CN106848079B

CN106848079B - Shine-charge transmission compound, the ink containing it, preparation method and QLED device

Info

Publication number: CN106848079B
Application number: CN201710090459.9A
Authority: CN
Inventors: 谢松均
Original assignee: Najing Technology Corp Ltd
Current assignee: Najing Technology Corp Ltd
Priority date: 2017-02-20
Filing date: 2017-02-20
Publication date: 2019-08-27
Anticipated expiration: 2037-02-20
Also published as: CN106848079A

Abstract

The present invention provides-charge transmission compound, the ink containing it, preparation method and the QLED devices of shining.Luminous-charge transmission the compound includes: core-shell quanta dots, has core and shell；Charge transport part, charge transport part are inorganic nano-crystal；And crosslinking section, shell are attached with charge transport part by crosslinking section.Charge transport part in the prior art as the core-shell quanta dots of luminescent layer and as transport layer is crosslinked by crosslinking section, luminous and transfer function is realized to be integrated in a compound, and then when making QLED device, not only had the function of luminescent layer using the membrane structure that the luminous-charge transmission compound is formed but also had had the function of transport layer, therefore tool can be formed by a solwution method, and there are two types of the film layers of function, reduce the implementation number of solwution method, and then simplifies the production process of QLED device.

Description

Shine-charge transmission compound, ink, preparation method and QLED containing it Device

Technical field

The present invention relates to light emitting device field, in particular to it is a kind of shine-charge transmission compound, containing its Ink, preparation method and QLED device.

Background technique

Quantum dot (Quantum Dot, abbreviation QD) is usually a kind of nanometer being made of II-VI group or iii-v element Particle can emit fluorescence after being excited, and luminescent spectrum can be controlled by changing the size of quantum dot, and its fluorescence Strength and stability is all fine, is a kind of good electroluminescent material.There are many type of quantum dot, representative to have II-VI CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe of race etc. and iii-v GaAs, GaP, GaAs, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, AlSb etc., and the quantum dot of core-shell structure being made of above-mentioned element.

With general Organic Light Emitting Diode (Organic Light-Emitting Diode, abbreviation OLED) display device phase Than light emitting diode with quantum dots display device (Quantum Dot Light-Emitting Display, abbreviation QLED) is to make With the display equipment of quantum dot emitting layer material.Since quantum dot is inorganic material, luminous organic material can be overcome to oxygen With water vapor sensitive, stability is poor, the service life is short, encapsulation difficulty is big the disadvantages of, have vast potential for future development.

Conventional QLED device architecture includes anode/hole transmission layer (multilayer)/quantum dot light emitting layer/electricity being sequentially stacked Sub- barrier layer/electron transfer layer/cathode, and generalling use solwution method prepares each film layer structure at present, but solwution method prepares each film Excellent film layer can just be obtained by needing to adjust many parameters when layer, cause the preparation method of existing QLED device cumbersome.

Summary of the invention

The main purpose of the present invention is to provide a kind of-charge transmission compounds, the ink containing it, its preparation side of shining Method and QLED device, to solve the problems, such as that QLED device preparation method in the prior art is cumbersome.

To achieve the goals above, according to an aspect of the invention, there is provided a kind of luminous-charge transmits compound, Include: core-shell quanta dots, there is core and shell；Charge transport part, charge transport part are inorganic nano-crystal；And crosslinking section, shell Layer is attached with charge transport part by crosslinking section.

Further, above-mentioned charge transport part includes having the first inorganic nano-crystal of hole transport function or with electronics Second inorganic nano-crystal of transfer function, optionally the surface of the first inorganic nano-crystal has the first ligand, the first inorganic nano Crystalline substance is preferably NiO_XNanocrystalline, NiMgO_XNanocrystalline, p-type ZnO nano is brilliant, CuO is nanocrystalline, Cu₂O is nanocrystalline, Fe₃O₄Nanocrystalline, FeO is nanocrystalline, V₂O₅Nanocrystalline, MnTiO₃Nanocrystalline, BaTiO₃It is nanocrystalline, HgS is nanocrystalline, PbS is nanocrystalline, SnS is nanocrystalline, MnS is nanocrystalline, wherein 1≤x≤2；Optionally the surface of the second inorganic nano-crystal has Ligands, and the second inorganic nano-crystal is excellent It is selected as ZnO nano crystalline substance, TiO₂Nanocrystalline, SrTiO₂Nanocrystalline, MgTiO₃Nanocrystalline, In₂S₃It is nanocrystalline, TiS is nanocrystalline.

Further, the shell layer surface of above-mentioned core-shell quanta dots has a surface ligand, the first ligand and surface ligand it is molten Solution property is identical, and Ligands are identical as the dissolubility of surface ligand, and surface ligand is oil-soluble carboxylic acids ligand, alcohol-soluble sulfydryl Carboxylic acids ligand or alcohol-soluble sulfydryl alcohols ligand, preferably alcohol-soluble mercaptan carboxylic acid class ligand are thioacetic acid ligand, sulfydryl third Sour ligand or mercaptobutyric acid ligand, preferably alcohol-soluble mercaptoalcohol class ligand are mercaptoethanol ligand or sulfydryls hexanol ligand.

Further, the precursor for forming above-mentioned crosslinking section is selected from C₂~C₁₀And there are two the crosslinking agent of the above functional group, officials It can roll into a ball as amido, hydroxyl, carboxyl or sulfydryl, preferably crosslinking agent is ethanthiol or hexamethylene diamine.

According to another aspect of the present invention, a kind of-charge transmission ink that shines is provided, including any of the above-described kind of hair Optical-electronic lotus transmits compound and solvent.

Further, above-mentioned charge transport part includes having the first inorganic nano-crystal of hole transport function or with electronics Second inorganic nano-crystal of transfer function, the first ligand of the first inorganic nano-crystal are identical with the dissolubility of solvent；Second is inorganic Nanocrystalline Ligands are identical with the dissolubility of solvent；Preferred solvent includes oil soluble material liquid or alcohol-soluble substance liquid Body, more preferable oil soluble material are C₁~C₂₀Linear paraffin, C₁~C₂₀Branched paraffin including one or more pentacyclic C₁~C₂₀Alkane or C including one or more hexatomic rings₁~C₂₀Alkane, further preferably alcohol-soluble substance be C₁~C₁₀It is straight Chain alcohol, C₁~C₁₀Branched-chain alcoho including one or more pentacyclic C₁~C₁₀Monohydric alcohol and polyalcohol including one or more The C of a hexatomic ring₁~C₁₀Monohydric alcohol and polyalcohol.

Further, above-mentioned ink further includes anti-settling agent, and anti-settling agent is selected from epoxy resin, aldehyde ketone resin, acrylic resin And/or polyurethane resin, preferred acrylic resins be lauric acid acrylic resin, glycidyl methacrylate, more preferably The weight of anti-settling agent is the 10~50% of ink weight.

According to another aspect of the present invention, a kind of preparation method of luminous-charge transmission compound, the preparation side are provided Method includes: step S1, and the first organic solution containing core-shell quanta dots raw material and second containing charge transport materials is organic Solution mixing, forms to cross-linking agent, wherein and core-shell quanta dots raw material is the core-shell quanta dots that shell layer surface has surface ligand, Charge transport materials are the inorganic nano-crystal with ligand；Step S2, by the precursor to cross-linking agent and crosslinking section be mixed to form to Cross-linking system；And step S3, make to be crosslinked to cross-linking system, obtains the liquid body containing luminous-charge transmission compound System, wherein crosslinking section replacement at least partly surface ligand and at least partly ligand are to pass the shell of core-shell quanta dots and charge Defeated material is attached by crosslinking section.

Further, the weight ratio of above-mentioned core-shell quanta dots raw material and charge transport materials is 1:0.2~2；It is preferred that first The concentration of core-shell quanta dots raw material is 10~20mg/ml, charge transport materials in more preferable second organic solution in organic solution Concentration be 10~20mg/ml.

Further, above-mentioned charge transport materials include the first inorganic nano-crystal raw material or tool with hole transport function There is the second inorganic nano-crystal raw material of electron-transport function, the surface of the first inorganic nano-crystal raw material has the first ligand, and first Inorganic nano-crystal raw material is preferably NiO_XNanocrystalline, NiMgO_XNanocrystalline, p-type ZnO nano is brilliant, CuO is nanocrystalline, Cu₂O is nanocrystalline, Fe₃O₄It is nanocrystalline, FeO is nanocrystalline, V₂O₅Nanocrystalline, MnTiO₃Nanocrystalline, BaTiO₃It is nanocrystalline, HgS is nanocrystalline, PbS is nanocrystalline, SnS is nanocrystalline, MnS is nanocrystalline, 1≤x≤2；The surface of second inorganic nano-crystal raw material has Ligands, the second inorganic nano Brilliant raw material is preferably ZnO nano crystalline substance, TiO₂Nanocrystalline, SrTiO₂Nanocrystalline, MgTiO₃Nanocrystalline, In₂S₃Nanocrystalline, TiS nanometers It is brilliant.

Further, the solvent of above-mentioned first ligand, surface ligand, the solvent of the first organic solution and the second organic solution Dissolubility it is identical；Ligands, surface ligand, the solvent of the first organic solution and the second organic solution solvent dissolubility It is identical.

Further, above-mentioned surface ligand is oil-soluble carboxylic acids ligand, alcohol-soluble mercaptan carboxylic acid's class ligand or alcohol-soluble Sulfydryl alcohols ligand, preferably alcohol-soluble mercaptan carboxylic acid class ligand are that thioacetic acid ligand, mercaptopropionic acid ligand or mercaptobutyric acid are matched Body, preferably alcohol-soluble mercaptoalcohol class ligand are mercaptoethanol ligand or sulfydryls hexanol ligand, the first organic solution and second organic The solvent of solution includes oil soluble material liquid or alcohol-soluble material liq, oil soluble material C₁~C₂₀Linear paraffin, C₁ ~C₂₀Branched paraffin including one or more pentacyclic C₁~C₂₀Alkane or C including one or more hexatomic rings₁~ C₂₀Alkane, the precursor of crosslinking section includes ethanthiol, and alcohol-soluble substance is C₁~C₁₀Straight chain alcohol, C₁~C₁₀Branched-chain alcoho, Including one or more pentacyclic C₁~C₁₀Monohydric alcohol and polyalcohol, the C including one or more hexatomic rings₁~C₁₀One First alcohol and polyalcohol, the precursor of crosslinking section include hexamethylene diamine.

Further, above-mentioned steps S2 includes: that will mix to cross-linking agent with anti-settling agent, forms the first pre-composition；By first Pre-composition and the mixing of the precursor of crosslinking section, form to cross-linking system；It is preferred that anti-settling agent is selected from epoxy resin, aldehyde ketone resin, propylene Acid resin and/or polyurethane resin, acrylic resin be lauric acid acrylic resin, glycidyl methacrylate, it is anti-settling The weight of agent is the 10~50% of liquid system weight；Preferred steps S3 stirs 2~4h at 30~40 DEG C and is crosslinked.

According to another aspect of the present invention, a kind of QLED device is provided, QLED device includes the anode being sequentially stacked, sky Composite layer, electron transfer layer and cathode are transmitted-shone in cave, or shines including stacked anode, hole transmission layer, electron-transport- Composite layer and cathode, or the luminous composite layer of the anode including being stacked, hole transport-, the luminous composite layer of electron-transport-and cathode, Wherein, the luminous composite layer of hole transport-, the luminous composite layer of electron-transport-transmit ink using any of the above-described kind luminous-charge It is made.

Further, electron injecting layer and/or electronic barrier layer are additionally provided between above-mentioned electron transfer layer and cathode, or Electron-transport-shines and is additionally provided with electron injecting layer and/or electronic barrier layer between composite layer and cathode.

It applies the technical scheme of the present invention, it will be in the prior art as the core-shell quanta dots of luminescent layer and as transport layer Charge transport part is crosslinked by crosslinking section, is realized luminous and transfer function and is integrated in a compound, and then is making When QLED device, not only had the function of luminescent layer using the membrane structure that the luminous-charge transmission compound is formed but also there is transmission The function of layer, therefore tool can be formed by a solwution method there are two types of the film layer of function, reduce the implementation of solwution method Number, and then the production process of QLED device is simplified, reduce the probability of QLED device failure.

Specific embodiment

It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.

It is in the prior art due to needing to be respectively set hole transmission layer, quantum as documented by the application background technique Point luminescent layer and electron transfer layer, cause the preparation method of QLED device cumbersome, in order to solve this problem, this application provides one Plant shine-charge transmission compound, the ink containing it, preparation method and QLED device.

In a kind of typical embodiment of the application, a kind of-charge transmission compound that shines, including nucleocapsid amount are provided Sub- point, charge transport part and crosslinking section, core-shell quanta dots have core and shell, charge transport part be inorganic nano-crystal, shell with Charge transport part is attached by crosslinking section.

Charge transport part in the prior art as the core-shell quanta dots of luminescent layer and as transport layer is passed through into crosslinking section Crosslinking realizes and luminous and transfer function is integrated in a compound, and then when making QLED device, utilizes the hair The membrane structure that optical-electronic lotus transmission compound is formed not only had had the function of luminescent layer but also had had the function of charge transport layer, therefore led to The film layer at least two functions can be formed by crossing a solwution method, reduce the implementation number of solwution method, and then be simplified The production process of QLED device, also, since the preparation total quantity of film layer in device is reduced, it reduces because of a tunic layer not The probability for uniformly influencing the uniformity of entire device reduces a possibility that film layer production fails, improves QLED device Production stability.

In a preferred embodiment of the present application, above-mentioned charge transport part includes first nothing with hole transport function Machine is nanocrystalline, and the surface of the first inorganic nano-crystal can be without ligand, it is possible to have the first ligand, the first inorganic nano-crystal are excellent It is selected as NiO_XNanocrystalline, NiMgO_XNanocrystalline, p-type ZnO nano is brilliant, CuO is nanocrystalline, Cu₂O is nanocrystalline, Fe₃O₄Nanocrystalline, FeO receives Meter Jing, V₂O₅Nanocrystalline, MnTiO₃Nanocrystalline, BaTiO₃It is nanocrystalline, HgS is nanocrystalline, PbS is nanocrystalline, SnS is nanocrystalline, MnS receives Meter Jing, 1≤x≤2, wherein NiO_XNanocrystalline expression NiO₁Nanocrystalline or NiO₂Nanocrystalline or NiO₁Nanocrystalline and NiO₂Nanometer Brilliant mixture.

In the application another kind preferred embodiment, above-mentioned charge transport part includes second with electron-transport function The surface of inorganic nano-crystal, the second inorganic nano-crystal can not have ligand, it is possible to have Ligands, the second inorganic nano-crystal Preferably ZnO nano crystalline substance, TiO₂Nanocrystalline, SrTiO₂Nanocrystalline, MgTiO₃Nanocrystalline, In₂S₃It is nanocrystalline, TiS is nanocrystalline.

Either charge transport part has the function of that electron-transport still has the function of hole transport, the core cooperated with it The shell layer surface of shell quantum dot raw material has surface ligand, the ligand and core-shell quanta dots of charge transport materials in cross-linking process The ligand portion of being crosslinked of raw material replaces, in order to be easier to carry out above-mentioned replacement process, preferred the first of the first inorganic nano-crystal Ligand is identical as the dissolubility of surface ligand, and the Ligands of the second inorganic nano-crystal and the dissolubility of surface ligand are identical (molten Solution property is identical, and to refer to different ligands all be oil-soluble or is all alcohol-soluble).Usually as above-mentioned core-shell quanta dots raw material With charge transport materials it is each it is nanocrystalline be solwution method preparation, when preparation presoma used ligand species determine it is obtained Nanocrystalline ligand, the ligand of nanocrystalline institute's band determine it is nanocrystalline belong to oil-soluble or alcohol-soluble, it is nanocrystalline On ligand can be oil-soluble ligand or alcohol-soluble ligand, the ligand of the shell layer surface of core-shell quanta dots raw material may be oil Soluble ligand or alcohol-soluble ligand, in the process for being attached core-shell quanta dots raw material and charge transport materials by crosslinking section In, the dissolubility of the ligand of the shell layer surface of ligand and core-shell quanta dots raw material on charge transport materials, which is consistent, to be made to be crosslinked It becomes easier to, for example, the ligand of the shell layer surface of core-shell quanta dots raw material is oil-soluble carboxylic acids ligand, then charge transmits Material, which also selects, has the nanocrystalline of oil-soluble carboxylic acids ligand, if the nanocrystalline raw material prepared is band alcohol-soluble sulfydryl alcohols The alcohol-soluble sulfydryl alcohols ligand of nanocrystal surface is changed to oil-soluble carboxylic acids ligand by the method for ligand exchange by ligand, Then it being attached by crosslinking section, specifically, it is assumed that the precursor (i.e. crosslinking agent) of crosslinking section has G1 and G2 functional group, One of functional group G1 replaces the ligand A on nanocrystalline (abbreviation NC), another functional group G2 to replace core-shell quanta dots (referred to as QD the ligand B on), to obtain the-charge transmission compound that shines of NC-G1-C-G2-QD structure, wherein G1-C-G2 is to hand over Connection portion, C are carbochains, and at least partly ligand A is lost after NC reaction, at least partly ligand B is lost after QD reaction, because of a quantum Point or one it is nanocrystalline all have multiple ligands, crosslinking agent can have more than two functional groups for participating in cross-linking reactions, institute With the nanocrystalline network structure that will form crosslinking of a group quantum dot and a group, for example, the Zn atom on core-shell quanta dots raw material surface On there is oleic acid ligand to be coordinated therewith, the reaction of crosslinking agent hexamethylene diamine is added, makes amino in hexamethylene diamine and Zn Atomic coordinate, to replace Change original oleic acid ligand.Similarly, also can for the nanocrystalline Ni atom such as NiOx (1≤x≤2) surface of charge transmission Such ligand replacement occurs.It is crosslinked using above-mentioned charge transport materials and core-shell quanta dots raw material, realizes charge biography Transmission function and light-emitting function are integrated in a film layer, i.e., hole transmission layer and luminescent layer are merged into a functional layer or incited somebody to action Electron transfer layer and luminescent layer merge into a functional layer.

In addition, the first ligand of the first inorganic nano-crystal is identical as the dissolubility of core-shell quanta dots raw material surface ligand, the The Ligands of two inorganic nano-crystals and the dissolubility of surface ligand are identical, and identical dissolubility refers to be both oil-soluble or same Be it is water-soluble, the shell layer surfaces of preferably above-mentioned core-shell quanta dots has oil-soluble mercaptan carboxylic acid class ligand, oil-soluble carboxylic acids Ligand or alcohol-soluble sulfydryl alcohols ligand, preferably alcohol-soluble mercaptan carboxylic acid class ligand are thioacetic acid ligand, mercaptopropionic acid ligand Or mercaptobutyric acid ligand, preferably alcohol-soluble mercaptoalcohol class ligand is mercaptoethanol ligand or sulfydryls hexanol ligand.

It can be seen that the principle of crosslinking of core-shell quanta dots raw material, charge transport materials and crosslinking section precursor may be summarized as follows:

The shell layer surface of core-shell quanta dots raw material has one or more first ligands, and the surface of charge transport materials has One or more Ligands, crosslinking section precursor have at least two functional groups, and at least one of functional group replaces the At least one of one ligand connect crosslinking section with core-shell quanta dots surface, and at least one of another functional group replaces At least one of Ligands connect crosslinking section with charge transport materials surface, and shone-charge transmission compound.

Above-mentioned crosslinking section is the structure formed after crosslinking section precursor connects core-shell quanta dots with charge transport materials, preferably The precursor for forming crosslinking section is selected from C₂~C₁₀And there are two the above functional group crosslinking agent, functional group be amido, hydroxyl, carboxyl or Sulfydryl, preferably crosslinking agent are ethanthiol or hexamethylene diamine.Wherein, above-mentioned functional group can be with the metal (shell of core-shell quanta dots The metallic atom on surface and the metallic atom of nanocrystal surface) realize coordination.

In a kind of typical embodiment of the application, a kind of-charge transmission ink that shines is provided, including any of the above-described Luminous-charge transmission the compound and solvent of kind.

After luminous-charge transmission compound dispersion of the application is formed ink in a solvent, it is used directly for making The corresponding function layer of QLED device, using simple, and material can stablize preservation.

When charge transport part includes having the first inorganic nano-crystal of hole transport function or with electron-transport function When the second inorganic nano-crystal, in order to improve the stability of ink, the first ligand of preferably the first inorganic nano-crystal and solvent it is molten Solution property is identical；The Ligands of second inorganic nano-crystal and the dissolubility of solvent are identical, and more preferable above-mentioned solvent includes oil-soluble Material liq or alcohol-soluble material liq.Oil soluble material is C₁~C₂₀Linear paraffin, C₁~C₂₀Branched paraffin including one A or multiple pentacyclic C₁~C₂₀Alkane or C including one or more hexatomic rings₁~C₂₀Alkane.Alcohol-soluble substance is C₁~C₁₀Straight chain alcohol, C₁~C₁₀Branched-chain alcoho including one or more pentacyclic C₁~C₁₀Monohydric alcohol and polyalcohol, packet Include the C of one or more hexatomic rings₁~C₁₀Monohydric alcohol and polyalcohol.

In order to improve the stability in ink after luminous-charge transmission crosslinking complexes, the preferably ink further includes anti-settling Agent, wherein the anti-settling agent is selected from epoxy resin, aldehyde ketone resin, acrylic resin and/or polyurethane resin, preferred acrylic resins For lauric acid acrylic resin, glycidyl methacrylate, the weight of more preferable anti-settling agent be ink weight 10~ 50%.

In another typical embodiment of the application, a kind of preparation side of luminous-charge transmission compound is provided Method, the preparation method include: step S1, by the first organic solution containing core-shell quanta dots raw material and contain charge transport materials The second organic solution mixing, formed to cross-linking agent, wherein above-mentioned core-shell quanta dots raw material be shell layer surface have surface ligand Core-shell quanta dots, charge transport materials be the inorganic nano-crystal raw material with ligand；Step S2, will be to cross-linking agent and crosslinking section Precursor be mixed to form to cross-linking system；And step S3, make to be crosslinked to cross-linking system, obtain containing-charge the biography that shines The liquid system of defeated compound, wherein crosslinking section replacement at least partly quantum dot surface ligand and at least partly charge transmission material The ligand of material is the shell of core-shell quanta dots and charge transport part to be attached by crosslinking section.

Core-shell quanta dots raw material is dispersed in the form of the first organic solution, charge is transmitted by above-mentioned preparation method Material is dispersed in the form of the second organic solution, when mixing the first organic solution and the second organic solution, can be made It obtains core-shell quanta dots raw material and charge transport materials uniformly mixes；On the basis of mixed uniformly, the precursor pair of crosslinking section is utilized Core-shell quanta dots raw material and charge transport materials are crosslinked, on crosslinking section replacement at least partly core-shell quanta dots raw material shell Surface ligand also replaces the ligand of at least partly inorganic nano-crystal raw material, realizes core-shell quanta dots raw material and charge transport materials It is compound.Above-mentioned preparation method is easy to operate, easy to implement, and is formed by the liquid system warp containing luminous-charge transmission Precipitation purification, then with after the dissolution of corresponding solvent, can be used to make the composite layer of corresponding transfer function and light-emitting function, subtract Lack the implementation number of solwution method used by the production of functional layer, and then simplifies the production process of QLED device, and drop The low probability of failure for preparing QLED device.Wherein, being precipitated out with ethyl alcohol etc. for oily phase is dissolved with alkane, alcohol phase can It is dissolved with being precipitated out with n-hexane etc. with alcohols.

When by transfer function and integrated light-emitting function, on the basis for improving illumination effect and charge laser propagation effect as far as possible On, the uniformity of both optimization dispersion, the preferably weight ratio of core-shell quanta dots raw material and charge transport materials are 1:0.2~2；It is excellent The concentration for selecting core-shell quanta dots raw material in the first organic solution is 10~20mg/ml, and charge passes in more preferable second organic solution The concentration of defeated material is 10~20mg/ml.

In a preferred embodiment of the present application, above-mentioned charge transport materials include first with hole transport function The surface of inorganic nano-crystal raw material, the first inorganic nano-crystal raw material has the first ligand, and the first inorganic nano-crystal raw material is preferred For NiO_XNanocrystalline, NiMgO_XNanocrystalline, p-type ZnO nano is brilliant, CuO is nanocrystalline, Cu₂O is nanocrystalline, Fe₃O₄Nanocrystalline, FeO nanometers Brilliant, V₂O₅Nanocrystalline, MnTiO₃Nanocrystalline, BaTiO₃It is nanocrystalline, HgS is nanocrystalline, PbS is nanocrystalline, SnS is nanocrystalline, MnS nanometers Crystalline substance, x are the real number between 1 to 2, and including 1 and 2.

In the application another kind preferred embodiment, above-mentioned charge transport materials raw material includes having the function of electron-transport The second inorganic nano-crystal raw material, the surface of the second inorganic nano-crystal raw material has Ligands, the second inorganic nano-crystal raw material Preferably ZnO nano crystalline substance, TiO₂Nanocrystalline, SrTiO₂Nanocrystalline, MgTiO₃Nanocrystalline, In₂S₃It is nanocrystalline, TiS is nanocrystalline.

First inorganic nano-crystal raw material and the first inorganic nano-crystal above-mentioned are the material of crosslinking front and back respectively, wherein the One inorganic nano-crystal raw material has the first ligand, and the first inorganic nano-crystal is that at least partly the first ligand is crosslinked portion after cross-linking Substituted charge transport part；Second inorganic nano-crystal raw material and the second inorganic nano-crystal above-mentioned are the material of crosslinking front and back respectively Material, wherein the second inorganic nano-crystal raw material has Ligands, and the second inorganic nano-crystal is at least partly second to match after cross-linking The charge transport part that the body portion of being crosslinked replaces.

No matter charge transport materials have the function of electron-transport or have the function of hole transport, the core cooperated with it The shell layer surface of shell quantum dot has surface ligand, in order to more easily be crosslinked, preferred the first of the first inorganic nano-crystal raw material Ligand is identical as the dissolubility of surface ligand, the dissolubility phase of the Ligands and surface ligand of the second inorganic nano-crystal raw material Together.Usually as above-mentioned core-shell quanta dots and charge transport materials it is each it is nanocrystalline be solwution method preparation, when preparation, is used The ligand species of presoma determine that nanocrystalline ligand obtained, the ligand of nanocrystalline institute's band determine that nanocrystalline is to belong to oil Dissolubility or alcohol-soluble, it is nanocrystalline on ligand can be oil-soluble ligand or alcohol-soluble ligand, core-shell quanta dots raw material The ligand of shell layer surface may be oil-soluble ligand or alcohol-soluble ligand, by crosslinking section by core-shell quanta dots raw material with During charge transport materials are attached, the ligand of the shell layer surface of ligand and core-shell quanta dots on charge transport materials Dissolubility be consistent make crosslinking become easier to, for example, the ligand of the shell layer surface of core-shell quanta dots raw material be oil-soluble Carboxylic acids ligand, then charge transport materials, which also select, has the nanocrystalline of oil-soluble carboxylic acids ligand, if the nanometer prepared Crystalline substance is alcohol-soluble sulfydryl alcohols ligand, is changed to the alcohol-soluble sulfydryl alcohols ligand of nanocrystal surface by the method for ligand exchange Oil-soluble carboxylic acids ligand, is then attached by crosslinking section, specifically, it is assumed that the precursor (i.e. crosslinking agent) of crosslinking section With G1 and G2 functional group, one of functional group G1 replaces the ligand A on nanocrystalline (abbreviation NC), another functional group G2 to replace Fall the ligand B on core-shell quanta dots (abbreviation QD), so that-charge transmission the compound that shines of NC-G1-C-G2-QD structure is obtained, Wherein, G1-C-G2 is crosslinking section, and C is carbochain, and at least partly ligand A is lost after NC reaction, loses after QD reaction and at least partly matches Body B because a quantum dot or one it is nanocrystalline all have multiple ligands, crosslinking agent, which can have, more than two participates in crosslinking The functional group of reaction, so a group quantum dot and the nanocrystalline network structure that will form crosslinking of a group, for example, core-shell quanta dots are former Expect there is oleic acid ligand to be coordinated therewith on the Zn atom on surface, the reaction of crosslinking agent hexamethylene diamine is added, makes the amino and Zn in hexamethylene diamine Atomic coordinate, to replace original oleic acid ligand.Similarly, nanocrystalline raw material such as NiOx (1≤x for charge transmission ≤ 2) such ligand replacement can also occur for the Ni atom on surface.Using above-mentioned charge transport materials and core-shell quanta dots raw material into Row crosslinking, realize charge transfer function and light-emitting function be integrated in a film layer, i.e., by hole transmission layer and shine it is laminated And for a functional layer or electron transfer layer and luminescent layer are merged into a functional layer.

In addition, core-shell quanta dots raw material is in order to increase dispersibility of the charge transport materials in the first organic solution The Combination of the dispersibility of two organic solutions and the first organic solution and the second organic solution, preferably above-mentioned first inorganic receives Brilliant first ligand of raw material of rice, the surface ligand of core-shell quanta dots, the solvent of the first organic solution and the second organic solution it is molten The dissolubility of agent is identical.It is preferred that the surface ligand of the Ligands of above-mentioned second inorganic nano-crystal raw material, core-shell quanta dots, first The dissolubility of the solvent of organic solution and the solvent of the second organic solution is identical.Certainly, if not identical can be using stirring etc. Mode improves above-mentioned dispersibility and Combination.

Since molecular weight and volume increase after core-shell quanta dots raw material and charge transport materials crosslinking, it is easy aggregation, is It avoids when cross-linking reaction and generation that when holding time is longer settles, preferred above-mentioned steps S2 includes: will be to cross-linking agent and anti- Heavy agent mixing, forms the first pre-composition；First pre-composition and the precursor of crosslinking section are mixed, formed to cross-linking system, it is preferably anti- Heavy agent is selected from epoxy resin, aldehyde ketone resin, acrylic resin and/or polyurethane resin, and acrylic resin is laurel acid acrylic acid Resin, glycidyl methacrylate, in addition, in order to avoid excessive anti-settling agent is to charge laser propagation effect and illumination effect It influences, the weight of preferably above-mentioned anti-settling agent is the 10~50% of liquid system weight.

It is crosslinked furthermore it is preferred that above-mentioned steps S3 stirs 2~4h at 30~40 DEG C.Using above-mentioned crosslinking agent above-mentioned It is crosslinked under conditions of mild, enables to core-shell quanta dots and each nanocrystalline holding original function.

In the application in another typical embodiment, a kind of QLED device is provided, which includes successively Stacked anode, hole transport-shine composite layer, electron transfer layer and cathode, or including stacked anode, hole transmission layer, The luminous composite layer of electron-transport-and cathode, or shine including stacked anode, the luminous composite layer of hole transport-, electron-transport- Composite layer and cathode, wherein hole transport-composite layer, electron-transport-composite layer that shines that shines uses any of the above-described kind of hair Optical-electronic lotus transmission ink is made.Since luminous-charge transmission compound of the application being capable of integrated light-emitting-hole transport Function or integrated light-emitting-electron-transport function, therefore, the above-mentioned-charge transmission ink formation hole biography that can be shone using this Defeated-luminous composite layer of shine composite layer, electron-transport-, reduces the function layer number of QLED device.

In order to improve the stability of device, the preferably luminous composite layer of hole transport-and the luminous composite layer of electron-transport-is adjacent When, hole transport-shine composite layer hole mobile material the first ligand and electron-transport-shine composite layer electron-transport The dissolubility of the Ligands of material is different.I.e. core-shell quanta dots react the compound F1 generated with the first inorganic nano-crystal raw material It is adjacent that the film layer of compound F2 production generated is reacted with core-shell quanta dots, with the second inorganic nano-crystal raw material, then compound In the first inorganic nano-crystal surface ligand it is different from the dissolubility of the surface ligand of the second inorganic nano-crystal, for example, apparatus There is the first inorganic nano-crystal of sulfydryl alcohols ligand to react answering for generation with the same core-shell quanta dots with sulfydryl alcohols ligand Object F1 is closed, then is reacted with the second inorganic nano-crystal with carboxylic acids ligand with the same core-shell quanta dots with carboxylic acids ligand The compound F2 of generation, then using compound F1 and compound F2 as two film layers adjacent in QLED device.

Furthermore it is preferred that electron injecting layer and/or electronic barrier layer are additionally provided between above-mentioned electron transfer layer and cathode, or Electron-transport-shines and is additionally provided with electron injecting layer and/or electronic barrier layer between composite layer and cathode.It is transmitted with balance electronic With the speed of hole transport.

Below with reference to embodiment and comparative example, the beneficial effect of the application is further illustrated.

Embodiment 1

Hole mobile material NiO_XThe synthesis of (1≤x≤2) nanocrystalline (the first inorganic nano-crystal raw material): by the hard of 1mmol Resin acid nickel, the lithium stearate of 0.2mmol, 6mmol octadecyl alcolol be added in the 1- octadecylene of 10ml, be put into 50ml flask, It is warming up to 80 DEG C under inert gas shielding, vacuumizes 30min；It is warming up to 280 DEG C of heat preservation 120min under inert gas protection, it is cold But to room temperature, centrifugation obtains colloid NiO after precipitating reagent ethyl alcohol is added_XIt is nanocrystalline.

Quantum dot and hole mobile material NiO_XCrosslinking: use surface ligand for the red light quantum point CdSe/CdS of oleic acid (being purchased from NNCrystal Technology Co., Ltd.) be used as core-shell quanta dots, by 1ml concentration be 15mg/ml quantum dot hexane solution with The NiO hexane solution that 1ml concentration is 15mg/ml mixes, and the lauryl acrylate (trade mark LA) of 1wt% is added to prevent coagulation, 10 μ l crosslinking agent ethanthiols are reinjected, stir 3h at 35 DEG C.Using ethyl alcohol by after above-mentioned cross-linking reaction quantum dot and hole Transmission material NiO_XCarry out precipitation purification, after be dissolved in dodecane and be configured to-hole transport the ink that shines.

The crosslinking of quantum dot and electron transport material ZnO (the second inorganic nano-crystal raw material): red light quantum point CdSe/ is used CdS is core-shell quanta dots, first carries out mercaptopropionic acid ligand exchange to the core-shell quanta dots, and obtaining surface ligand is mercaptopropionic acid CdSe/CdS quantum dot is dissolved in ethyl alcohol, then is with 1ml concentration by the quantum dot ethanol solution that 1ml concentration is 15mg/ml The ZnO ethanol solution of 15mg/ml mixes, and the water-soluble acrylic rouge (LZ5005, blue bamboo chemical industry) that dosage is 1wt%, which is added, to be prevented Coagulation reinjects 10 μ l crosslinking agent hexamethylene diamines, stirs 3h at 35 DEG C.Using n-hexane by after above-mentioned cross-linking reaction quantum dot with Electron transport material NiO_XCarry out precipitation purification, after be dissolved in ethyl alcohol-electron-transport the ink that is configured to shine.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Implanted layer luminous-hole transport the ink is arranged on above-mentioned hole injection layer using spin-on techniques, after drying and forming-film The luminous composite layer of hole transport-is formed, luminous-electron-transport ink is arranged using spin coating technique and is shone again in hole transport- Layer is closed, forms the luminous composite layer of electron-transport-after drying and forming-film, metal Ag conduct is set on the luminous composite layer of electron-transport- Glass substrate is arranged in cathode on cathode, obtains QLED.

Embodiment 2

Hole mobile material NiO_XThe synthesis of nanocrystalline (the first inorganic nano-crystal raw material) is the same as embodiment 1.

Quantum dot and hole mobile material NiO_XThe crosslinking of (the first inorganic nano-crystal raw material): use surface ligand for oleic acid Red light quantum point CdSe/CdS (being purchased from NNCrystal Technology Co., Ltd.) be used as core-shell quanta dots, by 1ml concentration be 15mg/ The quantum dot hexane solution and 0.2ml concentration of ml are the NiO of 15mg/ml_XHexane solution mixing, is added the acrylic acid moon of 1wt% Osmanthus ester (trade mark LA) reinjects 10 μ l crosslinking agent ethanthiols, stirs 3h at 35 DEG C to prevent coagulation.Using ethyl alcohol by above-mentioned friendship Quantum dot and hole mobile material NiO after connection reaction_XCarry out precipitation purification, after be dissolved in dodecane be configured to shine-hole passes Inking water.

The crosslinking of quantum dot and electron transport material ZnO (the second inorganic nano-crystal raw material): red light quantum point CdSe/ is used CdS is core-shell quanta dots, first carries out mercaptopropionic acid ligand exchange to the core-shell quanta dots, and obtaining surface ligand is mercaptopropionic acid CdSe/CdS quantum dot, is dissolved in ethyl alcohol, then by 1ml concentration be 15mg/ml quantum dot ethanol solution and 2ml concentration be 15mg/ The ZnO ethanol solution of ml mixes, and the water-soluble acrylic rouge (LZ5005, blue bamboo chemical industry) that dosage is 1wt%, which is added, prevents coagulation, 10 μ l crosslinking agent hexamethylene diamines are reinjected, stir 3h at 35 DEG C.Using n-hexane by the quantum dot and electronics after above-mentioned cross-linking reaction Transmission material NiO_XCarry out precipitation purification, after be dissolved in ethyl alcohol-electron-transport the ink that is configured to shine.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Luminous-hole transport the ink is arranged on hole injection layer using spin-on techniques, is formed after drying and forming-film by implanted layer Hole transport-shines composite layer, this is shone-electron-transport ink is arranged using spin-on techniques and shines in hole transport- Composite layer forms electron-transport-after drying and forming-film and shines composite layer, makees in the electron-transport-setting metal Ag on composite layer that shines For cathode, glass substrate is set on cathode, obtains QLED.

Embodiment 3

Quantum dot and hole mobile material NiO_XCrosslinking: use surface ligand for the red light quantum point CdSe/CdS of oleic acid (being purchased from NNCrystal Technology Co., Ltd.) be used as core-shell quanta dots, by 1ml concentration be 15mg/ml quantum dot hexane solution with 2ml concentration is the NiO of 15mg/ml_XHexane solution mixing, is added the lauryl acrylate (trade mark LA) of 1wt% to prevent coagulation, 10 μ l crosslinking agent ethanthiols are reinjected, stir 3h at 35 DEG C.Using ethyl alcohol by after above-mentioned cross-linking reaction quantum dot and hole Transmission material NiO_XCarry out precipitation purification, after be dissolved in dodecane and be configured to-hole transport the ink that shines.

The crosslinking of quantum dot and electron transport material ZnO (the second inorganic nano-crystal raw material): red light quantum point CdSe/ is used CdS is core-shell quanta dots, first carries out mercaptopropionic acid ligand exchange to the core-shell quanta dots, and obtaining surface ligand is mercaptopropionic acid CdSe/CdS quantum dot is dissolved in ethyl alcohol, then is with 0.2ml concentration by the quantum dot ethanol solution that 1ml concentration is 15mg/ml The ZnO ethanol solution of 15mg/ml mixes, and the water-soluble acrylic rouge (LZ5005, blue bamboo chemical industry) that dosage is 1wt%, which is added, to be prevented Coagulation reinjects 10 μ l crosslinking agent hexamethylene diamines, stirs 3h at 35 DEG C.Using n-hexane by after above-mentioned cross-linking reaction quantum dot with Electron transport material NiO_XCarry out precipitation purification, after be dissolved in ethyl alcohol-electron-transport the ink that is configured to shine.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Implanted layer, luminous-hole transport ink is arranged on hole injection layer using spin-on techniques, is formed after drying and forming-film empty Composite layer is transmitted-is shone in cave, will shine-electron-transport ink be arranged using spin-on techniques shine in hole transport-it is compound Layer, the luminous composite layer of electron-transport-is formed after drying and forming-film, setting metal Ag is used as yin on the luminous composite layer of electron-transport- Glass substrate is arranged in pole on cathode, obtains QLED.

Embodiment 4

Quantum dot and hole mobile material NiO_XThe crosslinking of (the second inorganic nano-crystal raw material): red light quantum point is used CdSe/CdS as core-shell quanta dots, by 1ml concentration be 15mg/ml quantum dot hexane solution and 1ml concentration be 15mg/ml's NiO_XHexane solution mixing, the lauryl acrylate (trade mark LA) of 1wt% is added to prevent coagulation, reinject 10 μ l crosslinking agents oneself Two mercaptan stir 3h at 35 DEG C.Using ethyl alcohol by after above-mentioned cross-linking reaction quantum dot and hole mobile material NiO_XIt is sunk Form sediment purification, after be dissolved in dodecane and be configured to-hole transport the ink that shines.

Quantum dot and electron transport material TiO₂The crosslinking of (the second inorganic nano-crystal raw material): red light quantum point is used CdSe/CdS is core-shell quanta dots, first carries out mercaptopropionic acid ligand exchange to the core-shell quanta dots, and obtaining surface ligand is sulfydryl The CdSe/CdS quantum dot of propionic acid is dissolved in ethyl alcohol, then is with 1ml concentration by the quantum dot ethanol solution that 1ml concentration is 15mg/ml The TiO of 15mg/ml₂It is anti-that the water-soluble acrylic rouge (LZ5005, blue bamboo chemical industry) that dosage is 1wt% is added in ethanol solution mixing Only coagulation reinjects 10 μ l crosslinking agent hexamethylene diamines, stirs 3h at 35 DEG C.Using n-hexane by the quantum dot after above-mentioned cross-linking reaction With electron transport material NiO_XCarry out precipitation purification, after be dissolved in ethyl alcohol-electron-transport the ink that is configured to shine.

Embodiment 5

Quantum dot and hole mobile material NiMgO_XIt is nanocrystalline that (the first inorganic nano-crystal raw material is purchased from nano-crystal science and technology share Co., Ltd) crosslinking: using red light quantum point CdSe/CdS be used as core-shell quanta dots, by 1ml concentration be 15mg/ml quantum The NiMgO that point hexane solution and 1ml concentration are 15mg/ml_XHexane solution mixing, is added the lauryl acrylate (trade mark of 1wt% LA) to prevent coagulation, 10 μ l crosslinking agent ethanthiols is reinjected, stir 3h at 35 DEG C.It will be after above-mentioned cross-linking reaction using ethyl alcohol Quantum dot and hole mobile material NiMgO_XCarry out precipitation purification, after be dissolved in dodecane and be configured to-hole transport the ink that shines.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Implanted layer, luminous-hole transport ink is arranged on hole injection layer using spin-on techniques, is formed after drying and forming-film empty Composite layer is transmitted-is shone in cave, and electron transport material ZnO is configured to ink, which is arranged using spin-on techniques Electron transfer layer is formed after the luminous composite layer of hole transport-, drying and forming-film, setting metal Ag is as yin on electron transfer layer Glass substrate is arranged in pole on cathode, obtains QLED.

Embodiment 6

Quantum dot and hole mobile material Fe₃O₄It is nanocrystalline that (the first inorganic nano-crystal raw material, being purchased from nano-crystal science and technology share has Limit company) crosslinking: using red light quantum point CdSe/CdS be used as core-shell quanta dots, by 1ml concentration be 15mg/ml quantum dot The Fe that hexane solution and 1ml concentration are 15mg/ml₃O₄N-heptane solution mixing, is added the lauryl acrylate (trade mark LA) of 1wt% To prevent coagulation, 10 μ l crosslinking agent ethanthiols are reinjected, stir 3h at 35 DEG C.Using ethyl alcohol by the amount after above-mentioned cross-linking reaction Son point and hole mobile material Fe₃O₄Carry out precipitation purification, after be dissolved in dodecane and be configured to-hole transport the ink that shines.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Implanted layer, luminous-hole transport ink is arranged on hole injection layer using spin-on techniques, is formed after drying and forming-film empty Composite layer is transmitted-is shone in cave, and electron transport material ZnO is configured to ethyl alcohol ink, which is utilized spin-on techniques Setting forms electron transfer layer after the luminous composite layer of hole transport-, drying and forming-film, and metal Ag conduct is arranged on electron transfer layer Glass substrate is arranged in cathode on cathode, obtains QLED.

Embodiment 7

Quantum dot and hole mobile material V₂O₅It is nanocrystalline that (it is limited to be purchased from nano-crystal science and technology share for the first inorganic nano-crystal raw material Company) crosslinking: using red light quantum point CdSe/CdS be used as core-shell quanta dots, by 1ml concentration for 15mg/ml quantum dot oneself The V that alkane solution and 1ml concentration are 15mg/ml₂O₅Cyclohexane solution mixing, be added the lauryl acrylate (trade mark LA) of 1wt% with Coagulation is prevented, 10 μ l crosslinking agent ethanthiols is reinjected, stirs 3h at 35 DEG C.Using ethyl alcohol by the quantum after above-mentioned cross-linking reaction Point and hole mobile material V₂O₅Carry out precipitation purification, after be dissolved in dodecane and be configured to-hole transport the ink that shines.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Implanted layer, then by the quantum dot and hole mobile material V after above-mentioned cross-linking reaction₂O₅Carry out precipitation purification, after be dissolved in dodecane It is configured to ink, which is arranged on hole injection layer using spin-on techniques, forms hole transport-after drying and forming-film Shine composite layer, and electron transport material ZnO is configured to ethyl alcohol ink, which is arranged using spin-on techniques in sky Composite layer is transmitted-is shone in cave, forms electron transfer layer after drying and forming-film, on electron transfer layer setting metal Ag as cathode, Glass substrate is set on cathode, obtains QLED.

Embodiment 8

Quantum dot and hole mobile material BaTiO₃It is nanocrystalline that (the first inorganic nano-crystal raw material is purchased from nano-crystal science and technology share Co., Ltd) crosslinking: using red light quantum point CdSe/CdS be used as core-shell quanta dots, by 1ml concentration be 15mg/ml quantum The BaTiO that point hexane solution and 1ml concentration are 15mg/ml₃Isooctane solution mixing, is added the lauryl acrylate (board of 1wt% Number LA) to prevent coagulation, 10 μ l crosslinking agent ethanthiols are reinjected, stir 3h at 35 DEG C.Using ethyl alcohol by above-mentioned cross-linking reaction Quantum dot and hole mobile material BaTiO afterwards₃Carry out precipitation purification, after be dissolved in dodecane and be configured to shine-hole transport ink Water.

Embodiment 9

Nanocrystalline (it is limited to be purchased from nano-crystal science and technology share for the first inorganic nano-crystal raw material by quantum dot and hole mobile material PbS Company) crosslinking: using red light quantum point CdSe/CdS be used as core-shell quanta dots, by 1ml concentration for 15mg/ml quantum dot oneself Alkane solution and 1ml concentration are that the PbS isooctane solution of 15mg/ml mixes, be added the lauryl acrylate (trade mark LA) of 1wt% with Coagulation is prevented, 10 μ l crosslinking agent ethanthiols is reinjected, stirs 3h at 35 DEG C.Using ethyl alcohol by the quantum after above-mentioned cross-linking reaction Point carries out precipitation purification with hole mobile material PbS, after be dissolved in dodecane and be configured to-hole transport the ink that shines.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Luminous-electron-transport ink is arranged on hole injection layer using spin-on techniques, forms electricity after drying and forming-film by implanted layer Son transmits-shines composite layer, and glass base is arranged as cathode in setting metal Ag on cathode on the luminous composite layer of electron-transport- Plate obtains QLED.

Embodiment 10

Quantum dot and electron transport material SrTiO₂The crosslinking of (the second inorganic nano-crystal raw material): red light quantum point is used CdSe/CdS is core-shell quanta dots, first carries out mercaptopropionic acid ligand exchange to the core-shell quanta dots, and obtaining surface ligand is sulfydryl The CdSe/CdS quantum dot of propionic acid is dissolved in ethyl alcohol, then the quantum dot ethanol solution and 1ml concentration for being 15mg/ml by 1ml concentration For the SrTiO of 15mg/ml₂Ethanol solution mixing, the water-soluble acrylic rouge (trade mark THFA) that 1wt% is added prevent coagulation, then 10 μ l crosslinking agent hexamethylene diamines are injected, stir 3h at 35 DEG C.The quantum dot after above-mentioned cross-linking reaction is passed with electronics using n-hexane Defeated material SrTiO₂Carry out precipitation purification, after be dissolved in ethyl alcohol-electron-transport the ink that is configured to shine.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Luminous-electron-transport ink is arranged on hole injection layer using spin-on techniques, forms electricity after drying and forming-film by implanted layer Son transmission-luminous composite layer, electron-transport-shine composite layer setting metal Ag as cathode, glass substrate are arranged on cathode, Obtain QLED.

Embodiment 11

Quantum dot and electron transport material In₂S₃The crosslinking of (the second inorganic nano-crystal raw material): red light quantum point is used CdSe/CdS is core-shell quanta dots, first carries out mercaptoethanol ligand exchange to the core-shell quanta dots, and obtaining surface ligand is sulfydryl The CdSe/CdS quantum dot of ethyl alcohol is dissolved in ethyl alcohol, then the quantum dot ethanol solution and 1ml concentration for being 15mg/ml by 1ml concentration For the In of 15mg/ml₂S₃Ethanol solution mixing, the water-soluble acrylic rouge (trade mark THFA) that 1wt% is added prevents coagulation, then infuses Enter 10 μ l crosslinking agent hexamethylene diamines, stirs 3h at 35 DEG C.Using n-hexane by the quantum dot and electron-transport after above-mentioned cross-linking reaction Material In₂S₃Carry out precipitation purification, after be dissolved in ethyl alcohol-electron-transport the ink that is configured to shine.

Embodiment 12

Quantum dot and electron transport material In₂S₃The crosslinking of (the second inorganic nano-crystal raw material): red light quantum point is used CdSe/CdS is core-shell quanta dots, first carries out mercaptoethanol ligand exchange to the core-shell quanta dots, and obtaining surface ligand is sulfydryl The CdSe/CdS quantum dot of ethyl alcohol is dissolved in ethyl alcohol, then the quantum dot ethanol solution and 1ml concentration for being 15mg/ml by 1ml concentration For the In of 15mg/ml₂S₃Ethanol solution mixing, the water-soluble acrylic rouge (trade mark THFA) that 1wt% is added prevents coagulation, then infuses Enter 10 μ l crosslinking agent sulfydryl hexylamines, stirs 3h at 35 DEG C.The quantum dot after above-mentioned cross-linking reaction is passed with electronics using n-hexane Defeated material In₂S₃Carry out precipitation purification, after be dissolved in ethyl alcohol-electron-transport the ink that is configured to shine.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Luminous-electron-transport ink is arranged on hole injection layer using spin-on techniques, forms electricity after drying and forming-film by implanted layer Son transmission-luminous composite layer, glass is arranged as cathode in setting metal Ag on cathode on the luminous composite layer of electron-transport- Substrate obtains QLED.

Embodiment 13

Hole mobile material NiO_XThe synthesis of nanocrystalline (the second inorganic nano-crystal raw material) is the same as embodiment 1.

The crosslinking of quantum dot and hole mobile material NiO nanocrystalline (the second inorganic nano-crystal raw material): red quantum is used Point CdSe/CdS as core-shell quanta dots, by 1ml concentration be 15mg/ml quantum dot hexane solution and 1ml concentration be 15mg/ml NiO_XHexane solution mixing, is added the lauryl acrylate (trade mark LA) of 1wt% to prevent coagulation, reinjects 10 μ l crosslinking agents Diamines stirs 3h at 35 DEG C.Using n-hexane by after above-mentioned cross-linking reaction quantum dot and hole mobile material NiO_XIt carries out Precipitation purification, after be dissolved in ethyl alcohol-electron-transport the ink that is configured to shine.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Implanted layer, luminous-hole transport ink is arranged on hole injection layer using spin-on techniques, is formed after drying and forming-film empty Composite layer is transmitted-is shone in cave, and electron transport material ZnO is configured to ink, which is arranged using spin-on techniques Electron transfer layer is formed after the luminous composite layer of electron-transport-, drying and forming-film, setting metal Ag is as yin on electron transfer layer Glass substrate is arranged in pole on cathode, obtains QLED.

Comparative example 1

By the nanocrystalline carry out precipitation purification of above-mentioned NiO, after be dissolved in dodecane and be configured to ink, which is applied using rotation Cloth technology is arranged on the ito anode of substrate surface, and hole transmission layer is formed after drying and forming-film；By red light quantum point CdSe/CdS It is configured to ink, which is arranged on the hole transport layer using spin-on techniques, forms hole transport-after drying and forming-film Shine composite layer；Electron transport material ZnO is configured to ink, which is arranged using spin-on techniques and is passed in hole Defeated-shine composite layer, electron transfer layer is formed after drying and forming-film, setting metal Ag is as cathode on electron transfer layer, in cathode Upper setting glass substrate, obtains QLED.

Luminescent properties test is carried out to the QLED device of embodiment 1 to 13 and comparative example 1, detection method is to use Keithley2400 measures the current density voltage curve of quantum dot luminescent device QLED, is combined using integrating sphere (FOIS-1) The brightness of spectrometer (QE-6500) the measurement QLED luminescent device of marine optics, the current density and brightness obtained according to measurement The external quantum efficiency of quantum dot luminescent device is calculated, external quantum efficiency is characterized in the number of photons that luminescent device issues in observed direction Ratio between the electron number of injection device, is the important parameter of tokenizer luminescent device luminous efficiency, and external quantum efficiency is got over Height illustrates that the luminous efficiency of device is higher, and testing result is recorded in table 1.

Table 1

According to the data comparison in table 1 it can be found that forming the luminous composite layer of hole transport-using the compound of the application And/or the luminous composite layer of electron-transport-, since charge transport part and core-shell quanta dots being attached by crosslinking section, the two Between have stronger coupling, mutual efficiency of transmission is improved, so as to significantly improve the external quantum efficiency of device.

It can be seen from the above description that the above embodiments of the present invention realized the following chievements:

Charge transport part in the prior art as the core-shell quanta dots of luminescent layer and as transport layer is passed through into crosslinking section Crosslinking is realized and is shone and transfer function is integrated in a compound, and then when make QLED device, using this is luminous- The membrane structure that charge transmission compound is formed not only had had the function of luminescent layer but also had had the function of charge transport layer, therefore can lead to The film layer at least two functions can be formed by crossing a solwution method, reduce the implementation number of solwution method, and then be simplified The production process of QLED device, while reducing the probability of failure for preparing QLED device.

And the luminous composite layer of hole transport-and/or the luminous composite layer of electron-transport-are formed using the compound of the application External quantum efficiency during can also significantly improving.

The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims

- charge transmission the compound 1. one kind shines, which is characterized in that by following structure composition:

A kind of core-shell quanta dots have core and shell；

Charge transport part, the charge transport part are a kind of inorganic nano-crystal；And

Crosslinking section, the shell are attached with the charge transport part by the crosslinking section,

The precursor for forming the crosslinking section is selected from C₂~C₁₀And there are two the crosslinking agent of the above functional group, the functional group is hydroxyl Base, carboxyl or sulfydryl.
2.-charge transmission the compound according to claim 1 that shines, which is characterized in that the charge transport part includes tool There are the first inorganic nano-crystal of hole transfer function or the second inorganic nano-crystal with electron-transport function.
3.-charge transmission the compound according to claim 2 that shines, which is characterized in that first inorganic nano-crystal Surface has the first ligand.
4. it is according to claim 2 shine-charge transmits compound, which is characterized in that first inorganic nano-crystal is NiO_XNanocrystalline, NiMgO_XNanocrystalline, p-type ZnO nano is brilliant, CuO is nanocrystalline, Cu₂O is nanocrystalline, Fe₃O₄Nanocrystalline, FeO nanometers Brilliant, V₂O₅Nanocrystalline, MnTiO₃Nanocrystalline, BaTiO₃It is nanocrystalline, HgS is nanocrystalline, PbS is nanocrystalline, SnS is nanocrystalline, MnS nanometers Crystalline substance, wherein 1≤x≤2.
5.-charge transmission the compound according to claim 3 that shines, which is characterized in that second inorganic nano-crystal Surface has Ligands.
6. it is according to claim 2 shine-charge transmits compound, which is characterized in that second inorganic nano-crystal is ZnO nano crystalline substance, TiO₂Nanocrystalline, SrTiO₂Nanocrystalline, MgTiO₃Nanocrystalline, In₂S₃It is nanocrystalline, TiS is nanocrystalline.
7.-charge transmission the compound according to claim 5 that shines, which is characterized in that the shell of the core-shell quanta dots Surface has surface ligand, and first ligand is identical as the dissolubility of the surface ligand, the Ligands and the table The dissolubility of face ligand is identical, and the surface ligand is that oil-soluble carboxylic acids ligand, alcohol-soluble mercaptan carboxylic acid's class ligand or alcohol are molten Property sulfydryl alcohols ligand.
8.-charge transmission the compound according to claim 7 that shines, which is characterized in that the alcohol-soluble mercaptan carboxylic acid class Ligand is thioacetic acid ligand, mercaptopropionic acid ligand or mercaptobutyric acid ligand.
9.-charge transmission the compound according to claim 7 that shines, which is characterized in that the alcohol-soluble sulfydryl alcohols is matched Body is mercaptoethanol ligand or sulfydryls hexanol ligand.
10.-charge transmission the compound according to claim 1 that shines, which is characterized in that the crosslinking agent is oneself two sulphur Alcohol.
- charge transmission the ink 11. one kind shines, it is compound including luminous described in any one of claims 1 to 10-charge transmission Object and solvent.
12. ink according to claim 11, which is characterized in that the charge transport part includes having the function of hole transport The first inorganic nano-crystal or the second inorganic nano-crystal with electron-transport function, the first of first inorganic nano-crystal match Body is identical with the dissolubility of the solvent；The Ligands of second inorganic nano-crystal are identical with the dissolubility of the solvent.
13. ink according to claim 12, which is characterized in that the solvent includes oil soluble material liquid or alcohol-soluble Material liq.
14. ink according to claim 13, which is characterized in that the oil soluble material is C₁~C₂₀Linear paraffin, C₁ ~C₂₀Branched paraffin including one or more pentacyclic C₁~C₂₀Alkane or C including one or more hexatomic rings₁~ C₂₀Alkane.
15. ink according to claim 13, which is characterized in that the alcohol-soluble substance is C₁~C₁₀Straight chain alcohol, C₁~ C₁₀Branched-chain alcoho including one or more pentacyclic C₁~C₁₀Monohydric alcohol and polyalcohol including one or more hexatomic ring C₁~C₁₀Monohydric alcohol and polyalcohol.
16. ink according to claim 11, which is characterized in that the ink further includes anti-settling agent, the anti-settling agent choosing From one or more of epoxy resin, aldehyde ketone resin, acrylic resin and polyurethane resin.
17. ink according to claim 16, which is characterized in that the acrylic resin be lauric acid acrylic resin, Glycidyl methacrylate grease.
18. ink according to claim 16, which is characterized in that the weight of the anti-settling agent is the 10 of the ink weight ~50%.
19. a kind of-preparation method of charge transmission compound that shines, which is characterized in that the preparation method includes:

Step S1, by the first organic solution containing core-shell quanta dots raw material and the second organic solution containing charge transport materials Mixing is formed to cross-linking agent, wherein the core-shell quanta dots raw material is the nucleocapsid quantum that a kind of shell layer surface has surface ligand Point, the charge transport materials are a kind of inorganic nano-crystal with ligand；

The precursor to cross-linking agent and crosslinking section is mixed to form to cross-linking system by step S2；And

Step S3 makes the liquid body for being crosslinked to cross-linking system, obtaining transmitting compound containing the luminous-charge System, wherein the crosslinking section replaces at least partly described surface ligand and at least partly described ligand with by the nucleocapsid quantum The shell of point is attached with the charge transport materials by the crosslinking section,

The precursor for forming the crosslinking section is selected from C₂~C₁₀And there are two the crosslinking agent of the above functional group, the functional group is hydroxyl Base, carboxyl or sulfydryl.
20. preparation method according to claim 19, which is characterized in that the core-shell quanta dots raw material and the charge pass The weight ratio of defeated material is 1:0.2~2.
21. preparation method according to claim 20, which is characterized in that nucleocapsid quantum described in first organic solution The concentration of point raw material is 10~20mg/ml.
22. preparation method according to claim 20, which is characterized in that the transmission of charge described in second organic solvent The concentration of material is 10~20mg/ml.
23. preparation method according to claim 19, which is characterized in that the charge transport materials include that there is hole to pass First inorganic nano-crystal raw material of transmission function or the second inorganic nano-crystal raw material with electron-transport function, described first is inorganic The surface of nanocrystalline raw material has the first ligand, and the surface of the second inorganic nano-crystal raw material has Ligands.
24. preparation method according to claim 23, which is characterized in that the first inorganic nano-crystal raw material is NiO_XIt receives Meter Jing, NiMgO_XNanocrystalline, p-type ZnO nano is brilliant, CuO is nanocrystalline, Cu₂O is nanocrystalline, Fe₃O₄It is nanocrystalline, FeO is nanocrystalline, V₂O₅ Nanocrystalline, MnTiO₃Nanocrystalline, BaTiO₃It is nanocrystalline, HgS is nanocrystalline, PbS is nanocrystalline, SnS is nanocrystalline, MnS is nanocrystalline, 1≤x ≤2。
25. preparation method according to claim 23, which is characterized in that the second inorganic nano-crystal raw material is received for ZnO Meter Jing, TiO₂Nanocrystalline, SrTiO₂Nanocrystalline, MgTiO₃Nanocrystalline, In₂S₃It is nanocrystalline, TiS is nanocrystalline.
26. preparation method according to claim 23, which is characterized in that first ligand, the surface ligand, described The solvent of first organic solution is identical with the dissolubility of the solvent of second organic solution；The Ligands, the surface Ligand, the solvent of first organic solution are identical with the dissolubility of the solvent of second organic solution.
27. preparation method according to claim 26, which is characterized in that the surface ligand is that oil-soluble carboxylic acids is matched Body, alcohol-soluble mercaptan carboxylic acid's class ligand or alcohol-soluble sulfydryl alcohols ligand, first organic solution and described second organic molten The solvent of liquid includes oil soluble material liquid or alcohol-soluble material liq；

The oil soluble material is C₁~C₂₀Linear paraffin, C₁~C₂₀Branched paraffin including one or more pentacyclic C₁ ~C₂₀Alkane or C including one or more hexatomic rings₁~C₂₀Alkane, the precursor of the crosslinking section includes ethanthiol； Or

The alcohol-soluble substance is C₁~C₁₀Straight chain alcohol, C₁~C₁₀Branched-chain alcoho including one or more pentacyclic C₁~ C₁₀Monohydric alcohol and polyalcohol, the C including one or more hexatomic rings₁~C₁₀Monohydric alcohol and polyalcohol, the crosslinking section Precursor includes hexamethylene diamine.
28. preparation method according to claim 27, which is characterized in that the alcohol-soluble mercaptan carboxylic acid class ligand is sulfydryl Acetic acid Hgand, mercaptopropionic acid ligand or mercaptobutyric acid ligand.
29. preparation method according to claim 27, which is characterized in that the alcohol-soluble sulfydryl alcohols ligand is sulfydryl second Alcohol ligand or sulfydryls hexanol ligand.
30. preparation method according to claim 19, which is characterized in that the step S2 includes:

It described will be mixed to cross-linking agent with anti-settling agent, and form the first pre-composition；

First pre-composition and the precursor of crosslinking section are mixed, formed described to cross-linking system.
31. preparation method according to claim 30, which is characterized in that the anti-settling agent is selected from epoxy resin, aldehyde ketone tree One of rouge, acrylic resin and polyurethane resin are a variety of；The acrylic resin is lauric acid acrylic resin, methyl Glycidyl acrylate, the weight of the anti-settling agent are the 10~50% of the liquid system weight.
32. preparation method according to claim 19, which is characterized in that the step S3 stirs 2 at 30~40 DEG C~ 4h carries out the crosslinking.
33. a kind of QLED device, which is characterized in that the QLED device include the anode being sequentially stacked, hole transport-shine it is multiple Layer, electron transfer layer and cathode, or the luminous composite layer of anode, hole transmission layer, electron-transport-including being stacked and cathode are closed, Or including stacked anode, the luminous composite layer of hole transport-, the luminous composite layer of electron-transport-and cathode, wherein the hole Shine composite layer, the electron-transport-of transmission-shines composite layer using shining described in any one of claim 12 to 18- Charge transmission ink is made.
34. QLED device according to claim 33, which is characterized in that between the electron transfer layer and the cathode also It is provided with electron injecting layer and/or electronic barrier layer or the electron-transport-shines and is additionally provided with electricity between composite layer and cathode Sub- implanted layer and/or electronic barrier layer.