CN108807720A - Functionalization cathode, QLED and preparation method, illuminating module and display device - Google Patents
Functionalization cathode, QLED and preparation method, illuminating module and display device Download PDFInfo
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Abstract
Maniflest function cathode, QLED and preparation method of the present invention, illuminating module and display device, method include step：Deposit one layer of hydrosulphonyl silane on the electron transport layer first；Then one layer of cathode is deposited on hydrosulphonyl silane layer, obtains functionalization cathode.The present invention modifies one layer of hydrosulphonyl silane between electron transfer layer and metal electrode, silica bond energy in hydrosulphonyl silane is connect with electron transfer layer, and it is passivated the surface defect of electron transfer layer, and the sulfydryl for being exposed to the other end can closely be connect with metal electrode with covalent bond, it on the one hand can be in metal electrode deposition process as the close nuclearing centre of metal, it is grown into out uniformly regular metal electrode, on the other hand it can promote the close connection between electron transfer layer and metal electrode, keep interface stability and interfacial property, prevent infiltration of the metal electrode in electronic shell, corrosion, it aoxidizes or falls off, effectively improve service life and the stability of electron injection efficiency and QLED devices.
Description
Technical field
The present invention relates to LED technology field more particularly to it is a kind of include electron transfer layer functionalization it is cloudy
Pole, QLED devices and preparation method, illuminating module and display device.
Background technology
In recent years, the Colloidal Quantum Dots with nanocrystal size（Quantum dot, QD）As a kind of new and effective
Rate luminescent material is got the attention, with various unique optical characteristics, as energy gap easily tunes, extinction spectrum model
Enclose width, spectral purity height, light/stable chemical performance etc..Light emitting diode using quanta point material as luminescent layer is known as quantum
Point luminescent diode（Quantum dot light-emitting diode, QLED）, it is a kind of novel luminescence display skill
Art.In LED display fields, QLED and more Organic Light Emitting Diode is studied at present（Organic light-emitting
diode, OLED）It compares, shows the superiority of bigger, such as electro-optical efficiency higher, longer life expectancy, production cost be low, energy
Amount consumption is small, color purity is high etc., and huge potentiality are shown in next-generation display technology.
The QLED devices of mainstream research use ZnO, TiO mostly at present2Etc. broad-band gaps metal oxide semiconductor material make
For electron transfer layer, and on the electron transport layer by metals such as process deposits Ag, Al such as hot evaporation, the moon as QLED devices
Pole.In order to improve the injection efficiency and luminous efficiency of electronics, cathode generally selects the alap material of work function or by property
The high-work-function metal of active low workfunction metal and stable chemical performance is deposited together forms metallic cathode or alloy electrode,
Such as Mg:Ag（10:1）, Li:Al（0.6%Li）Deng.But this method cost is higher, and technique is relative complex.In addition, electronics passes
There is large effect at interface between defeated layer and metal electrode to QLED device performances and stability, such as ZnO layer and Al electrode layers
Contact tightness degree and the defect state etc. on the surfaces ZnO can all highly impact the injection efficiency of electronics.Meanwhile gold
Belong to metallic atom in electrode it is readily permeable in ZnO, in QLED device operational process, this infiltration can aggravate, and gold
Belong to electrode to be easy to fall off, the interfacial property between electron transfer layer and electrode is easy to be destroyed, and greatly affected device
Stability and luminescent lifetime.
Therefore, the existing technology needs to be improved and developed.
Invention content
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide it is a kind of include electron transfer layer function
Change cathode, QLED devices and preparation method, illuminating module and display device, it is intended to solve between existing electron transfer layer and cathode
Interface the problem of greatly affected QLED device performances and stability.
Technical scheme is as follows：
A kind of preparation method for the functionalization cathode including electron transfer layer, wherein including step：
Deposit one layer of hydrosulphonyl silane on the electron transport layer first；
Then one layer of cathode is deposited on hydrosulphonyl silane layer, obtains functionalization cathode.
Described includes the preparation method of the functionalization cathode of electron transfer layer, wherein further includes step：On cathode
Deposit the alkyl ammonium halide of one layer of band-SH.
Described includes the preparation method of the functionalization cathode of electron transfer layer, wherein the material of the electron transfer layer
Material is ZnO, TiO2、WO3、NiO、MoO3、Fe2O3、SnO2、Ta2O3, it is one or more in AlZnO, ZnSnO, InSnO.
Described includes the preparation method of the functionalization cathode of electron transfer layer, wherein the general formula of the hydrosulphonyl silane
For X3Si (CH2)nSH, X is one or more in chloro, methoxyl group, ethyoxyl, methoxy ethoxy, acetoxyl group in formula,
The value of n is 0 ~ 3.
Described includes the preparation method of the functionalization cathode of electron transfer layer, wherein the hydrosulphonyl silane is
(CH3O)3SiC3H6SH、(C2H5O)3SiC3H6One or both of SH.
Described includes the preparation method of the functionalization cathode of electron transfer layer, wherein the material of the cathode be Al,
One or more in Ag, Cu, Mo, Au, the form of the cathode is dense film, nano wire, nanosphere, nanometer rods, nanometer
It is one or more in cone, nano-hollow ball.
Described includes the preparation method of the functionalization cathode of electron transfer layer, wherein the alkyl halide of the band-SH
The general formula of ammonium is HS- (CH2)m(CH3)3NY, Y is halide ion, and/or acid ion in formula, and the halide ion is F-、Cl-、
Br-、I-In it is one or more, the acid ion be HSO4 -、COO-One or both of, the value of m is 0 ~ 16.
A kind of includes the functionalization cathode of electron transfer layer, wherein it includes electronics to use any one of them as above
The preparation method of the functionalization cathode of transport layer is prepared.
A kind of preparation method of QLED devices, wherein including：
Step A, deposition anode on substrate；
Step B, the deposition of hole implanted layer on anode；
Step C, the deposition of hole transport layer on hole injection layer；
Step D, quantum dot light emitting layer is deposited on the hole transport layer；
Step E, on quantum dot light emitting layer, deposition includes the functionalization cathode of electron transfer layer as described above, obtains QLED
Device.
A kind of QLED devices, wherein be prepared using the preparation method of QLED devices as described above, the QLED devices
Part includes successively：Substrate, hole injection layer, hole transmission layer, quantum dot light emitting layer, includes electronics as described above at anode
The functionalization cathode of transport layer.
A kind of illuminating module, wherein including QLED devices as described above.
A kind of display device, wherein including illuminating module as described above.
Advantageous effect：The present invention is in metal oxide electron transport layer and metal electrode（Cathode）Between modify one layer of sulfydryl
Silane, wherein the silica bond energy in hydrosulphonyl silane is connect with electron transfer layer, and is passivated the surface defect of electron transfer layer, and
The sulfydryl for being exposed to the other end can closely be connect with metal electrode with covalent bond, on the one hand can be in metal electrode deposition process
As the close nuclearing centre of metal, it is grown into out uniformly regular metal electrode, on the other hand electronics can be promoted to pass
Close connection between defeated layer and metal electrode keeps interface stability and interfacial property, prevents metal electrode in electronic shell
Infiltration, corrosion, oxidation or fall off, effectively improve service life and the stability of electron injection efficiency and QLED devices.
Description of the drawings
Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of QLED devices of the present invention.
Fig. 2 is (CH used in the embodiment of the present invention 13O)3SiC3H6The structural schematic diagram of SH.
Fig. 3 is the structural schematic diagram of functionalization cathode in the embodiment of the present invention 1.
Fig. 4 is the structural schematic diagram of light emitting diode with quantum dots obtained in the embodiment of the present invention 1.
Fig. 5 is the structural schematic diagram of (11- mercapto-undecanoics base) trimethylammonium bromide used in the embodiment of the present invention 2.
Fig. 6 is the structural schematic diagram of functionalization cathode in the embodiment of the present invention 2.
Fig. 7 is the structural schematic diagram of light emitting diode with quantum dots obtained in the embodiment of the present invention 2.
Specific implementation mode
It includes functionalization cathode, QLED devices and the preparation method of electron transfer layer, luminous mould that the present invention, which provides a kind of,
Group and display device, it is to make the purpose of the present invention, technical solution and effect clearer, clear and definite, further to the present invention below
It is described in detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to limit this hair
It is bright.
A kind of preparation method preferred embodiment of functionalization cathode including electron transfer layer of the present invention, wherein packet
Include step：
Deposit one layer of hydrosulphonyl silane layer on the electron transport layer first；
Then one layer of cathode is deposited on hydrosulphonyl silane layer, obtains functionalization cathode.
Specifically, the material of electron transfer layer of the present invention can be n-type metal oxide semiconductor, for example, described
The material of electron transfer layer can be but be not limited to ZnO, TiO2、WO3、NiO、MoO3、Fe2O3、SnO2、Ta2O3、AlZnO、
It is one or more in ZnSnO, InSnO etc..Preferably, the material of the electron transfer layer can be ZnO, TiO2One in
Kind or two kinds.
Specifically, the deposition method of hydrosulphonyl silane of the present invention can be chemical method or Physical, and wherein chemical method can
Think but be not limited to chemical vapour deposition technique, successive ionic layer adsorption and reaction method, anodizing, strike, coprecipitated
It is one or more in the method for shallow lake；Physical can be but be not limited to spin-coating method, print process, knife coating, dip-coating method, immersion
Method, spray coating method, roll coating process, casting method, slit coating method, strip rubbing method, thermal evaporation coating method, electron beam evaporation deposition
One in method, magnetron sputtering method, multi-arc ion coating embrane method, physical vaporous deposition, atomic layer deposition method, pulsed laser deposition
Kind is a variety of.Preferably, the deposition method of the hydrosulphonyl silane is spin-coating method, print process or dip-coating method.
Specifically, the hydrosulphonyl silane is that molecular end carries sulfydryl（-SH）Organo-silicon compound, general formula X3Si
(CH2)nSH, X is one or more, these bases in chloro, methoxyl group, ethyoxyl, methoxy ethoxy, acetoxyl group in formula
Silanol is generated when group's hydrolysis（Si(OH)3）, and combined with inorganic substances, siloxanes is formed, the value of n is 0 ~ 3.Preferably,
The hydrosulphonyl silane is mercaptopropyl trimethoxysilane (CH3O)3SiC3H6SH, mercaptopropyltriethoxysilane (C2H5O)3SiC3H6One or both of SH.
Specifically, the material of cathode of the present invention can be but be not limited to one kind in Al, Ag, Cu, Mo, Au or more
Kind, can also be their alloy.The form of the cathode can be but be not limited to dense film, nano wire, nanosphere, nanometer
It is one or more in stick, nanocone, nano-hollow ball.Preferably, the material of the cathode is one kind or two in Al, Ag
Kind.
The present invention is in metal oxide electron transport layer and metal electrode（Cathode）Between modify one layer of hydrosulphonyl silane,
In, the silica bond energy in hydrosulphonyl silane is connect with electron transfer layers such as ZnO, and is passivated the surface defect of ZnO, and is exposed to another
The sulfydryl at end can closely be connect with metal electrodes such as Ag with S-Ag covalent bonds, on the one hand can be made in metal electrode deposition process
For the close nuclearing centre of metal, it is grown into out uniformly regular metal electrode, on the other hand can promote electron-transport
Close connection between layer and metal electrode keeps interface stability and interfacial property, prevents metal electrode in electronic shell
Infiltration, corrosion, oxidation fall off, and effectively improve service life and the stability of electron injection efficiency and QLED devices.
Specifically, the present invention also provides another preferred embodiments of preparation method of the functionalization cathode, further include step
Suddenly：The alkyl ammonium halide of one layer of band-SH is deposited on cathode.The alkyl ammonium halide of the band-SH is that molecular end carries sulfydryl
（-SH）Quaternary ammonium salt, general formula be HS- (CH2)m(CH3)3NY, Y can be but be not limited to halide ion, and/or acid group in formula
Ion, the halide ion can be but be not limited to F-、Cl-、Br-、I-In it is one or more, the acid ion can be
But it is not limited to HSO4 -、COO-One or both of, the value of m is 0 ~ 16.Preferably, the halide ion is (11- sulfydryls ten
One alkyl) trimethylammonium bromide, (14- sulfydryls myristyl) dimethyl ethyl ammonium bromide.
The present invention is in metal dispatch from foreign news agency pole surface（That is cathode surface）It is surface modified place with the alkyl ammonium halide with sulfydryl
Reason makes surface of metal electrode generate interface dipole, so that the cathode of high work function is changed into the cathode of low work function, makes electricity
Meet Ohmic contact between pole and electron transfer layer, reduces electron injection and transmission potential barrier, improve the luminous efficiency of QLED devices
And luminescent lifetime.
A kind of functionalization cathode of the present invention, wherein using the preparation method of any one of them functionalization cathode as above
It is prepared.Interface of the one aspect of the present invention between metal oxide electron transport layer and metal electrode introduces hydrosulphonyl silane,
Being completely embedded degree, keeping interface stability and interfacial property for the two can be not only improved, but also metal electrode can be prevented
Infiltration, corrosion, oxidation in electron transfer layer fall off, to effectively improve electron injection efficiency and QLED devices
Service life and stability；On the other hand, it is handled with the alkyl ammonium halide with sulfydryl in metal electrode outer surface, it can be Gao Gong
The cathode of function is changed into the cathode of low work function, makes to meet Ohmic contact between electrode and electron transfer layer, reduces electronics note
Enter and transmit potential barrier, to further increase the luminous efficiency and luminescent lifetime of QLED devices.
Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of QLED devices of the present invention, as shown, it is wrapped
It includes：
Step S100, deposition anode on substrate；
Step S200, the deposition of hole implanted layer on anode；
Step S300, the deposition of hole transport layer on hole injection layer；
Step S400, quantum dot light emitting layer is deposited on the hole transport layer；
Step S500, on quantum dot light emitting layer, deposition includes the functionalization cathode of electron transfer layer as described above, is obtained
QLED devices.
A kind of QLED devices preferred embodiment of the present invention, using the preparation method preparation of QLED devices as described above
At the QLED devices include successively：Substrate, anode, hole injection layer, hole transmission layer, quantum dot light emitting layer, as described above
Include electron transfer layer functionalization cathode.
Specifically, include one layer of hydrosulphonyl silane between the electron transfer layer and cathode in the above-mentioned QLED devices of the present invention,
Wherein, the silica bond energy in hydrosulphonyl silane is connect with electron transfer layers such as ZnO, and is passivated the surface defect of ZnO, and is exposed to another
The sulfydryl of one end can closely be connect with metal electrodes such as Ag with S-Ag covalent bonds, on the one hand can be in metal electrode deposition process
As the close nuclearing centre of metal, it is grown into out uniformly regular metal electrode, on the other hand electronics can be promoted to pass
Close connection between defeated layer and metal electrode keeps interface stability and interfacial property, prevents metal electrode in electronic shell
Infiltration, corrosion, oxidation or fall off, effectively improve service life and the stability of electron injection efficiency and QLED devices.
Further, in the above-mentioned QLED devices of the present invention, the cathode surface also includes one layer of alkyl halide with sulfydryl
Ammonium, the present invention are surface modified processing with the alkyl ammonium halide with sulfydryl in metal dispatch from foreign news agency pole surface, make surface of metal electrode
Generate interface dipole, so that the cathode of high work function is changed into the cathode of low work function, make electrode and electron transfer layer it
Between meet Ohmic contact, reduce electron injection and transmission potential barrier, improve the luminous efficiency and luminescent lifetime of QLED devices.Especially
Ground, the present invention are applicable not only to conventional QLED devices, apply also for flexible QLED devices.
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, metal foil；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（PV）, polyethylene
（PE）, polyvinylpyrrolidone（PVP）, it is one or more in textile fabric.
Specifically, anode of the present invention can be selected from indium doping tin oxide（ITO）, fluorine-doped tin oxide（FTO）, Sb doped
Tin oxide（ATO）, aluminium-doped zinc oxide（AZO）It is one or more in.
Specifically, hole injection layer of the present invention can be but be not limited to poly- (3,4-rthylene dioxythiophene)-polyphenyl second
Alkene sulfonic acid（PEDOT:PSS）, CuPc（CuPc）, 2,3,5,6- tetra- fluoro- 7,7', 8,8'- tetra- cyanogen quinones-bismethane（F4-TCNQ）,
Six cyano -1,4,5,8,9,12- of 2,3,6,7,10,11-, six azepine benzophenanthrenes（HATCN）, doped or non-doped oxo transition metal
It is one or more in compound, doped or non-doped metal chalcogenide；Wherein, the transition metal oxide can be but
It is not limited to MoO3、VO2、WO3、CrO3, CuO or their mixture；The metal chalcogenide includes but not limited to
MoS2、MoSe2、WS2、WSe2, CuS or their mixture.
Specifically, hole transmission layer of the present invention can be selected from the organic material with cavity transmission ability, including but not
It is limited to poly- (9,9- dioctyl fluorenes-CO-N- (4- butyl phenyls) diphenylamines)（TFB）, polyvinylcarbazole（PVK）, it is poly- that (N, N' are bis-
Bis- (phenyl) benzidine of (4- butyl phenyls)-N, N'-)（poly-TPD）, it is poly- (double-N of 9,9- dioctyl fluorenes -co-s, phenyl -1 N-,
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- naphthalenes
Base）- 1,1 '-biphenyl -4,4 '-diamines（NPB）, doped graphene, undoped graphene, C60Or their mixture；
Specifically, hole transport layer material of the present invention is further selected from the inorganic material with cavity transmission ability, including
But it is not limited to doped or non-doped NiO, MoO3、VO2、WO3、CrO3、CuO、MoS2、MoSe2、WS2、WSe2, CuS or they
Mixture
Specifically, quantum dot of the present invention can be selected from doped or non-doped II-V compound semiconductors, iii-v chemical combination
It is one or more in object semiconductor, IV-VI compound semiconductors and its nucleocapsid.The optional auto-dope of quantum dot
Or it is one or more in undoped inorganic Ca-Ti ore type semiconductor, hybrid inorganic-organic Ca-Ti ore type semiconductor.Specifically
Ground, the inorganic Ca-Ti ore type semiconductor structure general formula are AMX3, wherein A is Cs+Ion；M is divalent metal, can
Think but is not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+In one kind；X is halogen
Plain anion can be but be not limited to Cl-、Br-、I-In one kind；The knot of the hybrid inorganic-organic Ca-Ti ore type semiconductor
Structure general formula 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-It is connected by way of total top, metal cation M
In the octahedral body-centered of halogen, organic amine cation B is filled in the gap between octahedron, forms the three-dimensional knot infinitely extended
Structure；As n > 2, the inorganic metal hal ide octahedron MX that is connected in a manner of total top6 4-Stratiform is extended to form in two-dimensional directional
Structure, Intercalation reaction organic amine cation bilayer（Protonate monoamine）Or organic amine cation monolayer（Protonation is double
Amine）, the organic layer two-dimensional layered structure stable with the mutually overlapping formation of inorganic layer；M is divalent metal, can be but not
It is limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+；X is halide anion, Ke Yiwei
But it is not limited to Cl-、Br-、I-。
Specifically, the material of electron transfer layer of the present invention is n-type metal oxide semiconductor, can be but be not limited to
Doped or non-doped ZnO, TiO2、WO3、NiO、MoO3、Fe2O3、SnO2、Ta2O3, one kind in AlZnO, ZnSnO, InSnO or
It is a variety of；Preferably, the electron transfer layer is ZnO, TiO2One or both of.
Specifically, QLED devices of the present invention with partial encapsulation, full encapsulation or can not encapsulate.
Specifically, the deposition 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
It is one or more；Physical include but not limited to spin-coating method, print process, knife coating, dip-coating method, infusion method, spray coating method,
Roll coating process, casting method, slit coating method, strip rubbing method, thermal evaporation coating method, electron beam evaporation deposition method, magnetron sputtering
It is 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 present invention is not limited to the QLED devices of above structure, can also further comprise interfactial work ergosphere or
Interface-modifying layer, including but not limited to electronic barrier layer, hole blocking layer, electrode modification layer, one kind in isolated protective layer or
It is a variety of.
It should be noted that QLED devices of the present invention, can be autologous QLED devices, can also be transoid knot
The QLED devices of structure.
A kind of illuminating module of the present invention, wherein including QLED devices as described above.
A kind of display device of the present invention, wherein including illuminating module as described above.
Below by embodiment, the present invention is described in detail.
Embodiment 1
A kind of light emitting diode with quantum dots of the cathode containing functionalization, preparation method are as follows：
One layer of PEDOT of spin coating on ITO substrates:PSS films are as hole injection layer；
In PEDOT:One layer of PVK of spin coating is as hole transmission layer on PSS hole injection layers；
One layer of CdSe/ZnS of spin coating is as quantum dot light emitting layer on PVK hole transmission layers；
Spin coating layer of ZnO is as electron transfer layer on CdSe/ZnS quantum dot light emitting layers；
Then, the mercaptopropyl trimethoxysilane of a concentration of 50 mM of 200 uL is taken（(CH3O)3SiC3H6SH）Toluene solution drop
It is added on above-mentioned ZnO electron transfer layers, with 5000 rpm, one layer of mercaptopropyl trimethoxysilane layer of spincoating conditions spin coating of 30s；
Finally, one layer of Ag is deposited on above-mentioned mercaptopropyl trimethoxysilane layer as cathode, obtains light emitting diode with quantum dots.
In the present embodiment, (CH used3O)3SiC3H6The structural schematic diagram of SH is shown in Fig. 2, the structural representation of functionalization cathode
Figure is shown in that Fig. 3, the structural schematic diagram of light emitting diode with quantum dots obtained are shown in Fig. 4, as shown in figure 4, two pole of the quantum dot light emitting
Pipe includes that substrate 1, anode 2, hole injection layer 3, hole transmission layer 4, quantum dot light emitting layer 5 and functionalization are cloudy successively from bottom to top
Pole 6, the functionalization cathode 6 specifically include electron transfer layer 61, hydrosulphonyl silane layer 62 and cathode 63.
Embodiment 2
A kind of light emitting diode with quantum dots of the cathode containing functionalization, preparation method are as follows：
One layer of PEDOT of spin coating on ITO substrates:PSS films are as hole injection layer；
In PEDOT:One layer of PVK of spin coating is as hole transmission layer on PSS hole injection layers；
One layer of CdSe/ZnS of spin coating is as quantum dot light emitting layer on PVK hole transmission layers；
Spin coating layer of ZnO is as electron transfer layer on CdSe/ZnS quantum dot light emitting layers；
Then, the mercaptopropyl trimethoxysilane of a concentration of 50 mM of 200 uL is taken（(CH3O)3SiC3H6SH）Toluene solution drop
It is added on above-mentioned ZnO electron transfer layers, with 5000 rpm, one layer of mercaptopropyl trimethoxysilane layer of spincoating conditions spin coating of 30s；
Then, one layer of Ag is deposited on above-mentioned mercaptopropyl trimethoxysilane layer as cathode；
Finally, the dimethyl sulfoxide (DMSO) of (11- mercapto-undecanoics base) trimethylammonium bromide of a concentration of 20 mM of 100 uL is taken（DMSO）
Solution is added dropwise on above-mentioned Ag cathode layers, with 5000 rpm, one layer of the spincoating conditions spin coating (11- mercapto-undecanoics base) three of 30s
Methyl bromide ammonium layer, is then dried up with nitrogen, obtains light emitting diode with quantum dots.
In the present embodiment, the structural schematic diagram of (11- mercapto-undecanoics base) trimethylammonium bromide used is shown in Fig. 5, function
The structural schematic diagram for changing cathode is shown in that Fig. 6, the structural schematic diagram of light emitting diode with quantum dots obtained are shown in Fig. 7, as shown in fig. 7, institute
It includes substrate 7, anode 8, hole injection layer 9, hole transmission layer 10, quantum dot successively to state light emitting diode with quantum dots from bottom to top
Luminescent layer 11 and functionalization cathode 12, the functionalization cathode 12 specifically include electron transfer layer 121, hydrosulphonyl silane layer 122, the moon
The alkyl ammonium halide 124 of pole 123 and band-SH.
Embodiment 3
A kind of light emitting diode with quantum dots of the cathode containing functionalization, preparation method are as follows：
One layer of PEDOT of spin coating on ITO substrates:PSS films are as hole injection layer；
In PEDOT:One layer of TFB of spin coating is as hole transmission layer on PSS hole injection layers；
One layer of CdSe/ZnS of spin coating is as quantum dot light emitting layer on TFB hole transmission layers；
Spin coating layer of ZnO is as electron transfer layer on CdSe/ZnS quantum dot light emitting layers；
Then, the mercaptopropyltriethoxysilane of a concentration of 60 mM of 200 uL is taken（(C2H5O)3SiC3H6SH）Toluene solution drop
It is added on above-mentioned ZnO electron transfer layers, with 5000 rpm, one layer of mercaptopropyltriethoxysilane layer of spincoating conditions spin coating of 30s；
Then, one layer of Ag is deposited on above-mentioned mercaptopropyltriethoxysilane layer as cathode；
Finally, the dimethyl sulfoxide (DMSO) of (11- mercapto-undecanoics base) trimethylammonium bromide of a concentration of 30 mM of 100 uL is taken（DMSO）
Solution is added dropwise on above-mentioned Ag cathode layers, with 5000 rpm, one layer of the spincoating conditions spin coating (11- mercapto-undecanoics base) three of 30s
Methyl bromide ammonium layer, is then dried up with nitrogen, obtains light emitting diode with quantum dots.
In conclusion a kind of functionalization cathode, QLED and preparation method provided by the invention, illuminating module are filled with display
It sets.The present invention is in metal oxide electron transport layer and metal electrode（Cathode）Between modify one layer of hydrosulphonyl silane, wherein sulfydryl
Silica bond energy in silane is connect with electron transfer layers such as ZnO, and is passivated the surface defect of ZnO, and is exposed to the mercapto of the other end
Base can closely be connect with metal electrodes such as Ag with S-Ag covalent bonds, and metal on the one hand can be used as in metal electrode deposition process
Close nuclearing centre, be grown into out uniformly regular metal electrode, on the other hand can promote electron transfer layer and gold
Belong to the close connection between electrode, keep interface stability and interfacial property, prevents metal electrode permeating, is rotten in electronic shell
It loses, aoxidize or falls off, effectively improve service life and the stability of electron injection efficiency and QLED devices.Further, this hair
It is bright in metal dispatch from foreign news agency pole surface（That is cathode surface）It is surface modified processing with the alkyl ammonium halide with sulfydryl, makes metal electrode
Surface generates interface dipole, so that the cathode of high work function is changed into the cathode of low work function, makes electrode and electron-transport
Meet Ohmic contact between layer, reduces electron injection and transmission potential barrier, improve the luminous efficiency and luminescent lifetime of QLED devices.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect range.
Claims (12)
1. a kind of preparation method for the functionalization cathode including electron transfer layer, which is characterized in that including step：
Deposit one layer of hydrosulphonyl silane on the electron transport layer first；
Then one layer of cathode is deposited on hydrosulphonyl silane layer, obtains functionalization cathode.
2. the preparation method of the functionalization cathode according to claim 1 for including electron transfer layer, which is characterized in that also
Including step：The alkyl ammonium halide of one layer of band-SH is deposited on cathode.
3. the preparation method of the functionalization cathode according to claim 1 for including electron transfer layer, which is characterized in that institute
The material for stating electron transfer layer is ZnO, TiO2、WO3、NiO、MoO3、Fe2O3、SnO2、Ta2O3, in AlZnO, ZnSnO, InSnO
It is one or more.
4. the preparation method of the functionalization cathode according to claim 1 for including electron transfer layer, which is characterized in that institute
The general formula for stating hydrosulphonyl silane is X3Si (CH2)nSH, X is chloro, methoxyl group, ethyoxyl, methoxy ethoxy, acetyl oxygen in formula
One or more in base, the value of n is 0 ~ 3.
5. the preparation method of the functionalization cathode according to claim 4 for including electron transfer layer, which is characterized in that institute
It is (CH to state hydrosulphonyl silane3O)3SiC3H6SH、(C2H5O)3SiC3H6One or both of SH.
6. the preparation method of the functionalization cathode according to claim 1 for including electron transfer layer, which is characterized in that institute
The material for stating cathode is one or more in Al, Ag, Cu, Mo, Au, and the form of the cathode is dense film, nano wire, receives
It is one or more in rice ball, nanometer rods, nanocone, nano-hollow ball.
7. the preparation method of the functionalization cathode according to claim 2 for including electron transfer layer, which is characterized in that institute
The general formula for stating the alkyl ammonium halide of band-SH is HS- (CH2)m(CH3)3NY, Y is halide ion, and/or acid ion, institute in formula
It is F to state halide ion-、Cl-、Br-、I-In it is one or more, the acid ion be HSO4 -、COO-One or both of,
The value of m is 0 ~ 16.
8. a kind of includes the functionalization cathode of electron transfer layer, which is characterized in that using as described in any one of claim 1 ~ 7
Include that the preparation method of functionalization cathode of electron transfer layer is prepared.
9. a kind of preparation method of QLED devices, which is characterized in that including：
Step A, deposition anode on substrate；
Step B, the deposition of hole implanted layer on anode；
Step C, the deposition of hole transport layer on hole injection layer；
Step D, quantum dot light emitting layer is deposited on the hole transport layer；
Step E, on quantum dot light emitting layer, deposition includes the functionalization cathode of electron transfer layer as claimed in claim 8,
Obtain QLED devices.
10. a kind of QLED devices, which is characterized in that using the preparation method preparation of QLED devices as claimed in claim 9
At the QLED devices include successively：Substrate, anode, hole injection layer, hole transmission layer, quantum dot light emitting layer, such as right are wanted
Ask described in 8 include electron transfer layer functionalization cathode.
11. a kind of illuminating module, which is characterized in that including QLED devices as claimed in claim 10.
12. a kind of display device, which is characterized in that including illuminating module as claimed in claim 11.
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