CN106784400A - Hole transmission layer and QLED and preparation method, illuminating module and display device - Google Patents
Hole transmission layer and QLED and preparation method, illuminating module and display device Download PDFInfo
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- CN106784400A CN106784400A CN201611183133.2A CN201611183133A CN106784400A CN 106784400 A CN106784400 A CN 106784400A CN 201611183133 A CN201611183133 A CN 201611183133A CN 106784400 A CN106784400 A CN 106784400A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/155—Hole transporting layers comprising dopants
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- H—ELECTRICITY
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Abstract
The present invention discloses hole transmission layer and QLED and preparation method, illuminating module and display device, and method includes step：Preparing Surface coating first has the FeS of lipophile organic ligand2Nanoparticles solution；Then by obtained FeS2Nanoparticles solution is deposited on PEDOT:On PSS hole injection layers, hole transmission layer is obtained.The present invention has the FeS of lipophile organic ligand using Surface coating2As hole transmission layer, PEDOT is deposited on:On PSS hole injection layers.On the one hand PEDOT is prevented:The PSS hole injection layers moisture absorption is damaged to each functional layer, improves QLED device stabilities and service life；On the other hand, the energy band between hole transmission layer and hole injection layer and quantum dot is more matched, reduce hole injection and transmission potential barrier, improve the luminous efficiency of QLED devices.
Description
Technical field
The present invention relates to LED technology field, more particularly to a kind of hole transmission layer and QLED devices and preparation side
Method, illuminating module and display device.
Background technology
Quantum dot（Quantum dot, QD）It is a kind of machinable semiconductor nanocrystal of solution, with luminescent spectrum
The advantages of narrow, emission wavelength controllable, spectral purity are high, light/chemical stabilization is good, most promises to be photophore of future generation
The core of part.Light emitting diode with quantum dots（Quantum dot light-emitting diode, QLED）Technology is base
In a kind of brand new technical of quantum dot, QLED has that preparation process is simple, good stability, excitation are high, colour temperature is good, long lifespan etc.
Outstanding advantages, have unrivaled technical advantage and application prospect compared with conventional light emitting diodes.
The QLED devices studied at present, it is most of to use Organic Light Emitting Diode（Organic light-emitting
diode, OLED）The organic semiconducting materials of middle ripe application inject or transport layer as carrier, such as poly- (3,4- ethylenes two
Oxygen thiophene)-polystyrolsulfon acid（PEDOT:PSS）, poly- (9,9- dioctyl fluorenes-CO-N- (4- butyl phenyls) diphenylamines)
（TFB）, polyvinylcarbazole（PVK）, poly- (N, N' double (4- butyl phenyls)-N, N'- double (phenyl) benzidine)（poly-TPD）、
Poly- (double-N of 9,9- dioctyl fluorenes -co-, N- phenyl -1,4- phenylenediamines)（PFB）, 4,4 ', 4 ' '-three (carbazole -9- bases) triphenylamine
（TCTA）, 4,4'- bis- (9- carbazoles) biphenyl（CBP）, N, N '-diphenyl-N, N '-two (3- aminomethyl phenyls) -1,1 '-biphenyl -4,
4 '-diamines（TPD）, N, N '-diphenyl-N, N '-（1- naphthyls）- 1,1 '-biphenyl -4,4 '-diamines（NPB）Deng.Wherein, PEDOT:
PSS has excellent hole mobility and outstanding filming performance, is the material for being most often used as hole injection layer.Excellent sky
Cave mobility can quickly be injected and be shifted to the hole on anode well, restrained effectively the product in hole
It is tired, and outstanding filming performance makes the simple controllable, repetitive rate of its process high, and greatly reduce process costs.Although
In this way, PEDOT:PSS is in faintly acid, and itself contains hygroscopic PSS units, and easily water suction is made moist, to being all organic half
The hole transmission layer of conductor material is produced and had a strong impact on, and eventually have impact on luminous efficiency, uniformity of luminance, the hair of QLED devices
Light life-span and device stability.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of hole transmission layer and QLED devices and
Preparation method, illuminating module and display device, it is intended to solve existing PEDOT:The PSS hole injection layers moisture absorption is caused to each functional layer
Destruction, and between existing hole transmission layer and hole injection layer and quantum dot can be with the relatively low problem of matching.
Technical scheme is as follows：
A kind of preparation method of hole transmission layer, wherein, including step：
Preparing Surface coating first has the FeS of lipophile organic ligand2Nanoparticles solution；
Then by obtained FeS2Nanoparticles solution is deposited on PEDOT:On PSS hole injection layers, hole transmission layer is obtained.
The preparation method of described hole transmission layer, wherein, the lipophile organic ligand is alkyl acid, alkylamine, alkane
One or more in base mercaptan, phosphine, phosphine oxide, alkyl phosphoric acid, stearic acid.
The preparation method of described hole transmission layer, wherein, FeS2In nanoparticles solution, FeS2Nano particle is doping
The FeS of metal ion2Nano particle, the metal ion of doping is sodium ion, potassium ion, magnesium ion, calcium ion, chromium ion, molybdenum
Ion, tungsten ion, manganese ion, cobalt ions, nickel ion, copper ion, zinc ion, cadmium ion, aluminium ion, indium ion, germanium ion, tin
One or more in ion, lead ion, antimony ion, tellurium ion.
The preparation method of described hole transmission layer, wherein, Surface coating has the FeS of lipophile organic ligand2Nanometer
The form of grain is one or more in dense film, nano wire, nanosphere, nanometer rods, nanocone, nano-hollow ball.
The preparation method of described hole transmission layer, wherein, preparing Surface coating has the FeS of lipophile organic ligand2Receive
The method of rice grain solution includes step：Iron dichloride tetrahydrate is dissolved in octadecylamine, iron salt solutions are obtained；Simultaneously lazy
Sulphur powder is dissolved in diphenyl ether under property gas shield, obtains sulphur solution；Then the sulphur that will be prepared under inert gas shielding is molten
Drop is added in iron salt solutions, after mixed solution then is heated into 100 ~ 300 °C, reacts 5 ~ 360 min；After reaction terminates
Cleaning purifying and centrifugal sedimentation are carried out to mixed solution, obtaining Surface coating has the FeS of octadecylamine2Nano particle, finally will
FeS2Nano particle is dissolved in chloroform, obtains FeS2Nanoparticles solution.
A kind of hole transmission layer, wherein, the hole transmission layer uses the preparation of as above any described hole transmission layer
Method is prepared from.
A kind of preparation method of QLED devices, wherein, including：
Step A, PEDOT is prepared on the substrate containing anode:PSS hole injection layers；
Step B, in PEDOT:Hole transmission layer as described above is prepared on PSS hole injection layers；
Step C, quantum dot light emitting layer is prepared on hole transmission layer；
Step D, electron transfer layer and negative electrode are sequentially prepared on quantum dot light emitting layer, obtain QLED devices.
A kind of QLED devices, wherein, include successively from bottom to top：Substrate, PEDOT containing anode:PSS holes are injected
Layer, hole transmission layer as described above, quantum dot light emitting layer, electron transfer layer and negative electrode.
A kind of illuminating module, wherein, including QLED devices as described above.
A kind of display device, wherein, including illuminating module as described above.
Beneficial effect：The present invention has the FeS of lipophile organic ligand using Surface coating2As hole transmission layer, deposition
In PEDOT:On PSS hole injection layers.On the one hand PEDOT is prevented:The PSS hole injection layers moisture absorption is damaged to each functional layer,
Improve QLED device stabilities and service life；On the other hand, make between hole transmission layer and hole injection layer and quantum dot
Energy band is more matched, and reduces hole injection and transmission potential barrier, improves the luminous efficiency of QLED devices.
Brief description of the drawings
Fig. 1 is the FeS of octadecylamine cladding of the invention2The flow chart of the preparation method of nano particle.
Fig. 2 is a kind of flow chart of the preparation method preferred embodiment of QLED devices of the invention.
Fig. 3 is the structural representation of QLED devices in the embodiment of the present invention 1.
Fig. 4 is the band structure schematic diagram of QLED devices in the embodiment of the present invention 1.
Specific embodiment
The present invention provides a kind of hole transmission layer and QLED devices and preparation method, illuminating module and display device, to make
The purpose of the present invention, technical scheme and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that
The specific embodiments described herein are merely illustrative of the present invention, is not intended to limit the present invention.
A kind of preparation method preferred embodiment of hole transmission layer of the invention, wherein, including step：Surface is prepared first
It is coated with the FeS of lipophile organic ligand2Nanoparticles solution；
Then by obtained FeS2Nanoparticles solution is deposited on PEDOT:On PSS hole injection layers, hole transmission layer is obtained.
The present invention has the FeS of lipophile organic ligand using Surface coating2As hole transmission layer, PEDOT is deposited on:
On PSS hole injection layers.Wherein, FeS used2Not only material source is abundant, with low cost, environment-protecting asepsis, prepare it is simple, and
And it can band and PEDOT:PSS and quanta point material matching are good, can be effectively reduced hole injection and transmission potential barrier, improve
The luminous efficiency of QLED devices.More particularly, the FeS used by the present invention2Surface coating has oil loving organic ligand, makes gained
The FeS for arriving2Hole transmission layer has strong-hydrophobicity, is prevented from PEDOT:The PSS moisture absorptions are to hole transmission layer, quantum dot light emitting layer
And top various functions layers are impacted, so as to improve the stability and service life of QLED devices.Further, since FeS2Table
Bread is covered with oil loving organic ligand, favorably improves the hair of QLED devices with the deposition of part quantum dot light emitting layer thereon
Optical uniformity.
Specifically, Surface coating of the present invention has the FeS of lipophile organic ligand2Nano particle has hydrophobicity.The parent
Oiliness organic ligand can be but be not limited to alkyl acid, alkylamine, alkyl hydrosulfide, phosphine, phosphine oxide, alkyl phosphoric acid, stearic acid etc.
In one or more.For example, the lipophile organic ligand can be but be not limited to octadecylamine, cetylamine, tetradecy lamine, oil
Amine, oleic acid, three hexyl phosphines, tri octyl phosphine, tributylphosphine, trioctyl phosphine oxide, octadecylphosphonic acid, double (2,4,4- trimethyls
Amyl group) phosphonic acids, the positive octadecyl ester of phosphoric acid, 1,2- dithioglycols, 1,6- ethanthiols, 1,4- dimercaptobenzenes, 1,2- hexadecanes two
One or more in alcohol, 1,7- 1,5-DAPs, 1,4- diaminobenzenes, tetradecyl phosphonic acids etc..
Further, FeS of the present invention2In nanoparticles solution, FeS2Nano particle can also be doped metal ion
FeS2Nano particle, the metal ion of doping can be but be not limited to sodium ion, potassium ion, magnesium ion, calcium ion, chromium ion,
Molybdenum ion, tungsten ion, manganese ion, cobalt ions, nickel ion, copper ion, zinc ion, cadmium ion, aluminium ion, indium ion, germanium ion,
One or more in tin ion, lead ion, antimony ion, tellurium ion etc..
Specifically, Surface coating of the present invention has the FeS of lipophile organic ligand2The form of nano particle can be but not limit
One or more in dense film, nano wire, nanosphere, nanometer rods, nanocone, nano-hollow ball etc..
Specifically, Surface coating of the present invention has the FeS of lipophile organic ligand2The preparation method of nanoparticles solution
Can be chemical method or Physical, wherein chemical method can be but be not limited to sol-gel process, chemical bath deposition method, chemical gas
One or more in phase sedimentation, hydro-thermal method, coprecipitation, electrochemical deposition method；Physical can be but be not limited to hot steaming
One kind in hair coating method, electron beam evaporation deposition method, magnetron sputtering method, multi-arc ion coating embrane method, electrolysis, method of electrostatic spinning
Or it is various.
Specifically, as a example by with sol-gel process, with reference to shown in Fig. 1, preparing Surface coating has lipophile organic ligand
FeS2The method and step of nanoparticles solution is as follows：By the Iron dichloride tetrahydrate of 0.1 ~ 1 mmol（FeCl2·4H2O）It is dissolved in
The octadecylamine of 0.05 ~ 0.5 mol（ODA）In, obtain iron salt solutions；Simultaneously in inert gas（Such as nitrogen）By 1 ~ 10 under protection
Mmol sulphur powders are dissolved in 5 ~ 50 ml diphenyl ether, obtain sulphur solution.Then in inert gas（Such as nitrogen）By preparation under protection
Sulphur solution is dropwise added drop-wise in iron salt solutions, after mixed reaction solution then is heated into 100 ~ 300 °C, reacts 5 ~ 360 min.
After reaction terminates, to ethanol cleaning purifying, and centrifugal sedimentation is added in resulting solution, obtaining Surface coating has the FeS of octadecylamine2
Nano particle（ODA-FeS2）, finally it is dissolved in chloroform, obtain FeS2Nanoparticles solution.
Specifically, the method for above-mentioned deposition of the invention can be but be not limited to spin-coating method, knife coating, print process, dipping and carry
One kind in daraf(reciprocal of farad), infusion method, spraying process, roll coating process, casting method, slit coating method, strip rubbing method, strike or
It is various.
A kind of hole transmission layer of the invention, wherein, the hole transmission layer is using as above any described hole transport
The preparation method of layer is prepared from.On the one hand hole transmission layer of the present invention prevents PEDOT:The PSS hole injection layers moisture absorption is to each work(
Ergosphere is damaged, and improves QLED device stabilities and service life；On the other hand, make hole transmission layer and hole injection layer and
Energy band between quantum dot is more matched, and reduces hole injection and transmission potential barrier, improves the luminous efficiency of QLED devices.Additionally,
Due to FeS2Surface coating has oil loving organic ligand, favorably thereon with the deposition of part quantum dot light emitting layer, improves
The uniformity of luminance of QLED devices.
Fig. 2 is a kind of flow chart of the preparation method preferred embodiment of QLED devices of the invention, as illustrated, it is wrapped
Include：
Step S100, PEDOT is prepared on the substrate containing anode:PSS hole injection layers；
Step S200, in PEDOT:Hole transmission layer as described above is prepared on PSS hole injection layers；
Step S300, quantum dot light emitting layer is prepared on hole transmission layer；
Step S400, electron transfer layer and negative electrode are sequentially prepared on quantum dot light emitting layer, obtain QLED devices.
A kind of QLED devices preferred embodiment of the invention, it includes successively from bottom to top：Substrate containing anode,
PEDOT:PSS hole injection layers, hole transmission layer as described above, quantum dot light emitting layer, electron transfer layer and negative electrode.Using this
The QLED devices that hole transmission layer as described above is made are invented, not only with stability high and service life long, is also had
There is luminous efficiency high high and uniformity of luminance.
Specifically, substrate of the present invention can be rigid substrate or flexible substrate, wherein the rigid substrate can be
But it is not limited to one or more in glass, tinsel；The flexible substrate can be but be not limited to poly terephthalic acid second
Diol ester（PET）, ethylene glycol terephthalate（PEN）, polyether-ether-ketone（PEEK）, polystyrene（PS）, polyether sulfone（PES）、
Makrolon（PC）, poly- aryl acid esters（PAT）, polyarylate（PAR）, polyimides（PI）, polyvinyl chloride（PVC）, polyethylene
（PE）, polyvinylpyrrolidone（PVP）, one or more in textile fabric.
Specifically, anode of the present invention may be selected from indium doping tin oxide（ITO）, fluorine-doped tin oxide（FTO）, Sb doped
Tin oxide（ATO）, aluminium-doped zinc oxide（AZO）One or more in.
Specifically, quantum dot of the present invention may be selected from doped or non-doped II-V compound semiconductors, iii-v
One or more in compound semiconductor, IV-VI compound semiconductors and its core shell structure.The quantum dot may be selected from
One or more in doped or non-doped inorganic Ca-Ti ore type semiconductor, hybrid inorganic-organic Ca-Ti ore type semiconductor.Tool
Body ground, the inorganic Ca-Ti ore type semiconductor structure formula is AMX3, wherein A is Cs+Ion；M is divalent metal,
Can be but be not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+In one kind；X is
Halide anion, can be but be not limited to Cl-、Br-、I-In one kind；The hybrid inorganic-organic Ca-Ti ore type semiconductor
General structure is BMX3, wherein B is organic amine cation, can be but be not limited to CH3(CH2)n-2NH3 +(n >=2) or NH3
(CH2)nNH3 2+(n≥2).As n=2, inorganic metal hal ide octahedron MX6 4-Connected by way of common top, metal sun from
Sub- M is located at the octahedral body-centered of halogen, and organic amine cation B is filled in the space between octahedron, forms the three of unlimited extension
Dimension structure；As n ＞ 2, the inorganic metal hal ide octahedron MX connected in the way of common top6 4-Extend to be formed in two-dimensional directional
Layer structure, Intercalation reaction organic amine cation bilayer（Protonation monoamine）Or organic amine cation monolayer（Proton
Change diamine）, organic layer is mutually overlapping with inorganic layer to form stable two-dimensional layered structure；M is divalent metal, Ke Yiwei
But it is not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+；X is halide anion, can
Think but be not limited to Cl-、Br-、I-。
Specifically, electron transport layer materials of the present invention can be but be not limited to N-shaped ZnO, TiO2、SnO、Ta2O3、
AlZnO、ZnSnO、InSnO、Alq3、Ca、Ba、CsF、LiF、CsCO3In one or more；Preferably, the electric transmission
Layer is N-shaped ZnO, N-shaped TiO2。
Specifically, negative electrode of the present invention can be but be not limited to various conductive carbon materials, conducting metal oxide material,
One or more in metal material；Wherein conductive carbon material can be but be not limited to doped or non-doped CNT, doping
Or in undoped Graphene, doped or non-doped graphene oxide, C60, graphite, carbon fiber, many sky carbon or their mixture
One or more；Conducting metal oxide material can be but be not limited in ITO, FTO, ATO, AZO or their mixture
One or more；Metal material can be but be not limited in Al, Ag, Cu, Mo, Au or their alloy one or more；
In wherein described metal material, its form can be but be not limited to dense film, nano wire, nanosphere, nanometer rods, nanocone,
One or more in nano-hollow ball or their mixture；Preferably, the negative electrode is Ag or Al.
Specifically, QLED devices of the present invention with partial encapsulation, full encapsulation or can not encapsulated.
Specifically, the preparation method of hole transmission layer of the present invention can be but be not limited to spin-coating method, knife coating, printing
Method, dip-coating method, infusion method, spraying process, roll coating process, casting method, slit coating method, strip rubbing method, strike
One or more in.
Specifically, the preparation method of above layers of the present invention can be chemical method or Physical, wherein chemical method include but
It is not limited in chemical vapour deposition technique, successive ionic layer adsorption and reaction method, anodizing, strike, coprecipitation
One or more；Physical include but is not limited to spin-coating method, print process, knife coating, dip-coating method, infusion method, spraying process,
Roll coating process, casting method, slit coating method, strip rubbing method, thermal evaporation coating method, electron beam evaporation deposition method, magnetron sputtering
One or more in method, multi-arc ion coating embrane method, physical vaporous deposition, atomic layer deposition method, pulsed laser deposition.
It should be noted that, the invention is not restricted to the QLED devices of said structure, can also further include interfactial work ergosphere or
Interface-modifying layer, including but not limited to electronic barrier layer, hole blocking layer, electrode modification layer, the one kind in isolated protective layer or
It is various.
It should be noted that, the invention is not restricted to prepare above-mentioned autologous QLED devices, reciprocal form structure can also be prepared
QLED devices.And the QLED devices of reciprocal form structure can also further include interfactial work ergosphere or interface-modifying layer, including but not
It is limited to one or more in electronic barrier layer, hole blocking layer, electrode modification layer, isolated protective layer.
A kind of illuminating module of the invention, wherein, including QLED devices as described above.
A kind of display device of the invention, wherein, including illuminating module as described above.
Below by embodiment, the present invention is described in detail.
Embodiment 1
1）, octadecylamine cladding FeS2The preparation of nanoparticles solution：
By the Iron dichloride tetrahydrate of 0.5 mmol（FeCl2·4H2O）It is dissolved in the octadecylamine of 0.1 mol（ODA）In, obtain
Iron salt solutions；Meanwhile, 5 mmol sulphur powders are dissolved in 10 ml diphenyl ether under nitrogen protection, obtain sulphur solution.Then in nitrogen
The sulphur solution of preparation is dropwise added drop-wise in iron salt solutions under gas shielded, mixed solution is then heated to 200 °C, reaction 60
min.After reaction terminates, to ethanol cleaning purifying is added in resulting solution, sedimentation is then centrifuged for, obtaining Surface coating has octadecylamine
FeS2Nano particle, is finally dissolved in chloroform, obtains the FeS of octadecylamine cladding2Nanoparticles solution.
2）, QLED devices preparation：
One layer of PEDOT of spin coating on ITO substrates:PSS films are used as hole injection layer；
By above-mentioned 1）The FeS of the octadecylamine cladding of preparation2Nanoparticles solution is spin-coated on PEDOT:On PSS hole injection layers, system
Obtain hole transmission layer；
Then, one layer of CdSe@ZnS quantum dot luminescent layer of spin coating on hole transmission layer；
Then, on CdSe@ZnS quantum dot luminescent layers spin coating layer of ZnO layer as electron transfer layer；
Finally, one layer of Al is deposited with ZnO layer, QLED devices are obtained.Wherein, the structural representation of the QLED devices of the present embodiment
See Fig. 3, its band structure schematic diagram is shown in Fig. 4.
Embodiment 2
1）, octadecylamine cladding FeS2The preparation of nanoparticles solution：
By the Iron dichloride tetrahydrate of 0.1 mmol（FeCl2·4H2O）It is dissolved in the octadecylamine of 0.1 mol（ODA）In, obtain
Iron salt solutions；Meanwhile, 5 mmol sulphur powders are dissolved in 10 ml diphenyl ether under nitrogen protection, obtain sulphur solution.Then in nitrogen
The sulphur solution of preparation is dropwise added drop-wise in iron salt solutions under gas shielded, mixed solution is then heated to 150 °C, reaction 360
min.After reaction terminates, to ethanol cleaning purifying is added in resulting solution, sedimentation is then centrifuged for, obtaining Surface coating has octadecylamine
FeS2Nano particle, is finally dissolved in chloroform, obtains the FeS of octadecylamine cladding2Nanoparticles solution.
2）, QLED devices preparation：
One layer of PEDOT of spin coating on ITO substrates:PSS films are used as hole injection layer；
By above-mentioned 1）The FeS of the octadecylamine cladding of preparation2Nanoparticles solution is spin-coated on PEDOT:On PSS hole injection layers, system
Obtain hole transmission layer；
Then, one layer of CdSe@ZnS quantum dot luminescent layer of spin coating on hole transmission layer；
Then, on CdSe@ZnS quantum dot luminescent layers spin coating layer of ZnO layer as electron transfer layer；
Finally, one layer of Al is deposited with ZnO layer, QLED devices are obtained.
Embodiment 3
1）, oleyl amine cladding FeS2The preparation of nanoparticles solution：
By the Iron dichloride tetrahydrate of 0.5 mmol（FeCl2·4H2O）It is dissolved in the oleyl amine of 0.4 mol, obtains molysite molten
Liquid；Meanwhile, 10 mmol sulphur powders are dissolved in 50 ml diphenyl ether under nitrogen protection, obtain sulphur solution.Then protected in nitrogen
The sulphur solution of preparation is dropwise added drop-wise in iron salt solutions under shield, mixed solution is then heated to 300 °C, reaction 100
min.After reaction terminates, to ethanol cleaning purifying is added in resulting solution, sedimentation is then centrifuged for, obtaining Surface coating has oleyl amine
FeS2Nano particle, is finally dissolved in chloroform, obtains the FeS of oleyl amine cladding2Nanoparticles solution.
2）, QLED devices preparation：
One layer of PEDOT of spin coating on ITO substrates:PSS films are used as hole injection layer；
By above-mentioned 1）The FeS of the oleyl amine cladding of preparation2Nanoparticles solution is spin-coated on PEDOT:On PSS hole injection layers, it is obtained
Hole transmission layer；
Then, one layer of CdSe@CdS quantum dot luminescent layer of spin coating on hole transmission layer；
Then, on CdSe@CdS quantum dot luminescent layers spin coating layer of ZnO as electron transfer layer；
Finally, one layer of Al is deposited with ZnO layer, QLED devices are obtained.
Embodiment 4
1）, oleyl amine cladding FeS2The preparation of nanoparticles solution：
By the Iron dichloride tetrahydrate of 0.1 mmol（FeCl2·4H2O）It is dissolved in the oleyl amine of 0.05 mol, obtains molysite molten
Liquid；Meanwhile, 1 mmol sulphur powders are dissolved in 5 ml diphenyl ether under nitrogen protection, obtain sulphur solution.Then protected in nitrogen
It is lower to be dropwise added drop-wise in iron salt solutions the sulphur solution of preparation, mixed solution is then heated to 250 °C, react 5 min.Instead
After should terminating, to ethanol cleaning purifying is added in resulting solution, sedimentation is then centrifuged for, obtaining Surface coating has the FeS of oleyl amine2Receive
Rice grain, is finally dissolved in chloroform, obtains the FeS of oleyl amine cladding2Nanoparticles solution.
2）, QLED devices preparation：
One layer of PEDOT of spin coating on ITO substrates:PSS films are used as hole injection layer；
By above-mentioned 1）The FeS of the oleyl amine cladding of preparation2Nanoparticles solution is spin-coated on PEDOT:On PSS hole injection layers, it is obtained
Hole transmission layer；
Then, one layer of CdSe@CdS quantum dot luminescent layer of spin coating on hole transmission layer；
Then, on CdSe@CdS quantum dot luminescent layers spin coating layer of ZnO as electron transfer layer；
Finally, one layer of Al is deposited with ZnO layer, QLED devices are obtained.
Embodiment 5
1）, tri octyl phosphine cladding FeS2The preparation of nanoparticles solution：
By the Iron dichloride tetrahydrate of 1 mmol（FeCl2·4H2O）It is dissolved in the tri octyl phosphine of 0.5 mol, obtains molysite molten
Liquid；Meanwhile, 8 mmol sulphur powders are dissolved in 50 ml diphenyl ether under nitrogen protection, obtain sulphur solution.Then protected in nitrogen
It is lower to be dropwise added drop-wise in iron salt solutions the sulphur solution of preparation, mixed solution is then heated to 100 °C, react 30 min.Instead
After should terminating, to ethanol cleaning purifying is added in resulting solution, sedimentation is then centrifuged for, obtaining Surface coating has tri octyl phosphine
FeS2Nano particle, is finally dissolved in chloroform, obtains the FeS of tri octyl phosphine cladding2Nanoparticles solution.
2）, QLED devices preparation：
One layer of PEDOT of spin coating on ITO substrates:PSS films are used as hole injection layer；
By above-mentioned 1）The FeS of the tri octyl phosphine cladding of preparation2Nanoparticles solution is spin-coated on PEDOT:On PSS hole injection layers,
Hole transmission layer is obtained；
Then, one layer of CdSe@ZnS quantum dot luminescent layer of spin coating on hole transmission layer；
Then, on CdSe@ZnS quantum dot luminescent layers spin coating layer of ZnO as electron transfer layer；
Finally, one layer of Al is deposited with ZnO layer, QLED devices are obtained.
In sum, the present invention is provided a kind of hole transmission layer and QLED devices and preparation method, illuminating module with it is aobvious
Showing device.The present invention has the FeS of lipophile organic ligand using Surface coating2As hole transmission layer, PEDOT is deposited on:PSS
On hole injection layer.Wherein, FeS used2Not only material source is abundant, with low cost, environment-protecting asepsis, prepare it is simple, and
It can band and PEDOT:PSS and quanta point material matching are good, can be effectively reduced hole injection and transmission potential barrier, improve
The luminous efficiency of QLED devices.More particularly, the FeS used by the present invention2Surface coating has oil loving organic ligand, makes gained
The FeS for arriving2Hole transmission layer has strong-hydrophobicity, is prevented from PEDOT:The PSS moisture absorptions are to hole transmission layer, quantum dot light emitting layer
And top various functions layers are impacted, so as to improve the stability and service life of QLED devices.Further, since FeS2Table
Bread is covered with oil loving organic ligand, favorably improves the hair of QLED devices with the deposition of part quantum dot light emitting layer thereon
Optical uniformity.
It should be appreciated that application of the invention is not limited to above-mentioned citing, and for those of ordinary skills, can
To be improved according to the above description or converted, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Shield scope.
Claims (10)
1. a kind of preparation method of hole transmission layer, it is characterised in that including step：
Preparing Surface coating first has the FeS of lipophile organic ligand2Nanoparticles solution；
Then by obtained FeS2Nanoparticles solution is deposited on PEDOT:On PSS hole injection layers, hole transmission layer is obtained.
2. the preparation method of hole transmission layer according to claim 1, it is characterised in that the lipophile organic ligand is
One or more in alkyl acid, alkylamine, alkyl hydrosulfide, phosphine, phosphine oxide, alkyl phosphoric acid, stearic acid.
3. the preparation method of hole transmission layer according to claim 1, it is characterised in that FeS2In nanoparticles solution,
FeS2Nano particle is the FeS of doped metal ion2Nano particle, the metal ion of doping is sodium ion, potassium ion, magnesium ion,
Calcium ion, chromium ion, molybdenum ion, tungsten ion, manganese ion, cobalt ions, nickel ion, copper ion, zinc ion, cadmium ion, aluminium ion,
One or more in indium ion, germanium ion, tin ion, lead ion, antimony ion, tellurium ion.
4. the preparation method of hole transmission layer according to claim 1, it is characterised in that Surface coating has lipophile organic
The FeS of part2The form of nano particle is in dense film, nano wire, nanosphere, nanometer rods, nanocone, nano-hollow ball
One or more.
5. the preparation method of hole transmission layer according to claim 1, it is characterised in that preparing Surface coating has lipophile
The FeS of organic ligand2The method and step of nanoparticles solution is as follows：Iron dichloride tetrahydrate is dissolved in octadecylamine, is obtained
Iron salt solutions；Sulphur powder is dissolved in diphenyl ether under inert gas shielding simultaneously, sulphur solution is obtained；Then protected in inert gas
The sulphur solution of preparation is added drop-wise in iron salt solutions under shield, after mixed solution then is heated into 100 ~ 300 °C, reaction 5 ~ 360
min；Reaction carries out cleaning purifying and centrifugal sedimentation after terminating to mixed solution, and obtaining Surface coating has the FeS of octadecylamine2Receive
Rice grain, finally by FeS2Nano particle is dissolved in chloroform, obtains FeS2Nanoparticles solution.
6. a kind of hole transmission layer, it is characterised in that the hole transmission layer is using the hole as described in claim 1 ~ 5 is any
The preparation method of transport layer is prepared from.
7. a kind of preparation method of QLED devices, it is characterised in that including：
Step A, PEDOT is prepared on the substrate containing anode:PSS hole injection layers；
Step B, in PEDOT:Hole transmission layer as claimed in claim 6 is prepared on PSS hole injection layers；
Step C, quantum dot light emitting layer is prepared on hole transmission layer；
Step D, electron transfer layer and negative electrode are sequentially prepared on quantum dot light emitting layer, obtain QLED devices.
8. a kind of QLED devices, it is characterised in that include successively from bottom to top：Substrate, PEDOT containing anode:Note in PSS holes
Enter layer, hole transmission layer as claimed in claim 6, quantum dot light emitting layer, electron transfer layer and negative electrode.
9. a kind of illuminating module, it is characterised in that including QLED devices as claimed in claim 8.
10. a kind of display device, it is characterised in that including illuminating module as claimed in claim 9.
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