ni, but is not limited thereto.
Further in a preferred embodiment, the inorganic semiconductor nanocrystal is selected from ZnO particles, ZnS particles or SnO particles, and the metal doping element is Al, V or Y. The HOMO energy level of the inorganic semiconductor nanocrystals can be better matched with the HOMO energy level of the light-emitting layer quantum dots, and the preferred doped ions can reduce the injection barrier of the electron transport layer to the light-emitting layer, so that the effectiveness of electron transport between the material of the transport layer and the material of the light-emitting layer is ensured. More preferably, the metal doping element is Y.
The embodiment of the invention also provides a preparation method of the quantum dot light-emitting diode with the formal structure as shown in figure 1, which comprises the following steps:
providing a substrate, and forming an anode on the substrate;
preparing a hole transport layer on the anode;
preparing a quantum dot light emitting layer on the hole transport layer;
preparing an electron transport layer on the quantum dot light emitting layer;
preparing a cathode on the electron transport layer to obtain the quantum dot light-emitting diode;
wherein the electron transport layer comprises at least one first electron transport layer, the first electron transport layer material comprising: the organic semiconductor nano-particle comprises a particle, a halogen ligand and an oil-soluble organic ligand, wherein the halogen ligand and the oil-soluble organic ligand are combined on the surface of the particle, and the particle is an inorganic semiconductor nano-crystal.
In the present invention, the preparation method of each layer may be a chemical method or a physical method, wherein the chemical method includes, but is not limited to, one or more of a chemical vapor deposition method, a continuous ionic layer adsorption and reaction method, an anodic oxidation method, an electrolytic deposition method, and a coprecipitation method; the physical method includes, but is not limited to, one or more of solution method (such as spin coating, printing, knife coating, dip-coating, dipping, spraying, roll coating, casting, slit coating, or bar coating), evaporation method (such as thermal evaporation, electron beam evaporation, magnetron sputtering, or multi-arc ion plating), deposition method (such as physical vapor deposition, atomic layer deposition, pulsed laser deposition, etc.).
The following describes in detail the preparation method of the first electron transport layer material according to the embodiment of the present invention:
the embodiment of the invention provides a preparation method of a first electron transport layer material, which comprises the following steps:
dispersing a cation precursor and a first oil-soluble organic ligand into a solvent, and heating at a first temperature to obtain a first mixture, wherein the cation precursor is a metal halide;
dispersing an anion precursor into a solvent, and heating at a second temperature to obtain a second mixture, wherein the anion precursor is organic alcohol;
and heating the first mixture at a third temperature, and injecting the second mixture in the heating process to perform crystal growth of inorganic semiconductor nanocrystals to obtain the first electron transport layer material, wherein the third temperature is higher than the first temperature and the second temperature.
In the embodiment, organic alcohol is used as an anion precursor, a halogen-containing cation precursor and the organic alcohol are subjected to alcoholysis reaction at a high temperature to obtain the metal oxide semiconductor nanocrystal, and halogen ions in the halogen-containing cation precursor and a first oil-soluble organic ligand are bonded to the surface of the metal oxide semiconductor nanocrystal. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The surface of the metal oxide semiconductor nanocrystal has mixed ligands: a halogen ligand and a first oil-soluble organic ligand that renders the first electron transport layer material oil-soluble. In the first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of the luminous layer can be improved.
In a preferred embodiment, the metal halide is selected from the group consisting of: one or more of chloride, bromide and iodide of zinc element; or,
one or more of chlorides, bromides and iodides of cadmium element; or,
one or more of chlorides, bromides and iodides of tin element; or,
one or more of chlorides, bromides and iodides of germanium elements. By way of example, the metal halide is selected from: ZnCl2、ZnBr2And ZnI2One or more of the following; alternatively, CdCl2、CdBr2And CdI2One or more of the following; or, SnCl2、SnBr2And SnI2One or more of the following; or, GeCl2、GeBr2And GeI2And the like.
Further in a preferred embodiment, the metal halide is selected from ZnCl2、CdCl2、SnCl2And GeCl2And the like. Since chlorine has a small atomic radius relative to bromine and iodine, the distance over which electrons need to travel when the surface of the particle is used as a surface ligand is short, and thus the electron transport property can be improved.
In a preferred embodiment, the first oil-soluble organic ligand is selected from one or more of organic carboxylic acids having 8 or more carbon atoms, organic phosphoric acids having 8 or more carbon atoms, primary amines having 8 or more carbon atoms, and secondary or tertiary amines having 4 or more branched carbon atoms.
In a further preferred embodiment, the first oil-soluble organic ligand is an organic phosphoric acid having 8 or more carbon atoms. Wherein, the organic phosphoric acid is combined with the metal oxide particles by ionic bonds, and the combination ability is stronger. The metal oxide particles can not be directly combined with-OH and are not easy to be hydrolyzed and deteriorated.
In a preferred embodiment, the organic alcohol is selected from one or more of octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, and the like. In a preferred embodiment, the first temperature is 110-.
In a preferred embodiment, the second temperature is 110-.
In this example, the prepared inorganic semiconductor nanocrystals were metal oxide particles. Preferably, the metal oxide particles are selected from ZnO particles, CdO particles, SnO particles, or GeO particles, but are not limited thereto. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The higher temperature is the third temperature in this embodiment. Preferably, the third temperature is 210-. More preferably, the third temperature is 230-300 ℃.
In a preferred embodiment, the first mixture is heated at a third temperature, the second mixture is injected during the heating process to perform crystal growth of the semiconductor nanocrystal, and after the crystal growth is completed, a third oil-soluble organic ligand is added during the cooling process to bond the third oil-soluble organic ligand on the surface of the semiconductor nanocrystal to obtain the first electron transport layer material, wherein the third oil-soluble organic ligand is thiol with a carbon atom number of 8 or more, and the third temperature is higher than the first temperature and the second temperature.
In a preferred embodiment, the step of dispersing the cation precursor and the first oil-soluble organic ligand in a solvent and heating at a first temperature to obtain a first mixture specifically comprises: dispersing a doped metal salt, a cation precursor and a first oil-soluble organic ligand into a solvent, and heating at a first temperature to obtain the first mixture.
Further in a preferred embodiment, the doping metal salt is selected from one or more of Mg salt, Mn salt, Al salt, Y salt, V salt and Ni salt, but not limited thereto. By way of example, the Mg salt may be chosen from MgCl2、MgI2、Mg(NO3)2May be selected from MnCl2、MnI2、Mn (NO3)2May be selected from AlCl3、AlI3、Al(CH3COO)3May be selected from YCl2、Y(CH3COO)2、Y(NO3)2May be selected from VCl2、V(CH3COO)2、V(NO3)2May be selected from NiCl2、Ni(CH3COO)2、Ni(NO3)2But is not limited thereto.
In a further preferred embodiment, in the material of the first electron transport layer, the inorganic semiconductor nanocrystals are selected from ZnO particles or SnO particles, and the inorganic semiconductor nanocrystals contain a metal doping element Al, V or Y. The HOMO energy level of the inorganic semiconductor nanocrystals can be better matched with the HOMO energy level of the light-emitting layer quantum dots, and the preferred doped ions can reduce the injection barrier of the electron transport layer to the light-emitting layer, so that the effectiveness of electron transport between the material of the transport layer and the material of the light-emitting layer is ensured. Preferably, the metal doping element is Y.
The embodiment of the invention provides a preparation method of a first electron transport layer material, which comprises the following steps:
dispersing a cation precursor into a solvent, and heating at a first temperature to obtain a first mixture, wherein the cation precursor is a metal halide;
dispersing an anion precursor and a second oil-soluble organic ligand into a solvent, and heating at a second temperature to obtain a second mixture, wherein the anion precursor is organic alcohol;
and heating the first mixture at a third temperature, and injecting the second mixture in the heating process to perform crystal growth of semiconductor nanocrystals to obtain the first electron transport layer material, wherein the third temperature is higher than the first temperature and the second temperature.
In the embodiment, organic alcohol is used as an anion precursor, a halogen-containing cation precursor and the organic alcohol are subjected to alcoholysis reaction at a high temperature to obtain the metal oxide semiconductor nanocrystal, and halogen ions in the halogen-containing cation precursor and a second oil-soluble organic ligand are bonded to the surface of the metal oxide semiconductor nanocrystal. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The surface of the metal oxide semiconductor nanocrystal has mixed ligands: a halogen ligand and a second oil-soluble organic ligand that renders the first electron transport layer material oil-soluble. In the first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of the luminous layer can be improved.
In a preferred embodiment, the metal halide is selected from the group consisting of: one or more of chloride, bromide and iodide of zinc element; or,
one or more of chlorides, bromides and iodides of cadmium element; or,
one or more of chlorides, bromides and iodides of tin element; or,
one or more of chlorides, bromides and iodides of germanium elements. By way of example, the metal halide is selected from: ZnCl2、ZnBr2And ZnI2One or more of the following; alternatively, CdCl2、CdBr2And CdI2One or more of the following; or, SnCl2、SnBr2And SnI2One or more of the following; or, GeCl2、GeBr2And GeI2And the like.
Further in a preferred embodiment, the metal halide is selected from ZnCl2、CdCl2、SnCl2And GeCl2And the like. Since chlorine has a small atomic radius relative to bromine and iodine, the distance over which electrons need to travel when the surface of the particle is used as a surface ligand is short, and thus the electron transport property can be improved.
In a preferred embodiment, the second oil-soluble organic ligand is selected from one or more of substituted or unsubstituted alkylaminophosphines, substituted or unsubstituted alkoxyphosphines, substituted or unsubstituted silylphosphines, and alkylphosphines having a branched carbon number of 4 or more.
In a preferred embodiment, the organic alcohol is selected from one or more of octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, and the like.
In a preferred embodiment, the first temperature is 110-.
In a preferred embodiment, the second temperature is 110-.
In this example, the prepared inorganic semiconductor nanocrystals were metal oxide particles. Preferably, the metal oxide particles are selected from ZnO particles, CdO particles, SnO particles, or GeO particles, but are not limited thereto. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The higher temperature is the third temperature in this embodiment. Preferably, the third temperature is 210-. More preferably, the third temperature is 230-300 ℃.
In a preferred embodiment, the first mixture is heated at a third temperature, the second mixture is injected during the heating process to perform crystal growth of the semiconductor nanocrystal, and after the crystal growth is completed, a third oil-soluble organic ligand is added during the cooling process to bond the third oil-soluble organic ligand on the surface of the semiconductor nanocrystal to obtain the first electron transport layer material, wherein the third oil-soluble organic ligand is thiol with a carbon atom number of 8 or more, and the third temperature is higher than the first temperature and the second temperature.
In a preferred embodiment, the step of dispersing the cationic precursor in the solvent and heating at a first temperature to obtain a first mixture specifically comprises: and dispersing the doped metal salt and the cation precursor into a solvent, and heating at a first temperature to obtain the first mixture.
Further in a preferred embodiment, the doping metal salt is selected from one or more of Mg salt, Mn salt, Al salt, Y salt, V salt and Ni salt, but not limited thereto. By way of example, the Mg salt may be chosen from MgCl2、MgI2、Mg(NO3)2May be selected from MnCl2、MnI2、Mn (NO3)2May be selected from AlCl3、AlI3、Al(CH3COO)3May be selected from YCl2、Y(CH3COO)2、Y(NO3)2But are not limited thereto, theThe V salt may be selected from VCl2、V(CH3COO)2、V(NO3)2May be selected from NiCl2、Ni(CH3COO)2、Ni(NO3)2But is not limited thereto.
In a further preferred embodiment, in the material of the first electron transport layer, the inorganic semiconductor nanocrystals are selected from ZnO particles or SnO particles, and the inorganic semiconductor nanocrystals contain a metal doping element Al, V or Y. The HOMO energy level of the inorganic semiconductor nanocrystals can be better matched with the HOMO energy level of the light-emitting layer quantum dots, and the preferred doped ions can reduce the injection barrier of the electron transport layer to the light-emitting layer, so that the effectiveness of electron transport between the material of the transport layer and the material of the light-emitting layer is ensured. Preferably, the metal doping element is Y.
The embodiment of the invention provides a preparation method of a first electron transport layer material, which comprises the following steps:
dispersing a cation precursor and a first oil-soluble organic ligand into a solvent, and heating at a first temperature to obtain a first mixture, wherein the cation precursor is a metal halide;
dispersing an anion precursor and a second oil-soluble organic ligand into a solvent, and heating at a second temperature to obtain a second mixture, wherein the anion precursor is organic alcohol;
and heating the first mixture at a third temperature, and injecting the second mixture in the heating process to perform crystal growth of semiconductor nanocrystals to obtain the first electron transport layer material, wherein the third temperature is higher than the first temperature and the second temperature.
In the embodiment, organic alcohol is used as an anion precursor, a halogen-containing cation precursor and the organic alcohol are subjected to alcoholysis reaction at a high temperature to obtain the metal oxide semiconductor nanocrystal, and halogen ions, the first oil-soluble organic ligand and the second oil-soluble organic ligand in the halogen-containing cation precursor are combined to the surface of the metal oxide semiconductor nanocrystal. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The surface of the metal oxide semiconductor nanocrystal has mixed ligands: a halogen ligand, a first oil-soluble organic ligand, and a second oil-soluble organic ligand, the oil-soluble organic ligand rendering the first electron transport layer material oil-soluble. In the first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of the luminous layer can be improved.
In a preferred embodiment, the metal halide is selected from the group consisting of: one or more of chloride, bromide and iodide of zinc element; or,
one or more of chlorides, bromides and iodides of cadmium element; or,
one or more of chlorides, bromides and iodides of tin element; or,
one or more of chlorides, bromides and iodides of germanium elements. By way of example, the metal halide is selected from: ZnCl2、ZnBr2And ZnI2One or more of the following; alternatively, CdCl2、CdBr2And CdI2One or more of the following; or, SnCl2、SnBr2And SnI2One or more of the following; or, GeCl2、GeBr2And GeI2And the like.
Further in a preferred embodiment, the metal halide is selected from ZnCl2、CdCl2、SnCl2And GeCl2And the like. Since chlorine has a small atomic radius relative to bromine and iodine, the distance over which electrons need to travel when the surface of the particle is used as a surface ligand is short, and thus the electron transport property can be improved.
In a preferred embodiment, the first oil-soluble organic ligand is selected from one or more of an organic carboxylic acid having 8 or more carbon atoms, an organic phosphoric acid having 8 or more carbon atoms, a secondary or tertiary amine having 4 or more branched carbon atoms, and a primary amine having 8 or more carbon atoms;
and/or the second oil-soluble organic ligand is selected from one or more of substituted or unsubstituted alkylaminophosphine, substituted or unsubstituted alkoxyphosphine, substituted or unsubstituted silylphosphine, and alkylphosphine with branched carbon atom number greater than or equal to 4.
In a further preferred embodiment, the first oil-soluble organic ligand is an organic phosphoric acid having 8 or more carbon atoms, and the second oil-soluble organic ligand is a substituted or unsubstituted alkylaminophosphine. Because the organic phosphoric acid is combined with the cation on the surface of the inorganic semiconductor nanocrystal by an ionic bond, the alkylamino phosphine and the cation on the surface of the inorganic semiconductor nanocrystal can simultaneously adopt P lone electron pair or-NH2The two ligands are combined with the surface ions of the inorganic semiconductor nanocrystalline through-OH, and hydrolysis cannot occur.
In a preferred embodiment, the organic alcohol is selected from one or more of octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, and the like.
In a preferred embodiment, the first temperature is 110-.
In a preferred embodiment, the second temperature is 110-.
In this example, the prepared inorganic semiconductor nanocrystals were metal oxide particles. Preferably, the metal oxide particles are selected from ZnO particles, CdO particles, SnO particles, or GeO particles, but are not limited thereto. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The higher temperature is the third temperature in this embodiment. Preferably, the third temperature is 210-. More preferably, the third temperature is 230-300 ℃.
In a preferred embodiment, the first mixture is heated at a third temperature, the second mixture is injected during the heating process to perform crystal growth of the semiconductor nanocrystal, and after the crystal growth is completed, a third oil-soluble organic ligand is added during the cooling process to bond the third oil-soluble organic ligand on the surface of the semiconductor nanocrystal to obtain the first electron transport layer material, wherein the third oil-soluble organic ligand is thiol with a carbon atom number of 8 or more, and the third temperature is higher than the first temperature and the second temperature. In this embodiment, organic alcohol is used as an anion precursor, a halogen-containing cation precursor and the organic alcohol are subjected to alcoholysis reaction at a high temperature to obtain the metal oxide semiconductor nanocrystal, and halogen ions in the halogen-containing cation precursor, the first oil-soluble organic ligand, the second oil-soluble organic ligand and the third oil-soluble organic ligand are bound to the surface of the metal oxide semiconductor nanocrystal.
In a further preferred embodiment, the first oil-soluble organic ligand is an organophosphate having 8 or more carbon atoms, the second oil-soluble organic ligand is a substituted or unsubstituted alkylaminophosphine, and the third oil-soluble organic ligand is a thiol having 8 or more carbon atoms. Because the organic phosphoric acid and the thiol ligand are respectively combined with the cations on the surface of the inorganic semiconductor nanocrystal by ionic bonds and hydrogen bonds, the alkylamino phosphine and the cations on the surface of the inorganic semiconductor nanocrystal can simultaneously adopt P lone electron pair or-NH2The first electron transport layer material has strong binding capacity and is not easy to fall off, the solubility and the transport property of the first electron transport layer material can be ensured, and the ligands and the inorganic semiconductor nanocrystalline surface ions can not be bound by-OH and can not be hydrolyzed.
In a preferred embodiment, the step of dispersing the cation precursor and the first oil-soluble organic ligand in a solvent and heating at a first temperature to obtain a first mixture specifically comprises: dispersing a doped metal salt, a cation precursor and a first oil-soluble organic ligand into a solvent, and heating at a first temperature to obtain the first mixture.
Further in a preferred embodiment, the doping metal salt is selected from one or more of Mg salt, Mn salt, Al salt, Y salt, V salt and Ni salt, but not limited thereto. By way of example, the Mg salt may be chosen from MgCl2、MgI2、Mg(NO3)2May be selected from MnCl2、MnI2、Mn (NO3)2May be selected from AlCl3、AlI3、Al(CH3COO)3May be selected from YCl2、Y(CH3COO)2、Y(NO3)2May be selected from VCl2、V(CH3COO)2、V(NO3)2May be selected from NiCl2、Ni(CH3COO)2、Ni(NO3)2But is not limited thereto.
In a further preferred embodiment, in the material of the first electron transport layer, the inorganic semiconductor nanocrystals are selected from ZnO particles or SnO particles, and the inorganic semiconductor nanocrystals contain a metal doping element Al, V or Y. The HOMO energy level of the inorganic semiconductor nanocrystals can be better matched with the HOMO energy level of the light-emitting layer quantum dots, and the preferred doped ions can reduce the injection barrier of the electron transport layer to the light-emitting layer, so that the effectiveness of electron transport between the material of the transport layer and the material of the light-emitting layer is ensured. Preferably, the metal doping element is Y.
The embodiment of the invention provides a preparation method of a first electron transport layer material, which comprises the following steps:
dispersing a cation precursor into a solvent, and heating at a first temperature to obtain a first mixture, wherein the cation precursor is a metal halide;
dispersing an anion precursor into a solvent, and heating at a second temperature to obtain a second mixture, wherein the anion precursor is organic alcohol;
and heating the first mixture at a third temperature, injecting the second mixture in the heating process to perform crystal growth of the semiconductor nanocrystal, and adding a third oil-soluble organic ligand in the cooling process after the crystal growth is completed so that the third oil-soluble organic ligand is combined on the surface of the semiconductor nanocrystal to obtain the first electron transport layer material, wherein the third oil-soluble organic ligand is mercaptan with the carbon atom number of more than or equal to 8, and the third temperature is higher than the first temperature and the second temperature.
In the embodiment, organic alcohol is used as an anion precursor, a halogen-containing cation precursor and the organic alcohol are subjected to alcoholysis reaction at a high temperature to obtain the metal oxide semiconductor nanocrystal, and halogen ions in the halogen-containing cation precursor and a third oil-soluble organic ligand are bonded to the surface of the metal oxide semiconductor nanocrystal. The first electron transport layer material obtained by the reaction of the method has small and uniform size, few surface defects, no emission peak in a visible waveband and no interference with the emission of a light emitting layer in a device structure. The surface of the metal oxide semiconductor nanocrystal has mixed ligands: a halogen ligand and a third oil-soluble organic ligand that renders the first electron transport layer material oil-soluble. In the first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of the luminous layer can be improved.
In a preferred embodiment, the metal halide is selected from the group consisting of: one or more of chloride, bromide and iodide of zinc element; or,
one or more of chlorides, bromides and iodides of cadmium element; or,
one or more of chlorides, bromides and iodides of tin element; or,
one or more of chlorides, bromides and iodides of germanium elements. By way of example, the metal halide is selected from: ZnCl2、ZnBr2And ZnI2One or more of the following; alternatively, CdCl2、CdBr2And CdI2One or more of the following; or, SnCl2、SnBr2And SnI2One or more of the following; or, GeCl2、GeBr2And GeI2And the like.
Further in a preferred embodiment, the metal halide is selected from ZnCl2、CdCl2、SnCl2And GeCl2And the like. Since chlorine has a small atomic radius relative to bromine and iodine, the distance over which electrons need to travel when the surface of the particle is used as a surface ligand is short, and thus the electron transport property can be improved.
In a preferred embodiment, the organic alcohol is selected from one or more of octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, and the like.
In a preferred embodiment, the first temperature is 110-.
In a preferred embodiment, the second temperature is 110-.
In this example, the prepared inorganic semiconductor nanocrystals were metal oxide particles. Preferably, the metal oxide particles are selected from ZnO particles, CdO particles, SnO particles, or GeO particles, but are not limited thereto. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The higher temperature is the third temperature in this embodiment. Preferably, the third temperature is 210-. More preferably, the third temperature is 230-300 ℃.
In a preferred embodiment, the step of dispersing the cationic precursor in the solvent and heating at a first temperature to obtain a first mixture specifically comprises: and dispersing the doped metal salt and the cation precursor into a solvent, and heating at a first temperature to obtain the first mixture.
Further in a preferred embodiment, the doping metal salt is selected from one or more of Mg salt, Mn salt, Al salt, Y salt, V salt and Ni salt, but not limited thereto. By way of example, the Mg salt may be chosen from MgCl2、MgI2、Mg(NO3)2May be selected from MnCl2、MnI2、Mn (NO3)2May be selected from AlCl3、AlI3、Al(CH3COO)3May be selected from YCl2、Y(CH3COO)2、Y(NO3)2May be selected from VCl2、V(CH3COO)2、V(NO3)2May be selected from NiCl2、Ni(CH3COO)2、Ni(NO3)2But is not limited thereto.
In a further preferred embodiment, in the material of the first electron transport layer, the inorganic semiconductor nanocrystals are selected from ZnO particles or SnO particles, and the inorganic semiconductor nanocrystals contain a metal doping element Al, V or Y. The HOMO energy level of the inorganic semiconductor nanocrystals can be better matched with the HOMO energy level of the light-emitting layer quantum dots, and the preferred doped ions can reduce the injection barrier of the electron transport layer to the light-emitting layer, so that the effectiveness of electron transport between the material of the transport layer and the material of the light-emitting layer is ensured. Preferably, the metal doping element is Y.
The embodiment of the invention provides a preparation method of a first electron transport layer material, which comprises the following steps:
dispersing a cation precursor and a first oil-soluble organic ligand into a solvent, and heating at a first temperature to obtain a first mixture, wherein the cation precursor is a metal halide;
dispersing an anion precursor into a solvent, and heating at a second temperature to obtain a second mixture, wherein the anion precursor is mercaptan and/or elemental sulfur with the carbon atom number of more than or equal to 8;
and heating the first mixture at a third temperature, and injecting the second mixture in the heating process to perform crystal growth of semiconductor nanocrystals to obtain the first electron transport layer material, wherein the third temperature is higher than the first temperature and the second temperature.
In this embodiment, the halogen-containing cation precursor reacts with the sulfur-containing anion precursor at a high temperature to obtain the metal sulfide semiconductor nanocrystal. The halide ions in the halogen-containing cation precursor and the first oil-soluble organic ligand bind to the surface of the metal sulfide semiconductor nanocrystal. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The surface of the metal sulfide semiconductor nanocrystal is provided with a mixed ligand: a halogen ligand and a first oil-soluble organic ligand that renders the first electron transport layer material oil-soluble. In the first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of the luminous layer can be improved.
In one embodiment, the anionic precursor is a thiol having 8 or more carbon atoms. And carrying out alcoholysis reaction on the halogen-containing cation precursor and mercaptan at high temperature to obtain the metal sulfide semiconductor nanocrystal. The halide ions in the halogen-containing cation precursor and the first oil-soluble organic ligand bind to the surface of the metal sulfide semiconductor nanocrystal. In addition, excess thiol can also bind to the surface of the metal sulfide semiconductor nanocrystal as a surface ligand. Wherein, when the amount of the thiol added is larger than that of the growth nucleation of the metal sulfide semiconductor nanocrystal, the thiol is in excess.
In another embodiment, the anionic precursor is elemental sulfur. Wherein the elemental sulfur is added in the form of a sulfur-non-coordinating solvent after being mixed with the non-coordinating solvent. The elemental sulfur is dispersed in a non-coordinating solvent to form a uniform liquid, which facilitates subsequent injection. And reacting the halogen-containing cation precursor with the elemental sulfur at high temperature to obtain the metal sulfide semiconductor nanocrystal. The halide ions in the halogen-containing cation precursor and the first oil-soluble organic ligand bind to the surface of the metal sulfide semiconductor nanocrystal.
In a preferred embodiment, the sulfur-non-coordinating solvent is selected from one or more of sulfur-dodecene, sulfur-tetradecene, sulfur-hexadecene, sulfur-octadecene.
In yet another embodiment, the anionic precursor is thiol with a carbon number of 8 or more and elemental sulfur. Wherein the elemental sulfur is added in the form of a sulfur-non-coordinating solvent after being mixed with the non-coordinating solvent. The elemental sulfur is dispersed in a non-coordinating solvent to form a uniform liquid, which facilitates subsequent injection. And (3) reacting the halogen-containing cation precursor with mercaptan and sulfur simple substance at high temperature to obtain the metal sulfide semiconductor nanocrystalline. The halide ions in the halogen-containing cation precursor and the first oil-soluble organic ligand bind to the surface of the metal sulfide semiconductor nanocrystal. In addition, excess thiol can also bind to the surface of the metal sulfide semiconductor nanocrystal as a surface ligand. Wherein, when the amount of the thiol added is larger than that of the growth nucleation of the metal sulfide semiconductor nanocrystal, the thiol is in excess.
In a preferred embodiment, the sulfur-non-coordinating solvent is selected from one or more of sulfur-dodecene, sulfur-tetradecene, sulfur-hexadecene, sulfur-octadecene.
In a preferred embodiment, the thiol having 8 or more carbon atoms is one or more selected from the group consisting of octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecanethiol, pentadecathiol, hexadecanethiol, heptadecanethiol, and octadecanethiol.
In a preferred embodiment, the metal halide is selected from the group consisting of: one or more of chloride, bromide and iodide of zinc element; or,
one or more of chlorides, bromides and iodides of tin element; or,
one or more of chlorides, bromides and iodides of germanium elements. By way of example, the metal halide is selected from: ZnCl2、ZnBr2And ZnI2One or more of the following; or, SnCl2、SnBr2And SnI2One or more of the following; or, GeCl2、GeBr2And GeI2And the like.
Further in a preferred embodiment, the metal halide is selected from ZnCl2、SnCl2And GeCl2And the like. Since chlorine has a small atomic radius relative to bromine and iodine, the distance over which electrons need to travel when the surface of the particle is used as a surface ligand is short, and thus the electron transport property can be improved.
In a preferred embodiment, the first oil-soluble organic ligand is selected from one or more of an organic carboxylic acid having 8 or more carbon atoms, an organic phosphoric acid having 8 or more carbon atoms, a secondary or tertiary amine having 4 or more branched carbon atoms, and a primary amine having 8 or more carbon atoms.
In a preferred embodiment, the first temperature is 110-.
In a preferred embodiment, the second temperature is 110-.
In this example, the prepared inorganic semiconductor nanocrystals were metal sulfide particles. Preferably, the metal sulfide particles are selected from ZnS particles, SnS particles or GeS particles, but are not limited thereto. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The higher temperature is the third temperature in this embodiment. Preferably, the third temperature is 210-. More preferably, the third temperature is 230-300 ℃.
In a preferred embodiment, the step of dispersing the cation precursor and the first oil-soluble organic ligand in the solvent, and heating at a first temperature to obtain the first mixture specifically includes: dispersing the doped metal salt, the cation precursor and the first oil-soluble organic ligand into a solvent, and heating at a first temperature to obtain the first mixture.
Further in a preferred embodiment, the doping metal salt is selected from one or more of Mg salt, Mn salt, Al salt, Y salt, V salt and Ni salt, but not limited thereto. By way of example, the Mg salt may be chosen from MgCl2、MgI2、Mg(NO3)2May be selected from MnCl2、MnI2、Mn (NO3)2May be selected from AlCl3、AlI3、Al(CH3COO)3May be selected from YCl2、Y(CH3COO)2、Y(NO3)2May be selected from VCl2、V(CH3COO)2、V(NO3)2May be selected from NiCl2、Ni(CH3COO)2、Ni(NO3)2But is not limited thereto.
In still further another preferred embodiment, in the material for the first electron transport layer, the inorganic semiconductor nanocrystal is selected from ZnS particles, and the inorganic semiconductor nanocrystal contains a metal doping element Al, V or Y. The HOMO energy level of the inorganic semiconductor nanocrystal can be well matched with the HOMO energy level of the light-emitting layer quantum dot, and the preferred doped ions can reduce the injection barrier of the electron transport layer to the light-emitting layer, so that the effectiveness of electron transport between the material of the transport layer and the material of the light-emitting layer is ensured. Preferably, the metal doping element is Y.
The embodiment of the invention provides a preparation method of a first electron transport layer material, which comprises the following steps:
dispersing a cation precursor into a solvent, and heating at a first temperature to obtain a first mixture, wherein the cation precursor is a metal halide;
dispersing an anion precursor and a second oil-soluble organic ligand into a solvent, and heating at a second temperature to obtain a second mixture, wherein the anion precursor is mercaptan and/or elemental sulfur with the carbon atom number of more than or equal to 8;
and heating the first mixture at a third temperature, and injecting the second mixture in the heating process to perform crystal growth of semiconductor nanocrystals to obtain the first electron transport layer material, wherein the third temperature is higher than the first temperature and the second temperature.
In this embodiment, the halogen-containing cation precursor reacts with the sulfur-containing anion precursor at a high temperature to obtain the metal sulfide semiconductor nanocrystal. The halide ions in the halogen-containing cation precursor and the second oil-soluble organic ligand bind to the surface of the metal sulfide semiconductor nanocrystal. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The surface of the metal sulfide semiconductor nanocrystal is provided with a mixed ligand: a halogen ligand and a second oil-soluble organic ligand that renders the first electron transport layer material oil-soluble. In the first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of the luminous layer can be improved.
In one embodiment, the anionic precursor is a thiol having 8 or more carbon atoms. And carrying out alcoholysis reaction on the halogen-containing cation precursor and mercaptan at high temperature to obtain the metal sulfide semiconductor nanocrystal. The halide ions in the halogen-containing cation precursor and the second oil-soluble organic ligand bind to the surface of the metal sulfide semiconductor nanocrystal. In addition, excess thiol can also bind to the surface of the metal sulfide semiconductor nanocrystal as a surface ligand. Wherein, when the amount of the thiol added is larger than that of the growth nucleation of the metal sulfide semiconductor nanocrystal, the thiol is in excess.
In another embodiment, the anionic precursor is elemental sulfur. And after the sulfur simple substance is mixed with the second oil-soluble organic ligand, the formed sulfur ions react with metal ions in the cation precursor at high temperature to nucleate to obtain the sulfide semiconductor nanocrystalline, and the halogen ions in the halogen-containing cation precursor and the second oil-soluble organic ligand are combined to the surface of the metal sulfide semiconductor nanocrystalline after nucleation.
In yet another embodiment, the anionic precursor is thiol with a carbon number of 8 or more and elemental sulfur. And after the sulfur simple substance is mixed with the second oil-soluble organic ligand, the formed sulfur ions and mercaptan react with metal ions in the cation precursor at high temperature to nucleate to obtain the sulfide semiconductor nanocrystalline, and the halogen ions in the halogen-containing cation precursor and the second oil-soluble organic ligand are combined to the surface of the metal sulfide semiconductor nanocrystalline after nucleation. In addition, excess thiol can also bind to the surface of the metal sulfide semiconductor nanocrystal as a surface ligand. Wherein, when the amount of the thiol added is larger than that of the growth nucleation of the metal sulfide semiconductor nanocrystal, the thiol is in excess.
In a preferred embodiment, the thiol having 8 or more carbon atoms is one or more selected from the group consisting of octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecanethiol, pentadecathiol, hexadecanethiol, heptadecanethiol, and octadecanethiol.
In a preferred embodiment, the metal halide is selected from the group consisting of: one or more of chloride, bromide and iodide of zinc element; or,
one or more of chlorides, bromides and iodides of tin element; or,
one or more of chlorides, bromides and iodides of germanium elements. By way of example, the metal halide is selected from: ZnCl2、ZnBr2And ZnI2One or more of the following; or, SnCl2、SnBr2And SnI2One or more of the following; or, GeCl2、GeBr2And GeI2And the like.
Further in a preferred embodiment, the metal halide is selected from ZnCl2、SnCl2And GeCl2And the like. Since chlorine has a small atomic radius relative to bromine and iodine, the distance over which electrons need to travel when the surface of the particle is used as a surface ligand is short, and thus the electron transport property can be improved.
In a preferred embodiment, the second oil-soluble organic ligand is selected from one or more of substituted or unsubstituted alkylaminophosphines, substituted or unsubstituted alkoxyphosphines, substituted or unsubstituted silylphosphines, and alkylphosphines having a branched carbon number of 4 or more.
In a further preferred embodiment, the second oil-soluble organic ligand is a substituted or unsubstituted alkylaminophosphine. Wherein the substituted or unsubstituted alkylaminophosphine and the cation on the surface of the particle can simultaneously adopt P lone electron pair or-NH2The halogen ligand has strong ionic bond, strong combination with the particle surface and difficult shedding. In addition, when the alkylamino phosphine and iodine ligands are combined with the metal sulfide particles, no-OH is combined with the surfaces of the metal sulfide particles, and the metal sulfide particles are not hydrolyzed or oxidized.
In a preferred embodiment, the first temperature is 110-.
In a preferred embodiment, the second temperature is 110-.
In this example, the prepared inorganic semiconductor nanocrystals were metal sulfide particles. Preferably, the metal sulfide particles are selected from ZnS particles, SnS particles or GeS particles, but are not limited thereto. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The higher temperature is the third temperature in this embodiment. Preferably, the third temperature is 210-. More preferably, the third temperature is 230-300 ℃.
In a preferred embodiment, the step of dispersing the cationic precursor in the solvent and heating at a first temperature to obtain a first mixture specifically comprises: and dispersing the doped metal salt and the cation precursor into a solvent, and heating at a first temperature to obtain the first mixture.
In a preferred embodiment, the doping metal salt is selected from one or more of Mg salt, Mn salt, Al salt, Y salt, V salt, and Ni salt, but is not limited thereto. By way of example, the Mg salt may be chosen from MgCl2、MgI2、Mg(NO3)2May be selected from MnCl2、MnI2、Mn (NO3)2May be selected from AlCl3、AlI3、Al(CH3COO)3May be selected from YCl2、Y(CH3COO)2、Y(NO3)2May be selected from VCl2、V(CH3COO)2、V(NO3)2May be selected from NiCl2、Ni(CH3COO)2、Ni(NO3)2But is not limited thereto.
In a further preferred embodiment, in the material of the first electron transport layer, the inorganic semiconductor nanocrystals are selected from ZnS particles, and the inorganic semiconductor nanocrystals contain a metal-doped element Al, V or Y. The HOMO energy level of the inorganic semiconductor nanocrystal can be well matched with the HOMO energy level of the light-emitting layer quantum dot, and the preferred doped ions can reduce the injection barrier of the electron transport layer to the light-emitting layer, so that the effectiveness of electron transport between the material of the transport layer and the material of the light-emitting layer is ensured. Preferably, the metal doping element is Y.
The embodiment of the invention provides a preparation method of a first electron transport layer material, which comprises the following steps:
dispersing a cation precursor and a first oil-soluble organic ligand into a solvent, and heating at a first temperature to obtain a first mixture, wherein the cation precursor is a metal halide;
dispersing an anion precursor and a second oil-soluble organic ligand into a solvent, and heating at a second temperature to obtain a second mixture, wherein the anion precursor is mercaptan and/or elemental sulfur with the carbon atom number of more than or equal to 8;
and heating the first mixture at a third temperature, and injecting the second mixture in the heating process to perform crystal growth of semiconductor nanocrystals to obtain the first electron transport layer material, wherein the third temperature is higher than the first temperature and the second temperature.
In this embodiment, the halogen-containing cation precursor reacts with the sulfur-containing anion precursor at a high temperature to obtain the metal sulfide semiconductor nanocrystal. The halide ions, the first oil-soluble organic ligand, and the second oil-soluble organic ligand in the halogen-containing cation precursor bind to the surface of the metal sulfide semiconductor nanocrystal. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The surface of the metal sulfide semiconductor nanocrystal is provided with a mixed ligand: the organic ligand comprises a halogen ligand, a first oil-soluble organic ligand and a second oil-soluble organic ligand, wherein the oil-soluble organic ligand enables the first electron transport layer material to be still oil-soluble. In the first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of the luminous layer can be improved.
In one embodiment, the anionic precursor is a thiol having 8 or more carbon atoms. And carrying out alcoholysis reaction on the halogen-containing cation precursor and mercaptan at high temperature to obtain the metal sulfide semiconductor nanocrystal. The halide ions, the first oil-soluble organic ligand, and the second oil-soluble organic ligand in the halogen-containing cation precursor bind to the surface of the metal sulfide semiconductor nanocrystal. In addition, excess thiol can also bind to the surface of the metal sulfide semiconductor nanocrystal as a surface ligand. Wherein, when the amount of the thiol added is larger than that of the growth nucleation of the metal sulfide semiconductor nanocrystal, the thiol is in excess.
In another embodiment, the anionic precursor is elemental sulfur. And after the nucleation, the halogen ions in the cation precursor containing halogen, the first oil-soluble organic ligand and the second oil-soluble organic ligand are combined to the surface of the metal sulfide semiconductor nanocrystal.
In yet another embodiment, the anionic precursor is thiol with a carbon number of 8 or more and elemental sulfur. And after the nucleation, the halogen ions in the cation precursor containing halogen, the first oil-soluble organic ligand and the second oil-soluble organic ligand are combined to the surface of the metal sulfide semiconductor nanocrystal. In addition, excess thiol can also bind to the surface of the metal sulfide semiconductor nanocrystal as a surface ligand. Wherein, when the amount of the thiol added is larger than that of the growth nucleation of the metal sulfide semiconductor nanocrystal, the thiol is in excess.
In a preferred embodiment, the thiol having 8 or more carbon atoms may be selected from one or more of octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecanethiol, pentadecathiol, hexadecanethiol, heptadecanethiol, and octadecanethiol.
In a preferred embodiment, the first oil-soluble organic ligand is selected from one or more of an organic carboxylic acid having 8 or more carbon atoms, an organic phosphoric acid having 8 or more carbon atoms, a secondary or tertiary amine having 4 or more branched carbon atoms, and a primary amine having 8 or more carbon atoms;
and/or the second oil-soluble organic ligand is selected from one or more of substituted or unsubstituted alkylaminophosphine, substituted or unsubstituted alkoxyphosphine, substituted or unsubstituted silylphosphine, and alkylphosphine with branched carbon atom number greater than or equal to 4.
In a further preferred embodiment, the first oil-soluble organic ligand is an organic phosphoric acid having 8 or more carbon atoms, and the second oil-soluble organic ligand is a substituted or unsubstituted alkylaminophosphine. Because the organic phosphoric acid is combined with the cation on the surface of the inorganic semiconductor nanocrystal by an ionic bond, the alkylamino phosphine and the cation on the surface of the inorganic semiconductor nanocrystal can simultaneously adopt P lone electron pair or-NH2The two ligands are combined with the surface ions of the inorganic semiconductor nanocrystalline through-OH, and hydrolysis cannot occur.
In a further preferred embodiment, the anion precursor is mercaptan with the carbon number of more than or equal to 8 or mercaptan and elemental sulfur, and the amount of the added mercaptan is more than that of the semiconductor nanocrystal nucleationThe first oil-soluble organic ligand is organic phosphoric acid with the carbon atom number being more than or equal to 8, and the second oil-soluble organic ligand is substituted or unsubstituted alkylamino phosphine. Wherein, when the amount of the thiol added is larger than that of the growth nucleation of the metal sulfide semiconductor nanocrystal, the thiol is in excess. Excess thiol can also bind to the surface of the metal sulfide semiconductor nanocrystal as a surface ligand. Because the organic phosphoric acid and the thiol ligand are respectively combined with the cations on the surface of the inorganic semiconductor nanocrystal by ionic bonds and hydrogen bonds, the alkylamino phosphine and the cations on the surface of the inorganic semiconductor nanocrystal can simultaneously adopt P lone electron pair or-NH2The first electron transport layer material has strong binding capacity and is not easy to fall off, the solubility and the transport property of the first electron transport layer material can be ensured, and the ligands and the inorganic semiconductor nanocrystalline surface ions can not be bound by-OH and can not be hydrolyzed.
In a preferred embodiment, the first temperature is 110-.
In a preferred embodiment, the second temperature is 110-.
In this example, the prepared inorganic semiconductor nanocrystals were metal sulfide particles. Preferably, the metal sulfide particles are selected from ZnS particles, SnS particles or GeS particles, but are not limited thereto. The inorganic semiconductor nanocrystals emit light mainly depending on the defect state in a small particle size (2 to 7 nm). The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The higher temperature is the third temperature in this embodiment. Preferably, the third temperature is 210-. More preferably, the third temperature is 230-300 ℃.
In a preferred embodiment, the step of dispersing the cation precursor and the first oil-soluble organic ligand in a solvent and heating at a first temperature to obtain a first mixture specifically comprises: dispersing a doped metal salt, a cation precursor and a first oil-soluble organic ligand into a solvent, and heating at a first temperature to obtain the first mixture.
In a preferred embodiment, the doping metal salt is selected from one or more of Mg salt, Mn salt, Al salt, Y salt, V salt, and Ni salt, but is not limited thereto. By way of example, the Mg salt may be chosen from MgCl2、MgI2、Mg(NO3)2May be selected from MnCl2、MnI2、Mn (NO3)2May be selected from AlCl3、AlI3、Al(CH3COO)3May be selected from YCl2、Y(CH3COO)2、Y(NO3)2May be selected from VCl2、V(CH3COO)2、V(NO3)2May be selected from NiCl2、Ni(CH3COO)2、Ni(NO3)2But is not limited thereto.
In a further preferred embodiment, in the material of the first electron transport layer, the inorganic semiconductor nanocrystals are selected from ZnS particles, and the inorganic semiconductor nanocrystals contain a metal-doped element Al, V or Y. The HOMO energy level of the inorganic semiconductor nanocrystal can be well matched with the HOMO energy level of the light-emitting layer quantum dot, and the preferred doped ions can reduce the injection barrier of the electron transport layer to the light-emitting layer, so that the effectiveness of electron transport between the material of the transport layer and the material of the light-emitting layer is ensured. Preferably, the metal doping element is Y.
The embodiment of the invention provides a preparation method of a first electron transport layer material, which comprises the following steps:
dispersing a cation precursor into a solvent, and heating at a first temperature to obtain a first mixture, wherein the cation precursor is a metal halide;
dispersing an anion precursor into a solvent, and heating at a second temperature to obtain a second mixture, wherein the anion precursor is mercaptan and/or elemental sulfur with the carbon atom number of more than or equal to 8;
and heating the first mixture at a third temperature, injecting the second mixture in the heating process to perform crystal growth of the semiconductor nanocrystal, and adding a third oil-soluble organic ligand in the cooling process after the crystal growth is completed so that the third oil-soluble organic ligand is combined on the surface of the semiconductor nanocrystal to obtain the first electron transport layer material, wherein the third oil-soluble organic ligand is mercaptan with the carbon atom number of more than or equal to 8, and the third temperature is higher than the first temperature and the second temperature.
In this embodiment, the halogen-containing cation precursor reacts with the sulfur-containing anion precursor at a high temperature to obtain the metal sulfide semiconductor nanocrystal. The halide ions in the halogen-containing cation precursor and the third oil-soluble organic ligand bind to the surface of the metal sulfide semiconductor nanocrystal. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The surface of the metal sulfide semiconductor nanocrystal is provided with a mixed ligand: a halogen ligand and an oil-soluble organic ligand which renders the first electron transport layer material oil-soluble. In the first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of the luminous layer can be improved.
In one embodiment, the anionic precursor is a thiol having 8 or more carbon atoms. And carrying out alcoholysis reaction on the halogen-containing cation precursor and mercaptan at high temperature to obtain the metal sulfide semiconductor nanocrystal. The halide ions in the halogen-containing cation precursor and the third oil-soluble organic ligand bind to the surface of the metal sulfide semiconductor nanocrystal. In addition, excess thiol can also bind to the surface of the metal sulfide semiconductor nanocrystal as a surface ligand. Wherein, when the amount of the thiol added is larger than that of the growth nucleation of the metal sulfide semiconductor nanocrystal, the thiol is in excess.
In another embodiment, the anionic precursor is elemental sulfur. Wherein the elemental sulfur is added in the form of a sulfur-non-coordinating solvent after being mixed with the non-coordinating solvent. The elemental sulfur is dispersed in a non-coordinating solvent to form a uniform liquid, which facilitates subsequent injection. And reacting the halogen-containing cation precursor with the elemental sulfur at high temperature to obtain the metal sulfide semiconductor nanocrystal. The halide ions in the halogen-containing cation precursor and the third oil-soluble organic ligand bind to the surface of the metal sulfide semiconductor nanocrystal.
In a preferred embodiment, the sulfur-non-coordinating solvent is selected from one or more of sulfur-dodecene, sulfur-tetradecene, sulfur-hexadecene, sulfur-octadecene.
In yet another embodiment, the anionic precursor is thiol with a carbon number of 8 or more and elemental sulfur. Wherein the elemental sulfur is added in the form of a sulfur-non-coordinating solvent after being mixed with the non-coordinating solvent. The elemental sulfur is dispersed in a non-coordinating solvent to form a uniform liquid, which facilitates subsequent injection. And (3) reacting the halogen-containing cation precursor with mercaptan and sulfur simple substance at high temperature to obtain the metal sulfide semiconductor nanocrystalline. The halide ions in the halogen-containing cation precursor and the third oil-soluble organic ligand bind to the surface of the metal sulfide semiconductor nanocrystal. In addition, excess thiol can also bind to the surface of the metal sulfide semiconductor nanocrystal as a surface ligand. Wherein, when the amount of the thiol added is larger than that of the growth nucleation of the metal sulfide semiconductor nanocrystal, the thiol is in excess.
In a preferred embodiment, the sulfur-non-coordinating solvent is selected from one or more of sulfur-dodecene, sulfur-tetradecene, sulfur-hexadecene, sulfur-octadecene.
In a preferred embodiment, the thiol having 8 or more carbon atoms may be selected from one or more of octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecanethiol, pentadecathiol, hexadecanethiol, heptadecanethiol, and octadecanethiol.
In a preferred embodiment, the metal halide is selected from the group consisting of: one or more of chloride, bromide and iodide of zinc element; or,
one or more of chlorides, bromides and iodides of tin element; or,
one or more of chlorides, bromides and iodides of germanium elements. By way of example, the metal halide is selected from: ZnCl2、ZnBr2And ZnI2One or more of the following; or, SnCl2、SnBr2And SnI2One or more of the following; or, GeCl2、GeBr2And GeI2And the like.
Further in a preferred embodiment, the metal halide is selected from ZnCl2、SnCl2And GeCl2And the like. Since chlorine has a small atomic radius relative to bromine and iodine, the distance over which electrons need to travel when the surface of the particle is used as a surface ligand is short, and thus the electron transport property can be improved.
In a preferred embodiment, the first temperature is 110-.
In a preferred embodiment, the second temperature is 110-.
In this example, the prepared inorganic semiconductor nanocrystals were metal sulfide particles. Preferably, the metal sulfide particles are selected from ZnS particles, SnS particles or GeS particles, but are not limited thereto. The inorganic semiconductor nanocrystalline prepared by the method of the embodiment at a higher temperature and by controlling the particle size (preferably 2-7 nm) has small surface defects, realizes no emission peak in a visible waveband, and does not interfere with the emission of a light emitting layer in a device structure. The higher temperature is the third temperature in this embodiment. Preferably, the third temperature is 210-. More preferably, the third temperature is 230-300 ℃.
In a preferred embodiment, the step of dispersing the cationic precursor in the solvent and heating at a first temperature to obtain a first mixture specifically comprises: and dispersing the doped metal salt and the cation precursor into a solvent, and heating at a first temperature to obtain the first mixture.
In a preferred embodiment, the doping metal salt is selected from one or more of Mg salt, Mn salt, Al salt, Y salt, V salt, and Ni salt, but is not limited thereto. By way of example, the Mg salt may be chosen from MgCl2、MgI2、Mg(NO3)2May be selected from MnCl2、MnI2、Mn (NO3)2May be selected from AlCl3、AlI3、Al(CH3COO)3May be selected from YCl2、Y(CH3COO)2、Y(NO3)2May be selected from VCl2、V(CH3COO)2、V(NO3)2May be selected from NiCl2、Ni(CH3COO)2、Ni(NO3)2But is not limited thereto.
In a further preferred embodiment, in the material of the first electron transport layer, the inorganic semiconductor nanocrystals are selected from ZnS particles, and the inorganic semiconductor nanocrystals contain a metal-doped element Al, V or Y. The HOMO energy level of the inorganic semiconductor nanocrystal can be well matched with the HOMO energy level of the light-emitting layer quantum dot, and the preferred doped ions can reduce the injection barrier of the electron transport layer to the light-emitting layer, so that the effectiveness of electron transport between the material of the transport layer and the material of the light-emitting layer is ensured. Preferably, the metal doping element is Y.
The present invention will be described in detail below with reference to examples.
Example 1:
the mixed ligand ZnO material was prepared as follows:
1) preparing a cation precursor solution: taking 4mmol of ZnCl2Mixing with 10mmol of octadecenoic acid and 10ml of ODE, heating to 150 ℃ under Ar atmosphere, and keeping the temperature for 60 min to obtain a cation precursor solution.
2) Preparing an anion precursor solution: and mixing 4.8mmol of octadecanol with 10ml of ODE, heating to 180 ℃ under Ar atmosphere, and preserving heat for 60 min to obtain an anion precursor solution.
3) Preparing mixed ligand quantum dots: heating the cation precursor solution to 280 deg.C, injecting anion precursor solution, keeping the temperature for 10 min, cooling to 150 deg.C, adding 1ml of dodecyl mercaptan, stirring for 30 min to obtain surface ligands of octadecenoic acid, dodecyl mercaptan and Cl-Precipitating the ZnO. The precipitate was dried and then formulated into a 20mg/ml mixed ligand ZnO heptane solution.
The device was prepared as follows: the device structure comprises a glass substrate, an ITO anode, a hole injection layer, a 35nm hole transmission layer, a 20nm quantum dot light emitting layer, a 40nm electron transmission layer and a 100nm cathode which are sequentially arranged from bottom to top. The electron transport layer comprises a 20nm polar ZnO layer and a 20nm ZnO layer, wherein the ZnO layer is laminated, and the surface ligand of the ZnO layer is octadecenoic acid, dodecanethiol and Cl < - >. The preparation method of the QLED device comprises the following steps:
1) a hole injection layer and a 35nm hole transport layer were sequentially coated on the ITO bottom electrode.
2) A20 nm quantum dot light-emitting layer was formed on the hole transport layer using a spin coating method at 2000rpm using a 20mg/ml light-emitting quantum dot heptane solution.
3) And sequentially coating a ZnO methanol solution and a ZnO heptane solution with mixed ligands of octadecenoic acid, dodecanethiol and Cl & lt- & gt on the quantum dot light-emitting layer by using a spin coating method, wherein the film thickness of each layer of the solution is 20nm respectively.
4) An Ag electrode with a thickness of 100nm was prepared on the electron transport layer using an evaporation method.
5) And finally, packaging the manufactured QLED device by using ultraviolet curing glue to obtain the quantum dot device.
Example 2:
mixed ligand ZnO: the Y material was prepared as follows:
1) preparing a cation precursor solution: 0.4 mmol of Y (CH) was taken3COO)2、4 mmol ZnCl2Mixing with 10mmol of octadecenoic acid and 10ml of ODE, heating to 150 ℃ under Ar atmosphere, and keeping the temperature for 60 min to obtain a cation precursor solution.
2) Preparing an anion precursor solution: and mixing 4.8mmol of octadecanol with 10ml of ODE, heating to 180 ℃ under Ar atmosphere, and preserving heat for 60 min to obtain an anion precursor solution.
3) And (3) preparing the mixed ligand quantum dots. Heating the cation precursor solution to 280 deg.C, injecting anion precursor solution, keeping the temperature for 10 min, cooling to 150 deg.C, adding 1ml of dodecyl mercaptan, stirring for 30 min to obtain surface ligands of octadecenoic acid, dodecyl mercaptan and Cl-ZnO of (2): and Y is precipitated. The precipitate was dried and then formulated into 20mg/ml of mixed ligand ZnO: and Y is a heptane solution.
The device was prepared as follows: the device structure comprises a glass substrate, an ITO anode, a hole injection layer, a 35nm hole transmission layer, a 20nm quantum dot light emitting layer, a 40nm electron transmission layer and a 100nm cathode which are sequentially arranged from bottom to top. The electron transport layer comprises a 20nm polar ZnO layer and 20nm ZnO with surface ligands of octadecenoic acid, dodecanethiol and Cl & lt- & gt, which are arranged in a stacking manner: and Y layers. The preparation method of the QLED device comprises the following steps:
1) a hole injection layer and a 35nm hole transport layer were sequentially coated on the ITO bottom electrode.
2) A20 nm quantum dot light-emitting layer was formed on the hole transport layer using a spin coating method at 2000rpm using a 20mg/ml light-emitting quantum dot heptane solution.
3) And (2) coating ZnO methanol solution and ZnO with mixed ligands of octadecenoic acid, dodecanethiol and Cl-on the quantum dot light-emitting layer in sequence by using a spin coating method: y heptane solution, each layer film thickness of which was 20 nm.
4) An Ag electrode with a thickness of 100nm was prepared on the electron transport layer using an evaporation method.
5) And finally, packaging the manufactured QLED device by using ultraviolet curing glue to obtain the quantum dot device.
In the above embodiments 1 and 2, all the devices have the same structure, except that the electron transport layer material is different from the electron transport layer material in that Y is doped with ZnO, the external quantum efficiency of the quantum dot device in which undoped ZnO is used as the electron transport layer is 12.5%, and the external quantum efficiency of ZnO: the external quantum efficiency of the quantum dot device with Y as the electron transport layer was 14.3%. The result shows that the ZnO doped with Y is beneficial to improving the luminous efficiency of the quantum dot device.
Example 3: the device structure comprises a glass substrate, an ITO anode, a hole injection layer, a 35nm hole transmission layer, a 20nm quantum dot light emitting layer, a 40nm electron transmission layer and a 100nm cathode which are sequentially arranged from bottom to top; the electron transport layer comprises a 20nm polar ZnO layer and 20nm surface ligands of OA and Cl-And (3) a ZnO quantum dot layer. The preparation method of the QLED device comprises the following steps:
coating a hole injection layer and a 35nm hole transmission layer on the ITO bottom electrode in sequence;
forming a 20nm quantum dot light-emitting layer on the hole transport layer by using a 20mg/ml light-emitting quantum dot heptane solution and a spin coating method with a rotating speed of 2000 rpm;
coating ZnO methanol solution and ZnO heptane with mixed ligands of OA and Cl-on the quantum dot light-emitting layer in sequence by using a spin coating method, wherein the film thickness of each layer of the solution is 20nm respectively;
preparing an Ag electrode with the thickness of 100nm on the electron transmission layer by using an evaporation method;
and finally, packaging the manufactured QLED device by using ultraviolet curing glue to obtain the quantum dot device.
Example 4: the device structure comprises a glass substrate, an ITO anode, a hole injection layer, a 35nm hole transmission layer, a 20nm quantum dot light emitting layer, a 50nm electron transmission layer and a 100nm cathode which are sequentially arranged from bottom to top; the electron transport layer comprises a 10nm polar ZnO layer arranged in a stacked manner, and 10nm surface ligands are octadecyl phosphoric acid and Cl-The ZnO quantum dot layer, the polar ZnO layer with the thickness of 10nm, and the surface ligand with the thickness of 10nm are octadecyl phosphoric acid and Cl-ZnO quantum dot layer, and polar ZnO layer of 10 nm. The preparation method of the QLED device comprises the following steps:
coating a hole injection layer and a 35nm hole transmission layer on the ITO bottom electrode in sequence;
forming a 20nm quantum dot light-emitting layer on the hole transport layer by using a 20mg/ml light-emitting quantum dot heptane solution and a spin coating method with a rotating speed of 2000 rpm;
and sequentially coating a ZnO methanol solution, a ZnO heptane solution with surface ligands of octadecyl phosphoric acid and Cl-, a ZnO methanol solution, a ZnO heptane solution with surface ligands of octadecyl phosphoric acid and Cl-and a ZnO methanol solution on the quantum dot light-emitting layer by using a spin coating method, wherein the thickness of each layer of film is 10nm respectively.
Preparing an Ag electrode with the thickness of 100nm on the electron transmission layer by using an evaporation method;
and finally, packaging the manufactured QLED device by using ultraviolet curing glue to obtain the quantum dot device.
Example 5: the device structure comprises a glass substrate, an ITO anode, a hole injection layer, a 20nm hole transmission layer, a 40nm quantum dot light emitting layer, a 60nm electron transmission layer and an 80nm cathode which are sequentially arranged from bottom to top; the electron transport layer comprises a 10nm polar ZnO layer which is stacked, and 10nm surface ligands are octathiol and Br-The ZnS of (1) comprises a Y quantum dot layer, a 10nm polar ZnO layer, a ZnS Y layer with 10nm surface ligands of octylmercaptan and Br-, a 10nm polar ZnO layer and a ZnS Y layer with 10nm surface ligands of octylmercaptan and Br-. The preparation method of the QLED device comprises the following steps:
coating a hole injection layer and a 20nm hole transport layer on the ITO bottom electrode in sequence;
forming a 40nm quantum dot light-emitting layer on the hole transport layer by using a spin coating method with the rotating speed of 2000rpm and a light-emitting quantum dot heptane solution with the concentration of 20 mg/ml;
coating a ZnO methanol solution, a ZnS: Y heptane solution with surface ligands of octanethiol and Br-, a ZnO methanol solution, a ZnS: Y heptane solution with surface ligands of octanethiol and Br-on the quantum dot light-emitting layer in sequence by using a spin coating method, wherein the film thickness of each layer is 10nm respectively;
preparing an Al electrode with the thickness of 80nm on the electron transport layer by using an evaporation method;
and finally, packaging the manufactured QLED device by using ultraviolet curing glue to obtain the quantum dot device.
Example 6: the device structure comprises a glass substrate, an ITO anode, a hole injection layer, a 30nm hole transmission layer, a 50nm quantum dot light emitting layer, a 60nm electron transmission layer and a 60nm cathode which are sequentially arranged from bottom to top. The electron transport layer comprises a 20nm polar ZnO layer and a 20nm surface ligand which is a ZnO/Mg quantum dot layer with octadecyl acid and Cl & lt- & gt as surface ligands. The preparation method of the QLED device comprises the following steps:
a hole injection layer and a 30nm hole transport layer were sequentially coated on the ITO bottom electrode.
A50 nm quantum dot light-emitting layer was formed on the hole transport layer using a spin coating method at 2000rpm using a 20mg/ml luminescent quantum dot ethanol solution.
And coating a ZnO-Mg solution on the quantum dot light-emitting layer by using a spin coating method, wherein the thickness of the film is 60 nm.
A Cu electrode with a thickness of 60nm was prepared on the electron transport layer using an evaporation method.
And finally, packaging the manufactured QLED device by using ultraviolet curing glue to obtain the quantum dot device.
Example 7: the device structure comprises a glass substrate, an ITO anode, a hole injection layer, a 40nm hole transmission layer, a 60nm quantum dot light emitting layer, a 50nm electron transmission layer and a 70nm cathode which are sequentially arranged from bottom to top. The electron transport layer comprises a ZnS/Mn quantum layer with 10nm surface ligands of octyl mercaptan and mercapto 3-yl propionic acid, a polar ZnO layer with 10nm, a ZnS/Mn quantum layer with the surface ligands of octyl mercaptan and mercapto 3-yl propionic acid, a polar ZnO layer with 10nm, and a ZnS/Mn quantum layer with the surface ligands of octyl mercaptan and mercapto 3-yl propionic acid, which are arranged in a stacked mode. The preparation method of the QLED device comprises the following steps:
a hole injection layer and a 40nm hole transport layer were sequentially coated on the ITO bottom electrode.
A60 nm quantum dot light-emitting layer was formed on the hole transport layer using a spin coating method at 2000rpm using a 20mg/ml luminescent quantum dot ethanol solution.
And sequentially coating a ZnS: Mn more heptane solution with surface ligands of octyl mercaptan and mercapto 3-yl propionic acid, a polar ZnO solution, a ZnS: Mn more heptane solution with surface ligands of octyl mercaptan and mercapto 3-yl propionic acid on the quantum dot light-emitting layer by using a spin coating method, wherein the film thickness of each layer is 10 nm.
An Al electrode having a thickness of 70nm was prepared on the electron transport layer by evaporation.
And finally, packaging the manufactured QLED device by using ultraviolet curing glue to obtain the quantum dot device.
In summary, the present invention provides a quantum dot light emitting diode. In the first electron transport layer material of the present invention, the surface of the particle has a mixed ligand: a halogen ligand and an oil-soluble organic ligand which renders the first electron transport layer material oil-soluble. According to the oil-soluble first electron transport layer material, the halogen ligand can improve the electron transport performance, and the oil-soluble organic ligand can effectively reduce the electron transport rate, so that the electron transport performance of the material can be adjusted, the electron transport rate and the hole transport rate in a device can be adjusted, and the luminous efficiency of a luminous layer can be improved.
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 (20)
1. A quantum dot light emitting diode comprising: anode, negative pole and setting are in the stromatolite between anode and the negative pole the stromatolite includes quantum dot light-emitting layer and the electron transport layer of range upon range of setting, quantum dot light-emitting layer is close to anode one side sets up, the electron transport layer is close to negative pole one side sets up, its characterized in that, the electron transport layer includes the first electron transport layer of at least one deck, first electron transport layer material includes: the organic semiconductor nano-particle comprises a particle, a halogen ligand and an oil-soluble organic ligand, wherein the halogen ligand and the oil-soluble organic ligand are combined on the surface of the particle, and the particle is an inorganic semiconductor nano-crystal.
2. The quantum dot light-emitting diode of claim 1, wherein the inorganic semiconductor nanocrystal has a particle size of 2-7 nm.
3. The quantum dot light-emitting diode of claim 1, wherein the inorganic semiconductor nanocrystal is non-emissive in the visible wavelength band.
4. The quantum dot light-emitting diode of claim 1, wherein the inorganic semiconductor nanocrystals are metal oxide particles selected from ZnO particles, CdO particles, SnO particles, or GeO particles; or,
the inorganic semiconductor nanocrystal is metal sulfide particles, and the metal oxide particles are selected from ZnS particles, SnS particles or GeS particles.
5. The quantum dot light-emitting diode of claim 1, wherein the halogen ligand is selected from one or more of chloride, bromide, and iodide.
6. The quantum dot light-emitting diode of claim 1, wherein the oil-soluble organic ligand is selected from one or more of a linear organic ligand having 8 or more carbon atoms, a secondary or tertiary amine having 4 or more branched carbon atoms, a substituted or unsubstituted alkylaminophosphine, a substituted or unsubstituted alkoxyphosphine, a substituted or unsubstituted silylphosphine, and an alkylphosphine having 4 or more branched carbon atoms.
7. The quantum dot light-emitting diode of claim 6, wherein the linear organic ligand with the carbon number of 8 or more is selected from one or more of organic carboxylic acid with the carbon number of 8 or more, thiol with the carbon number of 8 or more, organic phosphoric acid with the carbon number of 8 or more, and primary amine with the carbon number of 8 or more.
8. The quantum dot light-emitting diode of claim 1, wherein the oil-soluble organic ligand is a plurality of thiol having 8 or more carbon atoms, organophosphate having 8 or more carbon atoms, and substituted or unsubstituted alkylaminophosphine.
9. The quantum dot light-emitting diode of claim 1, wherein the oil-soluble organic ligand is a substituted or unsubstituted alkylaminophosphine, and the particles are metal sulfide particles;
or the oil-soluble organic ligand is organic phosphoric acid with the carbon atom number more than or equal to 8, and the particles are metal oxide particles;
or the oil-soluble organic ligand is mercaptan with the carbon atom number of more than or equal to 8, and the particles are metal sulfide particles;
or the inorganic semiconductor nanocrystal contains a metal doping element.
10. The quantum dot light-emitting diode of claim 9, wherein the metal doping element is selected from one or more of Mg, Mn, Al, Y, V and Ni;
or, the inorganic semiconductor nanocrystals are selected from ZnO particles, ZnS particles, or SnO particles.
11. The quantum dot light-emitting diode of claim 1, wherein when the electron transport layer is a first electron transport layer, the material of the quantum dot light-emitting layer is a water-soluble quantum dot.
12. The quantum dot light-emitting diode of claim 1, wherein the electron transport layer further comprises at least one second electron transport layer, and the second electron transport layer is made of a water-soluble electron transport material.
13. The qd-led of claim 12, wherein when the material of the qd-light emitting layer is water-soluble qd, the first electron transport layer is disposed on the qd-light emitting layer, the first electron transport layer is disposed on the first electron transport layer, the second electron transport layer is disposed on the first electron transport layer, and each electron transport layer in the following is disposed on each of the preceding different electron transport layers.
14. The qd-led of claim 12, wherein when the material of the qd-light emitting layer is an oil-soluble qd, the first and second electron transport layers are disposed on the qd-light emitting layer, the first and second electron transport layers are disposed on the first and second electron transport layers, and each electron transport layer in the following is disposed on each of the preceding different electron transport layers.
15. The qd-led of claim 12, wherein the total number of layers of the first and second electron transport layers is 3-6.
16. The qd-led of claim 12, wherein the second electron transport layer material is selected from ZnO particles, TiO2Particles, Ca particles, Ba particles, ZrO2Particles, CsF particles, LiF particles, CsCO3Particles and Alq3 particles.
17. The qd-led of claim 11 or 13, wherein the water-soluble qds are qds with surface-bound water-soluble ligands.
18. The qd-led of claim 17, wherein the water soluble ligands are selected from one or more of halogen ion ligands, mercapto alcohols with less than 8 carbon atoms, mercapto amines with less than 8 carbon atoms, and mercapto acids with less than 8 carbon atoms.
19. The qd-led of claim 14, wherein the oil-soluble qds are qds with surface-bound oil-soluble organic ligands.
20. The quantum dot light-emitting diode of claim 19, wherein the oil-soluble organic ligand is selected from one or more of a linear organic ligand having 8 or more carbon atoms, a secondary or tertiary amine having 4 or more branched carbon atoms, a substituted or unsubstituted alkylaminophosphine, a substituted or unsubstituted alkoxyphosphine, a substituted or unsubstituted silylphosphine, and an alkylphosphine having 4 or more branched carbon atoms.
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| CN201811044363.XA CN110890467A (en) | 2018-09-07 | 2018-09-07 | Quantum dot light-emitting diode |
| PCT/CN2019/104762 WO2020048534A1 (en) | 2018-09-07 | 2019-09-06 | Composite material and preparation method therefor and quantum dot light-emitting diode |
| US17/039,516 US20210020838A1 (en) | 2018-09-07 | 2020-09-30 | Composite material and preparation method therefor and quantum dot light-emitting diode |
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