CN106848079A

CN106848079A - Luminous electric charge transmission compound, the ink containing it, its preparation method and QLED devices

Info

Publication number: CN106848079A
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: 2017-06-13
Anticipated expiration: 2037-02-20
Also published as: CN106848079B

Abstract

The invention provides luminous electric charge transmission compound, the ink containing it, its preparation method and QLED devices.The luminous electric charge transmission compound includes：Core-shell quanta dots, with core and shell；Electric charge transport part, electric charge transport part is inorganic nano-crystal；And crosslinking section, shell is attached with electric charge transport part by crosslinking section.Core-shell quanta dots in the prior art as luminescent layer and electric charge transport part as transport layer are crosslinked by crosslinking section, luminous and transfer function is realized to be integrated in a compound, and then when QLED devices are made, the membrane structure formed using the luminous electric charge transmission compound had not only been had the function of luminescent layer but also had had the function of transport layer, therefore the film layer with two kinds of functions can be formed by a solwution method, the implementation number of times of solwution method is reduced, and then simplifies the Making programme of QLED devices.

Description

Luminous-electric charge transmission compound, the ink containing it, its preparation method and QLED Device

Technical field

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

Background technology

Quantum dot (Quantum Dot, abbreviation QD) is typically a kind of nanometer being made up of II-VI group or iii-v element Particle, can launch 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.The species of quantum dot is a lot, representational 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 core shell structure being made up of above-mentioned element quantum dot.

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 device of quantum dot emitting layer material.Because quantum dot is inorganic material, luminous organic material can be overcome to oxygen The shortcomings of with water vapor sensitive, poor stability, short life, big encapsulation difficulty, with vast potential for future development.

Conventional QLED device architectures include anode/hole transmission layer (multilayer)/quantum dot light emitting layer/electricity being sequentially stacked Sub- barrier layer/electron transfer layer/negative electrode, and each film layer structure is generally prepared using solwution method at present, but solwution method prepares each film Need to adjust many parameters during layer and can just obtain excellent film layer, cause the preparation method of existing QLED devices cumbersome.

The content of the invention

It is a primary object of the present invention to provide a kind of luminous-electric charge transmission compound, the ink containing it, its preparation side Method and QLED devices, it is cumbersome to solve the problems, such as QLED devices preparation method of the prior art.

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

Further, above-mentioned electric charge transport part includes first inorganic nano-crystal with hole transport function or with electronics Second inorganic nano-crystal of transfer function, alternatively the surface of the first inorganic nano-crystal is with the first part, 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, BaTiO₃Nanocrystalline, HgS is nanocrystalline, PbS is nanocrystalline, SnS is nanocrystalline, MnS is nanocrystalline, wherein 1≤x≤2；Alternatively the surface of the second inorganic nano-crystal has Ligands, and the second inorganic nano-crystal is excellent Elect ZnO nano crystalline substance, TiO as₂Nanocrystalline, SrTiO₂Nanocrystalline, MgTiO₃Nanocrystalline, In₂S₃Nanocrystalline, TiS is nanocrystalline.

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

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

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

Further, above-mentioned electric charge transport part includes first inorganic nano-crystal with hole transport function or with electronics Second inorganic nano-crystal of transfer function, the first part of the first inorganic nano-crystal is 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 material liquid Body, more preferably oil soluble material are C₁~C₂₀Linear paraffin, C₁~C₂₀Branched paraffin, pentacyclic including one or more C₁~C₂₀Alkane or the C including one or more hexatomic rings₁~C₂₀Alkane, further preferably alcohol-soluble material be C₁~C₁₀It is straight Chain alcohol, C₁~C₁₀Branched-chain alcoho, including one or more pentacyclic C₁~C₁₀Monohydric alcohol and polyalcohol, including one or many The C of individual hexatomic ring₁~C₁₀Monohydric alcohol and polyalcohol.

Further, above-mentioned ink also 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 laurate acrylic resin, GMA, more preferably The weight of anti-settling agent is the 10~50% of ink weight.

According to another aspect of the present invention, there is provided a kind of luminous-electric charge transmits the preparation method of compound, the preparation side Method includes：Step S1, the first organic solution containing core-shell quanta dots raw material is organic with containing charge transport materials second Solution mixes, and cross-linking agent is treated in formation, wherein, core-shell quanta dots raw material has the core-shell quanta dots of surface ligand for shell layer surface, Charge transport materials are the inorganic nano-crystal with part；Step S2, will treat that cross-linking agent is mixed to form with the precursor of crosslinking section and treats Cross-linking system；And step S3, make to treat that cross-linking system is crosslinked, obtain being transmitted containing luminous-electric charge the liquid body of compound System, wherein, crosslinking section is replaced at least part of surface ligand and at least part of part and is passed with by the shell of core-shell quanta dots and electric charge Defeated material is attached by crosslinking section.

Further, above-mentioned core-shell quanta dots raw material and the weight ratio of charge transport materials are 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 preferably the 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 The surface for having the second inorganic nano-crystal raw material of electric transmission function, the first inorganic nano-crystal raw material has the first part, first Inorganic nano-crystal raw material is preferably NiO_XNanocrystalline, NiMgO_XNanocrystalline, p-type ZnO nano is brilliant, CuO is nanocrystalline, Cu₂O is nanocrystalline, Fe₃O₄Nanocrystalline, FeO is nanocrystalline, V₂O₅Nanocrystalline, MnTiO₃Nanocrystalline, BaTiO₃Nanocrystalline, HgS is nanocrystalline, PbS is nanocrystalline, SnS is nanocrystalline, MnS is nanocrystalline, 1≤x≤2；The surface of the 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 part, surface ligand, the solvent of the first organic solution and the second organic solution Dissolubility it is identical；The dissolubility of the solvent of Ligands, surface ligand, the solvent of the first organic solution and the second organic solution It is identical.

Further, above-mentioned surface ligand is oil-soluble carboxylic acids part, alcohol-soluble mercaptan carboxylic acid's class part or alcohol-soluble Sulfydryl alcohols part, preferably alcohol-soluble mercaptan carboxylic acid class part are matched somebody with somebody for TGA part, mercaptopropionic acid part or mercaptobutyric acid Body, preferably alcohol-soluble mercaptoalcohol class part are mercaptoethanol part or sulfydryl hexanol part, the first organic solution and second organic The solvent of solution includes oil soluble material liquid or alcohol-soluble material liq, and oil soluble material is C₁~C₂₀Linear paraffin, C₁ ~C₂₀Branched paraffin, including one or more pentacyclic C₁~C₂₀Alkane or the C including one or more hexatomic rings₁~ C₂₀Alkane, the precursor of crosslinking section includes ethanthiol, and alcohol-soluble material 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：To treat that cross-linking agent mixes with anti-settling agent, form the first pre-composition；By first Cross-linking system is treated in the precursor mixing of pre-composition and crosslinking section, formation；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 laurate acrylic resin, GMA, 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, there is provided a kind of QLED devices, QLED devices include the anode, the sky that are sequentially stacked Transmit-light composite bed, electron transfer layer and negative electrode, or anode, hole transmission layer, electric transmission-luminous including being stacked in cave Composite bed and negative electrode, or anode, hole transport-luminous composite bed, electric transmission-luminous composite bed and negative electrode including being stacked, Wherein, hole transport-luminous composite bed, electric transmission-luminous composite bed transmit ink using any of the above-described kind of luminous-electric charge It is made.

Further, electron injecting layer and/or electronic barrier layer are additionally provided between above-mentioned electron transfer layer and negative electrode, or Electric transmission-lighting is additionally provided with electron injecting layer and/or electronic barrier layer between composite bed and negative electrode.

Apply the technical scheme of the present invention, using in the prior art as the core-shell quanta dots of luminescent layer and as transport layer Electric charge transport part is crosslinked by crosslinking section, is realized luminous and transfer function and is integrated in a compound, and then is being made During QLED devices, the membrane structure formed using the luminous-electric charge transmission compound had not only been had the function of luminescent layer but also had had transmission The function of layer, therefore the film layer with two kinds of functions can be formed by a solwution method, reduce the implementation of solwution method Number of times, and then the Making programme of QLED devices is simplified, reduce the probability of QLED devices failure.

Specific embodiment

It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase Mutually combination.The present invention is described in detail below in conjunction with embodiment.

It is of the prior art due to needing to be respectively provided with hole transmission layer, quantum as described in the application background technology Point luminescent layer and electron transfer layer, cause the preparation method of QLED devices cumbersome, in order to solve the problem, this application provides one Plant luminous-electric charge transmission compound, the ink containing it, its preparation method and QLED devices.

In a kind of typical implementation method of the application, there is provided a kind of luminous-electric charge transmission compound, including nucleocapsid amount Sub- point, electric charge transport part and crosslinking section, core-shell quanta dots have core and a shell, and electric charge transport part is inorganic nano-crystal, shell with Electric charge transport part is attached by crosslinking section.

Core-shell quanta dots in the prior art as luminescent layer and electric charge transport part as transport layer are passed through into crosslinking section Crosslinking, realizes and luminous and transfer function is integrated in a compound, and then when QLED devices are made, using 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 logical The film layer with least two functions is formed by crossing a solwution method, the implementation number of times of solwution method is reduced, and then simplify The Making programme of QLED devices, also, because the preparation total quantity of film layer in device has been reduced, reduce because of tunic layer not Probability that is uniform and influenceing the uniformity of whole device, reduces the possibility that film layer makes failure, improves QLED devices Production stability.

In a kind of preferred embodiment of the application, above-mentioned electric charge transport part includes the first nothing with hole transport function Machine is nanocrystalline, and the surface of the first inorganic nano-crystal can be without part, it is possible to have the first part, the first inorganic nano-crystal is excellent Elect NiO as_XNanocrystalline, NiMgO_XNanocrystalline, p-type ZnO nano is brilliant, CuO is nanocrystalline, Cu₂O is nanocrystalline, Fe₃O₄Nanocrystalline, FeO receives Meter Jing, V₂O₅Nanocrystalline, MnTiO₃Nanocrystalline, BaTiO₃Nanocrystalline, HgS is nanocrystalline, PbS is nanocrystalline, SnS is nanocrystalline, MnS receives Meter Jing, 1≤x≤2, wherein, NiO_XNanocrystalline expression NiO₁Nanocrystalline or NiO₂It is nanocrystalline, or NiO₁Nanocrystalline and NiO₂Nanometer Brilliant mixture.

In the application another kind preferred embodiment, above-mentioned electric charge transport part includes with electric transmission function second Inorganic nano-crystal, the surface of the second inorganic nano-crystal can be without part, it is possible to have Ligands, the second inorganic nano-crystal Preferably ZnO nano is brilliant, TiO₂Nanocrystalline, SrTiO₂Nanocrystalline, MgTiO₃Nanocrystalline, In₂S₃Nanocrystalline, TiS is nanocrystalline.

Either electric charge transport part has electric transmission function still with hole transport function, the core coordinated with it The shell layer surface of shell quantum dot raw material has surface ligand, the part and core-shell quanta dots of charge transport materials in cross-linking process The part portion of being crosslinked of raw material replaces, in order that above-mentioned replacement process is easier to make for, preferred the first of the first inorganic nano-crystal Part is identical with the dissolubility of surface ligand, and the Ligands of the second inorganic nano-crystal are identical with the dissolubility of surface ligand (molten The identical different ligands that refer to of solution property are all oil-solubles or are all alcohol-solubles).Usually as above-mentioned core-shell quanta dots raw material Each nanocrystalline with charge transport materials is prepared by solwution method, and the ligand species of presoma used determine prepared during preparation Nanocrystalline part, the part of nanocrystalline institute's band determine it is nanocrystalline be belonging to it is oil-soluble or alcohol-soluble, it is nanocrystalline On part can be oil-soluble part or alcohol-soluble part, the part of the shell layer surface of core-shell quanta dots raw material can also be oil Soluble ligand or alcohol-soluble part, in the process for being attached core-shell quanta dots raw material and charge transport materials by crosslinking section In, the dissolubility of the part of the shell layer surface of part and core-shell quanta dots raw material on charge transport materials is consistent and makes crosslinking Become easier to, for example, the part of the shell layer surface of core-shell quanta dots raw material is oil-soluble carboxylic acids part, then electric charge is transmitted Material is also selected with the nanocrystalline of oil-soluble carboxylic acids part, if the nanocrystalline raw material prepared is band alcohol-soluble sulfydryl alcohols Part, oil-soluble carboxylic acids part is changed to by the method for ligand exchange by the alcohol-soluble sulfydryl alcohols part of nanocrystal surface, Then it is attached by crosslinking section, specifically, it is assumed that the precursor (i.e. crosslinking agent) of crosslinking section has G1 and G2 functional groups, One of functional group G1 replaces the part A on nanocrystalline (abbreviation NC), another functional group G2 to replace core-shell quanta dots (referred to as QD the part B on), so as to obtain the luminous-electric charge transmission compound of NC-G1-C-G2-QD structures, wherein, G1-C-G2 is friendship Connection portion, C is carbochain, and at least part of part A is lost after NC reactions, at least part of part B is lost after QD reactions, because a quantum Point or one it is nanocrystalline be respectively provided with multiple parts, crosslinking agent can have two or more to participate in the functional group of cross-linking reaction, institute With the nanocrystalline network structure that can form crosslinking of a group quantum dot and a group, for example, the Zn atoms on core-shell quanta dots raw material surface On there is oleic acid ligand to be coordinated therewith, add the reaction of crosslinking agent hexamethylene diamine, make amino and Zn Atomic coordinates in hexamethylene diamine, so as to replace Change original oleic acid ligand.Similarly, the nanocrystalline Ni atoms such as NiOx (1≤x≤2) surface for electric charge transmission also can There is such part to replace.It is crosslinked with core-shell quanta dots raw material using above-mentioned charge transport materials, is realized electric charge biography Transmission function and lighting function are integrated in a film layer, will hole transmission layer and luminescent layer merge into One function layer or will Electron transfer layer and luminescent layer merge into One function layer.

Additionally, the first part of the first inorganic nano-crystal is identical with the dissolubility of core-shell quanta dots raw material surface ligand, the The Ligands of two inorganic nano-crystals are identical with the dissolubility of surface ligand, identical dissolubility refer to be both it is oil-soluble or same It is water miscible, the shell layer surface of preferably above-mentioned core-shell quanta dots has oil-soluble mercaptan carboxylic acid's class part, oil-soluble carboxylic acids Part or alcohol-soluble sulfydryl alcohols part, preferably alcohol-soluble mercaptan carboxylic acid class part are TGA part, mercaptopropionic acid part Or mercaptobutyric acid part, preferably alcohol-soluble mercaptoalcohol class part is mercaptoethanol part or sulfydryl hexanol part.

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

The shell layer surface of core-shell quanta dots raw material has one or more first parts, and the surface of charge transport materials has One or more Ligands, crosslinking section precursor has at least one of at least two functional groups, functional group substitution the At least one of one part, makes crosslinking section be connected with core-shell quanta dots surface, the substitution of at least one of another functional group At least one of Ligands, make crosslinking section be connected with charge transport materials surface, and lighted-electric charge transmission compound.

Above-mentioned crosslinking section is the structure that crosslinking section precursor will be formed after core-shell quanta dots and charge transport materials connection, preferably The precursor for forming crosslinking section is selected from C₂~C₁₀And have a crosslinking agent of two or more functional group, 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.

It is in a kind of typical implementation method of the application, there is provided a kind of luminous-electric charge transmission ink including any of the above-described Luminous-electric charge transmission compound and the solvent planted.

After the luminous-electric charge transmission compound dispersion of the application is formed into ink in a solvent, it is used directly for making The corresponding function layer of QLED devices, using simple, and material can be stablized and preserve.

Include first inorganic nano-crystal with hole transport function or with electric transmission function when electric charge transport part During the second inorganic nano-crystal, in order to improve the stability of ink, the first part of preferably the first inorganic nano-crystal and solvent it is molten Solution property is identical；The Ligands of the second inorganic nano-crystal are identical with the dissolubility of solvent, and more preferably 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 Individual or multiple pentacyclic C₁~C₂₀Alkane or the C including one or more hexatomic rings₁~C₂₀Alkane.Alcohol-soluble material is C₁~C₁₀Straight chain alcohol, C₁~C₁₀Branched-chain alcoho, including one or more pentacyclic C₁~C₁₀Monohydric alcohol and polyalcohol, bag Include the C of one or more hexatomic rings₁~C₁₀Monohydric alcohol and polyalcohol.

In order to luminous-electric charge transmits the stability after crosslinking complexes in improving ink, the preferably ink also includes anti-settling Agent, the wherein anti-settling agent are selected from epoxy resin, aldehyde ketone resin, acrylic resin and/or polyurethane resin, preferred acrylic resins Be laurate acrylic resin, GMA, more preferably the weight of anti-settling agent for ink weight 10~ 50%.

In another typical implementation method of the application, there is provided a kind of luminous-electric charge transmits the preparation side of compound Method, the preparation method includes：Step S1, by the first organic solution containing core-shell quanta dots raw material with contain charge transport materials The second organic solution mixing, formation treat cross-linking agent, wherein, above-mentioned core-shell quanta dots raw material has surface ligand for shell layer surface Core-shell quanta dots, charge transport materials are the inorganic nano-crystal raw material with part；Step S2, will treat cross-linking agent and crosslinking section Precursor be mixed to form and treat cross-linking system；And step S3, make to treat that cross-linking system is crosslinked, obtain being passed containing luminous-electric charge The liquid system of defeated compound, wherein, crosslinking section replaces at least part of quantum dot surface part and at least part of electric charge transmission material The part of material is attached with electric charge transport part with by the shell of core-shell quanta dots by crosslinking section.

Above-mentioned preparation method, core-shell quanta dots raw material is disperseed in the form of the first organic solution, and electric charge is transmitted Material is disperseed in the form of the second organic solution, when the first organic solution and the second organic solution are mixed, can be made Obtain core-shell quanta dots raw material and charge transport materials uniformly mix；On the basis of mixed uniformly, using the precursor pair of crosslinking section Core-shell quanta dots raw material and charge transport materials are crosslinked, and crosslinking section is replaced at least part of core-shell quanta dots raw material shell Surface ligand, also replaces the part of at least part of inorganic nano-crystal raw material, realizes core-shell quanta dots raw material and charge transport materials It is compound.Above-mentioned preparation method is simple to operate, easy to implement, and the liquid system warp containing luminous-electric charge transmission for being formed Precipitation purification, then with after the dissolving of corresponding solvent, can be used for making the composite bed of corresponding transfer function and lighting function, subtract The implementation number of times of the solwution method that the making of functional layer is used is lacked, and then has simplified the Making programme of QLED devices, and dropped The low probability of failure for preparing QLED devices.Wherein, oil phase can with ethanol etc. be precipitated out with alkane dissolve, alcohol phase can Dissolved with alcohols with being precipitated out with n-hexane etc..

When by transfer function and integrated lighting function, the basis of illumination effect and electric charge laser propagation effect is being improved as far as possible On, the scattered uniformity of both optimization, preferably core-shell quanta dots raw material are 1 with the weight ratio of charge transport materials:0.2~2；It is excellent Select the concentration of core-shell quanta dots raw material in the first organic solution for 10~20mg/ml, electric charge is passed in more preferably the second organic solution The concentration of defeated material is 10~20mg/ml.

In a kind of preferred embodiment of the application, above-mentioned charge transport materials include with hole transport function first Inorganic nano-crystal raw material, the surface of the first inorganic nano-crystal raw material has the first part, and the first inorganic nano-crystal raw material is preferred It is NiO_XNanocrystalline, NiMgO_XNanocrystalline, p-type ZnO nano is brilliant, CuO is nanocrystalline, Cu₂O is nanocrystalline, Fe₃O₄Nanocrystalline, FeO nanometers Brilliant, V₂O₅Nanocrystalline, MnTiO₃Nanocrystalline, BaTiO₃Nanocrystalline, HgS is nanocrystalline, PbS is nanocrystalline, SnS is nanocrystalline, MnS nanometers Crystalline substance, x is 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 thering is electric transmission function 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 is brilliant, TiO₂Nanocrystalline, SrTiO₂Nanocrystalline, MgTiO₃Nanocrystalline, In₂S₃Nanocrystalline, TiS is nanocrystalline.

The first foregoing inorganic nano-crystal raw material and the first inorganic nano-crystal are respectively the materials before and after crosslinking, wherein, the One inorganic nano-crystal raw material has the first part, and the first inorganic nano-crystal is that at least part of first part is crosslinked portion after cross-linking Substituted electric charge transport part；The second foregoing inorganic nano-crystal raw material and the second inorganic nano-crystal are respectively the materials before and after crosslinking Material, wherein, the second inorganic nano-crystal raw material has a Ligands, and the second inorganic nano-crystal is at least part of second to match somebody with somebody after cross-linking The electric charge transport part of the body portion of being crosslinked substitution.

No matter charge transport materials have electric transmission function or have hole transport function, the core coordinated 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 Part is identical with the dissolubility of surface ligand, the Ligands of the second inorganic nano-crystal raw material and the dissolubility phase of surface ligand Together.It is prepared by solwution method usually as above-mentioned core-shell quanta dots and each nanocrystalline of charge transport materials, it is used during preparation The ligand species of presoma determine obtained nanocrystalline part, and the part of nanocrystalline institute's band is determined and nanocrystalline is belonging to oil Dissolubility or alcohol-soluble, it is nanocrystalline on part can be oil-soluble part or alcohol-soluble part, core-shell quanta dots raw material Shell layer surface part can also be oil-soluble part or alcohol-soluble part, by crosslinking section by core-shell quanta dots raw material with During charge transport materials are attached, the part of the shell layer surface of part and core-shell quanta dots on charge transport materials Dissolubility be consistent and become easier to crosslinking, for example, the part of the shell layer surface of core-shell quanta dots raw material is oil-soluble Carboxylic acids part, then charge transport materials are also selected with the nanocrystalline of oil-soluble carboxylic acids part, if the nanometer prepared Crystalline substance is alcohol-soluble sulfydryl alcohols part, is changed to the alcohol-soluble sulfydryl alcohols part of nanocrystal surface by the method for ligand exchange Oil-soluble carboxylic acids part, is then attached, specifically by crosslinking section, it is assumed that the precursor (i.e. crosslinking agent) of crosslinking section With G1 and G2 functional groups, one of functional group G1 replaces the part A on nanocrystalline (abbreviation NC), another functional group G2 to replace Fall the part B on core-shell quanta dots (abbreviation QD), so as to obtain the luminous-electric charge transmission compound of NC-G1-C-G2-QD structures, Wherein, G1-C-G2 is crosslinking section, and C is carbochain, and at least part of part A is lost after NC reactions, is lost after QD reactions and at least partly matched somebody with somebody Body B because a quantum dot or one it is nanocrystalline be respectively provided with multiple parts, crosslinking agent can have two or more to participate in crosslinking The functional group of reaction, so a group quantum dot and the nanocrystalline network structure that can form crosslinking of a group, for example, core-shell quanta dots are former There is oleic acid ligand to be coordinated therewith on the Zn atoms for expecting surface, add the reaction of crosslinking agent hexamethylene diamine, make the amino and Zn in hexamethylene diamine Atomic coordinate, so as to replace original oleic acid ligand.Similarly, for the nanocrystalline raw material such as NiOx (1≤x of electric charge transmission ≤ 2) the Ni atoms on surface such part can also occur replace.Entered with core-shell quanta dots raw material using above-mentioned charge transport materials Row crosslinking, realizes electric charge transfer function and lighting function is integrated in a film layer, will hole transmission layer and luminous laminated And merge into One function layer for One function layer or by electron transfer layer and luminescent layer.

Additionally, in order to increase dispersiveness of the charge transport materials in the first organic solution, core-shell quanta dots raw material is The dispersiveness of two organic solutions, and the first organic solution and the second organic solution Combination, preferably above-mentioned first inorganic receives First part of the brilliant 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 Ligands of above-mentioned second inorganic nano-crystal raw material, the surface ligand of core-shell quanta dots, first The dissolubility of the solvent of the solvent of organic solution and the second organic solution is identical.Certainly, can be using stirring etc. if differed Mode improves above-mentioned dispersiveness and Combination.

Because molecular weight and volume increase after core-shell quanta dots raw material and charge transport materials crosslinking, easily aggregation is The generation settled when avoiding cross-linking reaction and when the holding time is more long, preferably above-mentioned steps S2 includes：Cross-linking agent will be treated and prevented Heavy agent mixing, forms the first pre-composition；The precursor of the first pre-composition and crosslinking section is mixed, cross-linking system is treated in formation, preferably prevented Heavy agent is selected from epoxy resin, aldehyde ketone resin, acrylic resin and/or polyurethane resin, and acrylic resin is bay acid acrylic acid Resin, GMA, additionally, in order to avoid excessive anti-settling agent is to electric charge laser propagation effect and illumination effect Influence, the weight of preferably above-mentioned anti-settling agent is the 10~50% of liquid system weight.

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

In the application in another typical implementation method, there is provided a kind of QLED devices, the QLED devices are included successively Stacked anode, hole transport-luminous composite bed, electron transfer layer and negative electrode, or including be stacked anode, hole transmission layer, Electric transmission-luminous composite bed and negative electrode, or anode, hole transport-luminous composite bed, electric transmission-luminous including being stacked Composite bed and negative electrode, wherein, hole transport-luminous composite bed, electric transmission-luminous composite bed use any of the above-described kind of hair Optical-electronic lotus transmission ink is made.Due to the application it is luminous-electric charge transmission compound being capable of integrated light-emitting-hole transport Function or integrated light-emitting-electric transmission function, therefore, it is above-mentioned to transmit ink formation hole biography using the luminous-electric charge Defeated-luminous composite bed, electric transmission-luminous composite bed, reduce the function layer number of QLED devices.

In order to improve the stability of device, preferably hole transport-luminous composite bed and electric transmission-luminous composite bed is adjacent When, the electric transmission of first part and electric transmission of the hole mobile material of hole transport-luminous composite bed-luminous composite bed The dissolubility of the Ligands of material is different.The compound F1 that i.e. core-shell quanta dots and the first inorganic nano-crystal raw material reaction are generated It is adjacent with the film layer that the compound F2 that the second inorganic nano-crystal raw material reaction is generated makes with core-shell quanta dots, 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 are the first inorganic nano-crystal of sulfydryl alcohols part and answering for the same core-shell quanta dots reaction generation with sulfydryl alcohols part Compound F1, then reacted with the second inorganic nano-crystal with carboxylic acids part with the same core-shell quanta dots with carboxylic acids part The compound F2 of generation, then using compound F1 and compound F2 as two film layers adjacent in QLED devices.

Furthermore it is preferred that electron injecting layer and/or electronic barrier layer are additionally provided between above-mentioned electron transfer layer and negative electrode, or Electric transmission-lighting is additionally provided with electron injecting layer and/or electronic barrier layer between composite bed and negative electrode.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, the octadecyl alcolol of 6mmol are added in the 1- octadecylenes of 10ml, are put into 50ml flasks, 80 DEG C are warming up under inert gas shielding, 30min is vacuumized；280 DEG C are warming up under inert gas shielding and are incubated 120min, it is cold But to room temperature, centrifugation obtains colloid NiO after adding precipitating reagent ethanol_XIt is nanocrystalline.

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

The crosslinking of quantum dot and electron transport material ZnO (the second inorganic nano-crystal raw material)：Using red light quantum point CdSe/ CdS is core-shell quanta dots, first carries out mercaptopropionic acid ligand exchange to the core-shell quanta dots, and it is mercaptopropionic acid to obtain surface ligand CdSe/CdS quantum dots, are dissolved in ethanol, then by 1ml concentration for the quantum dot ethanol solution of 15mg/ml is with 1ml concentration The ZnO ethanol solutions mixing of 15mg/ml, adds consumption to be prevented for the water-soluble acrylic fat (LZ5005, blue bamboo chemical industry) of 1wt% Coagulation, reinjects 10 μ l crosslinking agent hexamethylene diamines, and 3h is stirred 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 ethanol and be configured to-electric transmission the ink that lights.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Implanted layer, the luminous-hole transport ink is arranged on above-mentioned hole injection layer using spin-on techniques, after drying and forming-film Hole transport-luminous composite bed is formed, luminous-electric transmission ink is arranged on hole transport-luminous multiple using spin coating technique Layer is closed, electric transmission-luminous composite bed is formed after drying and forming-film, metal Ag conducts are set on electric transmission-luminous composite bed Negative electrode, sets glass substrate on negative electrode, obtains QLED.

Embodiment 2

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

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

The crosslinking of quantum dot and electron transport material ZnO (the second inorganic nano-crystal raw material)：Using red light quantum point CdSe/ CdS is core-shell quanta dots, first carries out mercaptopropionic acid ligand exchange to the core-shell quanta dots, and it is mercaptopropionic acid to obtain surface ligand CdSe/CdS quantum dots, are dissolved in ethanol, then by 1ml concentration for the quantum dot ethanol solution and 2ml concentration of 15mg/ml are 15mg/ The ZnO ethanol solutions mixing of ml, adds consumption to prevent coagulation for the water-soluble acrylic fat (LZ5005, blue bamboo chemical industry) of 1wt%, 10 μ l crosslinking agent hexamethylene diamines are reinjected, 3h is stirred 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 ethanol and be configured to-electric transmission the ink that lights.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Implanted layer, the luminous-hole transport ink is arranged on hole injection layer using spin-on techniques, is formed after drying and forming-film Hole transport-luminous composite bed, hole transport-luminous is arranged on by the luminous-electric transmission ink using spin-on techniques Composite bed, forms electric transmission-luminous composite bed after drying and forming-film, setting metal Ag on electric transmission-luminous composite bed makees It is negative electrode, glass substrate is set on negative electrode, obtains QLED.

Embodiment 3

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

The crosslinking of quantum dot and electron transport material ZnO (the second inorganic nano-crystal raw material)：Using red light quantum point CdSe/ CdS is core-shell quanta dots, first carries out mercaptopropionic acid ligand exchange to the core-shell quanta dots, and it is mercaptopropionic acid to obtain surface ligand CdSe/CdS quantum dots, are dissolved in ethanol, then by 1ml concentration for the quantum dot ethanol solution of 15mg/ml is with 0.2ml concentration The ZnO ethanol solutions mixing of 15mg/ml, adds consumption to be prevented for the water-soluble acrylic fat (LZ5005, blue bamboo chemical industry) of 1wt% Coagulation, reinjects 10 μ l crosslinking agent hexamethylene diamines, and 3h is stirred 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 ethanol and be configured to-electric transmission the ink that lights.

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, forms empty after drying and forming-film Composite bed is transmitted-lighted in cave, and luminous-electric transmission ink is arranged on into hole transport-luminous compound using spin-on techniques Layer, forms electric transmission-luminous composite bed after drying and forming-film, metal Ag is set as the moon on electric transmission-luminous composite bed Pole, sets glass substrate on negative electrode, obtains QLED.

Embodiment 4

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

Quantum dot and electron transport material TiO₂The crosslinking of (the second inorganic nano-crystal raw material)：Using red light quantum point CdSe/CdS is core-shell quanta dots, first carries out mercaptopropionic acid ligand exchange to the core-shell quanta dots, obtains surface ligand for sulfydryl The CdSe/CdS quantum dots of propionic acid, are dissolved in ethanol, then by 1ml concentration for the quantum dot ethanol solution of 15mg/ml is with 1ml concentration The TiO of 15mg/ml₂Ethanol solution mixes, and adds consumption to prevent for the water-soluble acrylic fat (LZ5005, blue bamboo chemical industry) of 1wt% Only coagulation, reinjects 10 μ l crosslinking agent hexamethylene diamines, and 3h is stirred 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 ethanol and be configured to-electric transmission the ink that lights.

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：It is the quantum of 15mg/ml by 1ml concentration using red light quantum point CdSe/CdS as core-shell quanta dots Point hexane solution is the NiMgO of 15mg/ml with 1ml concentration_XHexane solution mixes, and adds the lauryl acrylate (trade mark of 1wt% LA) to prevent coagulation, 10 μ l crosslinking agent ethanthiols are reinjected, 3h is stirred at 35 DEG C.Using ethanol by after above-mentioned cross-linking reaction 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 lights.

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, forms empty after drying and forming-film Composite bed is transmitted-lighted in cave, and electron transport material ZnO is configured into ink, and the ink is set using spin-on techniques In hole transport-luminous composite bed, electron transfer layer is formed after drying and forming-film, metal Ag is set on electron transfer layer used as the moon Pole, sets glass substrate on negative electrode, 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：It is the quantum dot of 15mg/ml by 1ml concentration using red light quantum point CdSe/CdS as core-shell quanta dots Hexane solution is the Fe of 15mg/ml with 1ml concentration₃O₄N-heptane solution mixes, and adds the lauryl acrylate (trade mark LA) of 1wt% To prevent coagulation, 10 μ l crosslinking agent ethanthiols are reinjected, 3h is stirred at 35 DEG C.Using ethanol 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 lights.

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, forms empty after drying and forming-film Composite bed is transmitted-lighted in cave, and electron transport material ZnO is configured into ethanol ink, and the ink is utilized into spin-on techniques Hole transport-luminous composite bed is arranged on, electron transfer layer is formed after drying and forming-film, metal Ag conducts are set on electron transfer layer Negative electrode, sets glass substrate on negative electrode, obtains QLED.

Embodiment 7

Quantum dot and hole mobile material V₂O₅It is nanocrystalline that (the first inorganic nano-crystal raw material is purchased from nano-crystal science and technology share limited Company) crosslinking：Using red light quantum point CdSe/CdS as core-shell quanta dots, by 1ml concentration for 15mg/ml quantum dot oneself Alkane solution is the V of 15mg/ml with 1ml concentration₂O₅Cyclohexane solution mix, add 1wt% lauryl acrylate (trade mark LA) with Coagulation is prevented, 10 μ l crosslinking agent ethanthiols are reinjected, 3h is stirred at 35 DEG C.Using ethanol 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 lights.

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 after above-mentioned cross-linking reaction and hole mobile material V₂O₅Carry out precipitation purification, after be dissolved in dodecane Be configured to ink, the ink be arranged on hole injection layer using spin-on techniques, after drying and forming-film formed hole transport- Luminous composite bed, and electron transport material ZnO is configured to ethanol ink, the ink is arranged on sky using spin-on techniques Composite bed is transmitted-lighted in cave, and electron transfer layer is formed after drying and forming-film, and metal Ag is set on electron transfer layer as negative electrode, Glass substrate is set on negative electrode, QLED is obtained.

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：It is the quantum of 15mg/ml by 1ml concentration using red light quantum point CdSe/CdS as core-shell quanta dots Point hexane solution is the BaTiO of 15mg/ml with 1ml concentration₃Isooctane solution mixes, and adds 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 ethanol by above-mentioned cross-linking reaction Quantum dot afterwards and hole mobile material BaTiO₃Carry out precipitation purification, after be dissolved in dodecane and be configured to light-hole transport ink Water.

Embodiment 9

Quantum dot is nanocrystalline with hole mobile material PbS, and (the first inorganic nano-crystal raw material is purchased from nano-crystal science and technology share limited Company) crosslinking：Using red light quantum point CdSe/CdS as core-shell quanta dots, by 1ml concentration for 15mg/ml quantum dot oneself Alkane solution and 1ml concentration mixs for the PbS isooctane solutions of 15mg/ml, the lauryl acrylate (trade mark LA) of addition 1wt% with Coagulation is prevented, 10 μ l crosslinking agent ethanthiols are reinjected, 3h is stirred at 35 DEG C.Using ethanol 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 lights.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Implanted layer, luminous-electric transmission ink is arranged on hole injection layer using spin-on techniques, and electricity is formed after drying and forming-film Son transmission-luminous composite bed, metal Ag is set as negative electrode on electric transmission-luminous composite bed, and glass base is set on negative electrode Plate, obtains QLED.

Embodiment 10

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

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Implanted layer, luminous-electric transmission ink is arranged on hole injection layer using spin-on techniques, and electricity is formed after drying and forming-film Son transmission-luminous composite bed, electric transmission-luminous composite bed sets metal Ag as negative electrode, and glass substrate is set on negative electrode, Obtain QLED.

Embodiment 11

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

Embodiment 12

Quantum dot and electron transport material In₂S₃The crosslinking of (the second inorganic nano-crystal raw material)：Using red light quantum point CdSe/CdS is core-shell quanta dots, first carries out mercaptoethanol ligand exchange to the core-shell quanta dots, obtains surface ligand for sulfydryl The CdSe/CdS quantum dots of ethanol, are dissolved in ethanol, then are the quantum dot ethanol solution and 1ml concentration of 15mg/ml by 1ml concentration It is the In of 15mg/ml₂S₃Ethanol solution mixes, and adds water-soluble acrylic fat (trade mark THFA) of 1wt% and prevents coagulation, then notes Enter 10 μ l crosslinking agent sulfydryl hexylamines, 3h is stirred at 35 DEG C.The quantum dot after above-mentioned cross-linking reaction and electronics are passed using n-hexane Defeated material In₂S₃Carry out precipitation purification, after be dissolved in ethanol and be configured to-electric transmission the ink that lights.

By PEDOT (poly- 3,4-ethylene dioxythiophene monomer) rotary coating on the ito anode of substrate surface, hole is formed Implanted layer, luminous-electric transmission ink is arranged on hole injection layer using spin-on techniques, and electricity is formed after drying and forming-film Son transmission-luminous composite bed, metal Ag is set as negative electrode on electric transmission-luminous composite bed, and glass is set on negative electrode Substrate, obtains QLED.

Embodiment 13

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

The crosslinking of quantum dot and hole mobile material NiO nanocrystalline (the second inorganic nano-crystal raw material)：Using red quantum Quantum dot hexane solution and 1ml concentration that 1ml concentration is 15mg/ml, as core-shell quanta dots, are 15mg/ml by point CdSe/CdS NiO_XHexane solution mixes, and adds the lauryl acrylate (trade mark LA) of 1wt% to prevent coagulation, reinjects 10 μ l crosslinking agents Diamines, 3h is stirred at 35 DEG C.Using n-hexane by the quantum dot after above-mentioned cross-linking reaction and hole mobile material NiO_XCarry out Precipitation purification, after be dissolved in ethanol and be configured to-electric transmission the ink that lights.

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, forms empty after drying and forming-film Composite bed is transmitted-lighted in cave, and electron transport material ZnO is configured into ink, and the ink is set using spin-on techniques In electric transmission-luminous composite bed, electron transfer layer is formed after drying and forming-film, metal Ag is set on electron transfer layer used as the moon Pole, sets glass substrate on negative electrode, obtains QLED.

Comparative example 1

Precipitation purification is carried out by above-mentioned NiO is nanocrystalline, after be dissolved in dodecane and be configured to ink, the ink 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 Be configured to ink, the ink be arranged on hole transmission layer using spin-on techniques, after drying and forming-film formed hole transport- Luminous composite bed；Electron transport material ZnO is configured to ink, the ink is arranged on into hole using spin-on techniques passes Defeated-luminous composite bed, forms electron transfer layer after drying and forming-film, metal Ag is set on electron transfer layer as negative electrode, in negative electrode Upper setting glass substrate, obtains QLED.

QLED devices to embodiment 1 to 13 and comparative example 1 carry out luminescent properties test, and detection method is use Keithley2400 determines 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 measure QLED luminescent devices of marine optics, the current density obtained according to measure and brightness The external quantum efficiency of quantum dot luminescent device is calculated, external quantum efficiency is characterized in the number of photons that luminescent device in observed direction sends The ratio and electron number of injection device between, 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

Data Comparison in table 1 using the compound of the application it can be found that form hole transport-luminous composite bed And/or electric transmission-luminous composite bed, due to electric charge transport part and core-shell quanta dots being attached by crosslinking section, both Between have stronger coupling, improve mutual efficiency of transmission such that it is able to significantly improve the external quantum efficiency of device.

As can be seen from the above description, the above embodiments of the present invention realize following technique effect：

Core-shell quanta dots in the prior art as luminescent layer and electric charge transport part as transport layer are passed through into crosslinking section Crosslinking, realizes luminous and transfer function and is integrated in a compound, and then when QLED devices are made, using this is luminous- The membrane structure that electric 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 with least two functions is formed by crossing a solwution method, the implementation number of times of solwution method is reduced, and then simplify The Making programme of QLED devices, while reducing the probability of failure for preparing QLED devices.

And the compound using the application forms hole transport-luminous composite bed and/or electric transmission-luminous composite bed External quantum efficiency during can also significantly improving.

The preferred embodiments of the present invention are the foregoing is only, is not intended to limit the invention, for the skill of this area For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair Change, equivalent, improvement etc., should be included within the scope of the present invention.

Claims

1. a kind of luminous-electric charge transmits compound, it is characterised in that including：

Core-shell quanta dots, with core and shell；

Electric charge transport part, the electric charge transport part is inorganic nano-crystal；And

Crosslinking section, the shell is attached with the electric charge transport part by the crosslinking section.

2. luminous-electric charge according to claim 1 transmits compound, it is characterised in that the electric charge transport part includes tool There are first inorganic nano-crystal or the second inorganic nano-crystal with electric transmission function of hole transfer function, alternatively described The surface of one inorganic nano-crystal has the first part, and first inorganic nano-crystal is preferably NiO_XNanocrystalline, NiMgO_XNanometer Brilliant, p-type ZnO nano is brilliant, CuO is nanocrystalline, Cu₂O is nanocrystalline, Fe₃O₄Nanocrystalline, FeO is nanocrystalline, V₂O₅Nanocrystalline, MnTiO₃Receive Meter Jing, BaTiO₃Nanocrystalline, HgS is nanocrystalline, PbS is nanocrystalline, SnS is nanocrystalline, MnS is nanocrystalline, wherein 1≤x≤2；Alternatively The surface of second inorganic nano-crystal has Ligands, and second inorganic nano-crystal is preferably ZnO nano crystalline substance, TiO₂Receive Meter Jing, SrTiO₂Nanocrystalline, MgTiO₃Nanocrystalline, In₂S₃Nanocrystalline, TiS is nanocrystalline.

3. luminous-electric charge according to claim 2 transmits compound, it is characterised in that the shell of the core-shell quanta dots Surface has surface ligand, and first part is identical with the dissolubility of the surface ligand, the Ligands and the table The dissolubility of face part is identical, and the surface ligand is that oil-soluble carboxylic acids part, alcohol-soluble mercaptan carboxylic acid's class part or alcohol are molten Property sulfydryl alcohols part, preferably described alcohol-soluble mercaptan carboxylic acid class part be TGA part, mercaptopropionic acid part or sulfydryl Butyric acid part, preferably described alcohol-soluble sulfydryl alcohols part is mercaptoethanol part or sulfydryl hexanol part.

4. luminous-electric charge according to claim 1 transmits compound, it is characterised in that form the precursor of the crosslinking section Selected from C₂~C₁₀And having the crosslinking agent of two or more functional group, the functional group is amido, hydroxyl, carboxyl or sulfydryl, preferably institute Crosslinking agent is stated for ethanthiol or hexamethylene diamine.

5. a kind of luminous-electric charge transmission ink, the including luminous-electric charge transmission compound any one of Claims 1-4 And solvent.

6. ink according to claim 5, it is characterised in that the electric charge transport part is included with hole transport function First inorganic nano-crystal or the second inorganic nano-crystal with electric transmission function, the first part of first inorganic nano-crystal Dissolubility with the solvent is identical；The Ligands of second inorganic nano-crystal are identical with the dissolubility of the solvent；It is excellent Selecting the solvent includes oil soluble material liquid or alcohol-soluble material liq, and more preferably described oil soluble material is C₁~C₂₀It is straight Alkane, C₁~C₂₀Branched paraffin, including one or more pentacyclic C₁~C₂₀Alkane or including one or more six The C of yuan of rings₁~C₂₀Alkane, further preferably described alcohol-soluble material be C₁~C₁₀Straight chain alcohol, C₁~C₁₀Branched-chain alcoho, including one Individual or multiple pentacyclic C₁~C₁₀Monohydric alcohol and polyalcohol, the C including one or more hexatomic rings₁~C₁₀Monohydric alcohol and Polyalcohol.

7. ink according to claim 5, it is characterised in that the ink also includes anti-settling agent, the anti-settling agent is selected from Epoxy resin, aldehyde ketone resin, acrylic resin and/or polyurethane resin, preferably described acrylic resin are bay acid acrylic acid Resin, GMA, the weight of more preferably described anti-settling agent are the 10~50% of the ink weight.

8. a kind of luminous-electric charge transmits the preparation method of compound, it is characterised 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 Cross-linking agent is treated in mixing, formation, wherein, the core-shell quanta dots raw material has the core-shell quanta dots of surface ligand for shell layer surface, The charge transport materials are the inorganic nano-crystal with part；

Step S2, the precursor for treating cross-linking agent and crosslinking section is mixed to form and treats cross-linking system；And

Step S3, makes the liquid body treated that cross-linking system is crosslinked, obtain being transmitted containing the luminous-electric charge compound System, wherein, the crosslinking section replaces at least partly surface ligand and at least part of part with by the nucleocapsid quantum The shell of point is attached with the charge transport materials by the crosslinking section.

9. preparation method according to claim 8, it is characterised in that the core-shell quanta dots raw material is transmitted with the electric charge The weight ratio of material is 1:0.2~2；It is preferred that the concentration of core-shell quanta dots raw material described in first organic solution be 10~ 20mg/ml, the concentration of charge transport materials described in more preferably described second organic solution is 10~20mg/ml.

10. preparation method according to claim 8, it is characterised in that the charge transport materials include being passed with hole First inorganic nano-crystal raw material of transmission function or the second inorganic nano-crystal raw material with electric transmission function, described first is inorganic The surface of nanocrystalline raw material has the first part, and the first inorganic nano-crystal raw material is preferably NiO_XNanocrystalline, NiMgO_XNanometer Brilliant, p-type ZnO nano is brilliant, CuO is nanocrystalline, Cu₂O is nanocrystalline, Fe₃O₄Nanocrystalline, FeO is nanocrystalline, V₂O₅Nanocrystalline, MnTiO₃Receive Meter Jing, BaTiO₃Nanocrystalline, HgS is nanocrystalline, PbS is nanocrystalline, SnS is nanocrystalline, MnS is nanocrystalline, 1≤x≤2；Second nothing The surface of the nanocrystalline raw material of machine has Ligands, and the second inorganic nano-crystal raw material is preferably ZnO nano crystalline substance, TiO₂Nanometer Brilliant, SrTiO₂Nanocrystalline, MgTiO₃Nanocrystalline, In₂S₃Nanocrystalline, TiS is nanocrystalline.

11. preparation methods according to claim 10, it is characterised in that first part, the surface ligand, described The solvent of the first organic solution is identical with the dissolubility of the solvent of second organic solution；The Ligands, the surface Part, the solvent of first organic solution are identical with the dissolubility of the solvent of second organic solution.

12. preparation methods according to claim 11, it is characterised in that the surface ligand is matched somebody with somebody for oil-soluble carboxylic acids Body, alcohol-soluble mercaptan carboxylic acid's class part or alcohol-soluble sulfydryl alcohols part, preferably described alcohol-soluble mercaptan carboxylic acid class part are mercapto Guanidine-acetic acid part, mercaptopropionic acid part or mercaptobutyric acid part, preferably described alcohol-soluble sulfydryl alcohols part are matched somebody with somebody for mercaptoethanol The solvent of body or sulfydryl hexanol part, first organic solution and second organic solution include oil soluble material liquid or Alcohol-soluble material liq, the oil soluble material is C₁~C₂₀Linear paraffin, C₁~C₂₀Branched paraffin, including one or many Individual pentacyclic C₁~C₂₀Alkane or the C including one or more hexatomic rings₁~C₂₀Alkane, the precursor bag of the crosslinking section Ethanthiol is included, the alcohol-soluble material is C₁~C₁₀Straight chain alcohol, C₁~C₁₀Branched-chain alcoho, including one or more five-membered rings C₁~C₁₀Monohydric alcohol and polyalcohol, the C including one or more hexatomic rings₁~C₁₀Monohydric alcohol and polyalcohol, the friendship The precursor in connection portion includes hexamethylene diamine.

13. preparation methods according to claim 8, it is characterised in that the step S2 includes：

Treat that cross-linking agent mixes with anti-settling agent by described, form the first pre-composition；

The precursor of first pre-composition and crosslinking section is mixed, cross-linking system is treated described in formation；

It is preferred that the anti-settling agent is selected from epoxy resin, aldehyde ketone resin, acrylic resin and/or polyurethane resin, the acrylic acid Resin is laurate acrylic resin, GMA, and the weight of the anti-settling agent is the liquid system weight The 10~50% of amount；It is preferred that the step S3 stirs 2~4h at 30~40 DEG C carries out the crosslinking.

14. a kind of QLED devices, it is characterised in that the QLED devices include the anode, the hole transport-luminous multiple that are sequentially stacked Layer, electron transfer layer and negative electrode, or anode, hole transmission layer, electric transmission-luminous composite bed and negative electrode including being stacked are closed, Or anode, hole transport-luminous composite bed, electric transmission-luminous composite bed and negative electrode including being stacked, wherein, the hole Transmission-luminous composite bed, the electric transmission-luminous composite bed are using the hair optical-electronic any one of claim 6 to 8 Lotus transmission ink is made.

15. QLED devices according to claim 14, it is characterised in that between the electron transfer layer and the negative electrode also Electron injecting layer and/or electronic barrier layer are provided with, or the electric transmission-lighting is additionally provided with electricity between composite bed and negative electrode Sub- implanted layer and/or electronic barrier layer.