CN108807720B - Functionalized cathode, QLED, preparation method, light-emitting module and display device - Google Patents
Functionalized cathode, QLED, preparation method, light-emitting module and display device Download PDFInfo
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Abstract
The invention discloses a functionalized cathode, a QLED, a preparation method, a light-emitting module and a display device, wherein the method comprises the following steps: firstly, depositing a layer of mercaptosilane on an electron transport layer; and then, evaporating and plating a layer of cathode on the mercaptosilane layer to obtain the functionalized cathode. According to the invention, a layer of mercaptosilane is modified between the electron transport layer and the metal electrode, a silicon-oxygen bond in the mercaptosilane can be connected with the electron transport layer and passivates the surface defect of the electron transport layer, and a mercapto group exposed at the other end can be tightly connected with the metal electrode through a covalent bond, so that on one hand, the mercaptosilane can be used as a tight nucleation center of metal in the deposition process of the metal electrode to gradually grow a uniform and regular metal electrode, on the other hand, the tight connection between the electron transport layer and the metal electrode can be promoted, the interface stability and the interface property are maintained, the metal electrode is prevented from permeating, corroding, oxidizing or falling off in the electron layer, and the electron injection efficiency and the service life and stability of a QLED device are effectively.
Description
Technical Field
The invention relates to the technical field of light emitting diodes, in particular to a functional cathode comprising an electron transport layer, a QLED device, a preparation method of the QLED device, a light emitting module and a display device.
Background
In recent years, colloidal Quantum Dots (QDs) with a nanocrystal size have attracted much attention as a novel high-efficiency light-emitting material, which has various unique optical characteristics, such as easily tunable forbidden band width, wide light absorption spectrum range, high spectral purity, stable optical/chemical properties, and the like. A light emitting diode (QLED) using a Quantum dot material as a light emitting layer is called a Quantum dot light-emitting diode (QLED), and is a novel light emitting display technology. In the field of LED display, compared with the currently researched Organic light-emitting diodes (OLEDs), the QLEDs show greater superiority, such as higher electro-optical conversion efficiency, longer lifetime, low production cost, low energy consumption, high color purity, and the like, and show great potential in the next generation display technology.
At present, most of QLED devices in mainstream research use ZnO and TiO2The metal oxide semiconductor material with the same wide band gap is used as an electron transport layer,and depositing Ag, Al and other metals on the electron transport layer by thermal evaporation and other processes to be used as a cathode of the QLED device. In order to improve the electron injection efficiency and the light emitting efficiency, the cathode is generally made of a material with the lowest possible work function or a metal cathode or an alloy electrode is formed by evaporating a low work function metal with active properties and a high work function metal with stable chemical properties, such as Mg: Ag (10: 1), Li: Al (0.6% Li) and the like. However, this method is costly and relatively complicated. In addition, the interface between the electron transport layer and the metal electrode has a great influence on the performance and stability of the QLED device, such as the close contact between the ZnO layer and the Al electrode layer, and the defect state of the ZnO surface, which all seriously affect the electron injection efficiency. Meanwhile, metal atoms in the metal electrode easily permeate into ZnO, the permeation is aggravated in the operation process of the QLED device, the metal electrode is easy to fall off, the interface property between the electron transmission layer and the electrode is easy to damage, and the stability and the light-emitting service life of the device are greatly influenced.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, an object of the present invention is to provide a functionalized cathode including an electron transport layer, a QLED device, a method for manufacturing the same, a light emitting module and a display device, which are intended to solve the problem that the interface between the electron transport layer and the cathode greatly affects the performance and stability of the QLED device.
The technical scheme of the invention is as follows:
a method for preparing a functionalized cathode containing an electron transport layer comprises the following steps:
firstly, depositing a layer of mercaptosilane on an electron transport layer;
and then, evaporating and plating a layer of cathode on the mercaptosilane layer to obtain the functionalized cathode.
The preparation method of the functionalized cathode containing the electron transport layer comprises the following steps: depositing a layer of alkyl ammonium halide with-SH on the cathode.
The function containing an electron transport layerThe preparation method of the chemical cathode comprises the steps of preparing the electron transport layer from ZnO and TiO2、WO3、NiO、MoO3、Fe2O3、SnO2、Ta2O3One or more of AlZnO, ZnSnO and InSnO.
The preparation method of the functionalized cathode containing the electron transport layer is characterized in that the general formula of the mercaptosilane is X3Si (CH2)nSH, wherein X is one or more of chloro, methoxy, ethoxy, methoxyethoxy and acetoxyl, and n takes the value of 0 ~ 3.
The preparation method of the functionalized cathode containing the electron transport layer comprises the step of preparing the electron transport layer, wherein the mercaptosilane is (CH)3O)3SiC3H6SH、(C2H5O)3SiC3H6One or two of SH.
The preparation method of the functionalized cathode containing the electron transport layer comprises the following steps of preparing the cathode from one or more of Al, Ag, Cu, Mo and Au, and preparing the cathode from one or more of compact thin films, nanowires, nanospheres, nanorods, nanocones and hollow nanospheres.
The preparation method of the functionalized cathode containing the electron transport layer is characterized in that the general formula of the alkylammonium halide with-SH is HS- (CH)2)m(CH3)3NY, wherein Y is halogen ion and/or acid radical ion, and the halogen ion is F-、Cl-、Br-、I-The acid radical ion is HSO4 -、COO-And m is 0 ~ 16.
A functionalized cathode containing an electron transport layer is prepared by the preparation method of the functionalized cathode containing the electron transport layer.
A preparation method of a QLED device comprises the following steps:
step A, depositing an anode on a substrate;
step B, depositing a hole injection layer on the anode;
step C, depositing a hole transport layer on the hole injection layer;
d, depositing a quantum dot light-emitting layer on the hole transport layer;
and E, depositing the functional cathode containing the electron transmission layer on the quantum dot light-emitting layer to obtain the QLED device.
The QLED device is prepared by the preparation method of the QLED device, and sequentially comprises the following steps: the organic electroluminescent device comprises a substrate, an anode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer and the functionalized cathode containing the electron transport layer.
A light emitting module comprising a QLED device as described above.
A display device comprises the light-emitting module.
Has the advantages that: according to the invention, a layer of mercaptosilane is modified between a metal oxide electron transport layer and a metal electrode (cathode), wherein a silicon-oxygen bond in the mercaptosilane can be connected with the electron transport layer and passivates the surface defect of the electron transport layer, and a mercapto group exposed at the other end can be tightly connected with the metal electrode through a covalent bond, so that on one hand, the mercaptosilane can be used as a tight nucleation center of metal in the deposition process of the metal electrode to gradually grow a uniform and regular metal electrode, on the other hand, the tight connection between the electron transport layer and the metal electrode can be promoted, the interface stability and the interface property are maintained, the metal electrode is prevented from permeating, corroding, oxidizing or falling off in the electron layer, and the electron injection efficiency and the service life and stability of a QLED device are effectively improved.
Drawings
Fig. 1 is a flowchart of a method for manufacturing a QLED device according to a preferred embodiment of the present invention.
FIG. 2 shows (CH) used in example 1 of the present invention3O)3SiC3H6Schematic structure of SH.
Fig. 3 is a schematic structural diagram of a functionalized cathode in embodiment 1 of the invention.
Fig. 4 is a schematic structural diagram of a quantum dot light-emitting diode manufactured in embodiment 1 of the present invention.
FIG. 5 is a schematic structural view of (11-mercaptoundecyl) trimethylammonium bromide used in example 2 of the present invention.
Fig. 6 is a schematic structural diagram of a functionalized cathode in example 2 of the present invention.
Fig. 7 is a schematic structural diagram of a quantum dot light-emitting diode manufactured in embodiment 2 of the present invention.
Detailed Description
The invention provides a functional cathode comprising an electron transport layer, a QLED device, a preparation method, a light-emitting module and a display device, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention discloses a better embodiment of a preparation method of a functionalized cathode containing an electron transport layer, which comprises the following steps:
firstly, depositing a mercaptosilane layer on an electron transport layer;
and then, evaporating and plating a layer of cathode on the mercaptosilane layer to obtain the functionalized cathode.
Specifically, the material of the electron transport layer of the present invention may be an n-type metal oxide semiconductor, for example, the material of the electron transport layer may be, but is not limited to, ZnO, TiO2、WO3、NiO、MoO3、Fe2O3、SnO2、Ta2O3One or more of AlZnO, ZnSnO, InSnO and the like. Preferably, the material of the electron transport layer can be ZnO or TiO2And the like.
Specifically, the deposition method of the mercaptosilane of the present invention may be a chemical method or a physical method, wherein the chemical method may be, but is not limited to, one or more of a chemical vapor deposition method, a continuous ion layer adsorption and reaction method, an anodic oxidation method, an electrolytic deposition method, and a coprecipitation method; the physical method may be, but is not limited to, one or more of spin coating, printing, knife coating, dip coating, dipping, spraying, roll coating, casting, slit coating, bar coating, thermal evaporation, electron beam evaporation, magnetron sputtering, multi-arc ion coating, physical vapor deposition, atomic layer deposition, and pulsed laser deposition. Preferably, the deposition method of the mercaptosilane is a spin coating method, a printing method or a dip-draw method.
Specifically, the mercaptosilane is an organic silicon compound with a mercapto group (-SH) at the molecular terminal, and the general formula of the mercaptosilane is X3Si(CH2)nSH, wherein X is one or more of chloro, methoxy, ethoxy, methoxyethoxy and acetoxy, and these groups generate silanol (Si (OH) when hydrolyzed3) And combined with inorganic matter to form siloxane, n is 0 ~ 3, and the mercapto silane is preferably mercaptopropyltrimethoxy silane (CH)3O)3SiC3H6SH, mercaptopropyltriethoxysilane (C)2H5O)3SiC3H6One or two of SH.
Specifically, the material of the cathode of the present invention may be, but is not limited to, one or more of Al, Ag, Cu, Mo, and Au, and may also be an alloy thereof. The cathode may be in the form of, but not limited to, one or more of a dense thin film, a nanowire, a nanosphere, a nanorod, a nanocone, and a hollow nanosphere. Preferably, the material of the cathode is one or two of Al and Ag.
According to the invention, a layer of mercaptosilane is modified between a metal oxide electron transmission layer and a metal electrode (cathode), wherein a silicon-oxygen bond in the mercaptosilane can be connected with an electron transmission layer such as ZnO and the like, and passivates the surface defect of ZnO, while a mercapto group exposed at the other end can be tightly connected with a metal electrode such as Ag and the like through an S-Ag covalent bond, so that on one hand, the mercaptosilane can be used as a tight nucleation center of metal in the deposition process of the metal electrode to gradually grow a uniform and regular metal electrode, on the other hand, the tight connection between the electron transmission layer and the metal electrode can be promoted, the interface stability and the interface property are maintained, the metal electrode is prevented from permeating, corroding, oxidizing or falling off in the electron layer, and the electron injection efficiency and the service life and stability of.
Specifically, the invention further provides another preferred embodiment of the preparation method of the functionalized cathode, which further comprises the following steps: depositing a layer of alkyl ammonium halide with-SH on the cathode. The alkyl ammonium halide with-SH is quaternary ammonium salt with mercapto (-SH) at the molecular terminal, and the general formula is HS- (CH)2)m(CH3)3NY, wherein Y can be but is not limited to halogen ion, and/or acid radical ion, and the halogen ion can be but is not limited to F-、Cl-、Br-、I-The acid radical ion can be, but is not limited to, HSO4 -、COO-M is 0 ~ 16. preferably, the halide ion is (11-mercapto undecyl) trimethyl ammonium bromide, (14-mercapto tetradecyl) dimethyl ethyl ammonium bromide.
The invention uses alkyl ammonium halide with sulfydryl on the surface of the metal outer electrode (namely the surface of the cathode) to carry out surface modification treatment, so that interface dipoles are generated on the surface of the metal electrode, thereby converting the cathode with high work function into the cathode with low work function, enabling the electrode and the electron transmission layer to meet ohmic contact, reducing electron injection and transmission potential barriers, and improving the luminous efficiency and the luminous life of the QLED device.
The functionalized cathode is prepared by the preparation method of any one of the functionalized cathodes. On one hand, the mercaptosilane is introduced into the interface between the metal oxide electron transport layer and the metal electrode, so that the connection tightness of the metal oxide electron transport layer and the metal electrode can be improved, the interface stability and the interface property are kept, and the metal electrode can be prevented from permeating, corroding, oxidizing or falling off in the electron transport layer, so that the electron injection efficiency and the service life and stability of a QLED device are effectively improved; on the other hand, the outer surface of the metal electrode is treated by alkyl ammonium halide with sulfydryl, so that a cathode with a high work function can be converted into a cathode with a low work function, ohmic contact between the electrode and the electron transport layer is met, electron injection and transport barriers are reduced, and the luminous efficiency and the luminous life of the QLED device are further improved.
Fig. 1 is a flowchart of a method for manufacturing a QLED device according to a preferred embodiment of the present invention, as shown in the figure, the method includes:
step S100, depositing an anode on a substrate;
step S200, depositing a hole injection layer on the anode;
step S300, depositing a hole transport layer on the hole injection layer;
step S400, depositing quantum dot light-emitting layers on the hole transport layer;
and S500, depositing the functionalized cathode containing the electron transport layer on the quantum dot light-emitting layer to obtain the QLED device.
The invention discloses a preferred embodiment of a QLED device, which is prepared by the preparation method of the QLED device, and the QLED device sequentially comprises the following components: the organic electroluminescent device comprises a substrate, an anode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer and the functionalized cathode containing the electron transport layer.
Specifically, in the QLED device of the present invention, a layer of mercaptosilane is included between the electron transport layer and the cathode, wherein a silicon-oxygen bond in the mercaptosilane can be connected to an electron transport layer such as ZnO, and passivates surface defects of ZnO, and a mercapto group exposed at the other end can be tightly connected to a metal electrode such as Ag by an S-Ag covalent bond, so that on one hand, the mercaptosilane can be used as a tight nucleation center of the metal during deposition of the metal electrode to gradually grow a uniform and regular metal electrode, on the other hand, the tight connection between the electron transport layer and the metal electrode can be promoted, so as to maintain interface stability and interface properties, prevent the metal electrode from permeating, corroding, oxidizing or falling off in the electron layer, and effectively improve electron injection efficiency and life and stability of the QLED device.
Furthermore, in the QLED device of the present invention, the surface of the cathode further includes a layer of alkylammonium halide with mercapto, and the surface of the metal external electrode is modified with alkylammonium halide with mercapto to generate an interface dipole on the surface of the metal electrode, so that the cathode with high work function is converted into a cathode with low work function, ohmic contact between the electrode and the electron transport layer is satisfied, the electron injection and transport barrier is reduced, and the light emitting efficiency and the light emitting life of the QLED device are improved. In particular, the present invention is applicable not only to conventional QLED devices but also to flexible QLED devices.
In particular, the substrate of the present invention may be a rigid substrate or a flexible substrate, wherein the rigid substrate may be, but is not limited to, one or more of glass, metal foil; the flexible substrate may be, but is not limited to, one or more of polyethylene terephthalate (PET), ethylene terephthalate (PEN), Polyetheretherketone (PEEK), Polystyrene (PS), Polyethersulfone (PES), Polycarbonate (PC), Polyarylate (PAT), Polyarylate (PAR), Polyimide (PI), polyvinyl chloride (PV), Polyethylene (PE), polyvinylpyrrolidone (PVP), textile fibers.
Specifically, the anode of the present invention may be selected from one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), and the like.
Specifically, the hole injection layer of the present invention may be, but is not limited to, one or more of poly (3, 4-ethylenedioxythiophene) -polystyrenesulfonic acid (PEDOT: PSS), copper phthalocyanine (CuPc), 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinodimethane (F4-TCNQ), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazatriphenylene (HATCN), doped or undoped transition metal oxides, doped or undoped metal chalcogenide compounds; wherein the transition metal oxide may be, but is not limited to, MoO3、VO2、WO3、CrO3CuO, or mixtures thereof; the metal chalcogenide compound includes but is not limited to MoS2、MoSe2、WS2、WSe2CuS, or a mixture thereof.
Specifically, the hole transport layer of the present invention may be selected from organic materials having hole transport ability, including, but not limited to, poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB), Polyvinylcarbazole (PVK)poly-TPD, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-co-bis-N, N-phenyl-1, 4-Phenylenediamine) (PFB), 4', 4' '-tris (carbazol-9-yl) triphenylamine (TCTA), 4' -bis (9-Carbazol) Biphenyl (CBP), N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), Doped graphene, undoped graphene, C60Or mixtures thereof;
specifically, the hole transport layer material of the present invention can also be selected from inorganic materials with hole transport capability, including but not limited to doped or undoped NiO, MoO3、VO2、WO3、CrO3、CuO、MoS2、MoSe2、WS2、WSe2CuS, or mixtures thereof
Specifically, the quantum dot of the present invention may be selected from one or more of a doped or undoped II-V group compound semiconductor, a III-V group compound semiconductor, an IV-VI group compound semiconductor, and a core-shell structure thereof. The quantum dots can be selected from one or more of doped or undoped inorganic perovskite type semiconductors and organic-inorganic hybrid perovskite type semiconductors. Specifically, the structural general formula of the inorganic perovskite type semiconductor is AMX3Wherein A is Cs+Ions; m is a divalent metal cation, and may be, but is not limited to, Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+One of (1); x is a halide anion, which may be but is not limited to Cl-、Br-、I-One of (1); the structural general formula of the organic-inorganic hybrid perovskite type semiconductor is BMX3Wherein B is an organic amine cation which may be, but is not limited to CH3(CH2)n-2NH3 +(n.gtoreq.2) or NH3(CH2)nNH3 2+(n.gtoreq.2). When n =2, the inorganic metal halide octahedron MX6 4-The metal cations M are positioned in the center of a halogen octahedron through connection in a roof sharing mode, and the organic amine cations B are filled in gaps among the octahedrons to form an infinitely extending three-dimensional structure; inorganic metal halide octahedra MX linked in a coterminous manner when n > 26 4-The organic amine cation bilayer (protonated monoamine) or the organic amine cation monolayer (protonated diamine) is inserted between the layers, and the organic layer and the inorganic layer are overlapped with each other to form a stable two-dimensional layered structure; m is a divalent metal cation, and may be, but is not limited to, Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+(ii) a X is a halide anion, which may be but is not limited to Cl-、Br-、I-。
Specifically, the material of the electron transport layer is an n-type metal oxide semiconductor, and can be, but is not limited to, doped or undoped ZnO and TiO2、WO3、NiO、MoO3、Fe2O3、SnO2、Ta2O3One or more of AlZnO, ZnSnO and InSnO; preferably, the electron transport layer is ZnO or TiO2One or two of them.
In particular, the QLED devices of the present invention may be partially packaged, fully packaged, or unpackaged.
Specifically, the deposition method of each layer of the present invention may be a chemical method or a physical method, wherein the chemical method includes, but is not limited to, one or more of a chemical vapor deposition method, a successive ionic layer adsorption and reaction method, an anodic oxidation method, an electrolytic deposition method, and a coprecipitation method; the physical method includes, but is not limited to, one or more of spin coating, printing, knife coating, dip coating, dipping, spraying, roll coating, casting, slit coating, bar coating, thermal evaporation, electron beam evaporation, magnetron sputtering, multi-arc ion coating, physical vapor deposition, atomic layer deposition, and pulsed laser deposition.
It should be noted that the invention is not limited to the QLED device with the above structure, and may further include an interface functional layer or an interface modification layer, including but not limited to one or more of an electron blocking layer, a hole blocking layer, an electrode modification layer, and an isolation protection layer.
The QLED device of the present invention may be a positive-type QLED device or an inverted-type QLED device.
The light emitting module of the invention comprises the QLED device.
The display device of the invention comprises the light-emitting module.
The present invention will be described in detail below with reference to examples.
Example 1
A quantum dot light-emitting diode containing a functionalized cathode is prepared by the following steps:
spin-coating a layer of PEDOT on the ITO substrate, wherein the PSS film is used as a hole injection layer;
spin-coating a layer of PVK on a PEDOT (PSS) hole injection layer to be used as a hole transmission layer;
a CdSe/ZnS layer is spin-coated on the PVK hole transport layer to be used as a quantum dot light-emitting layer;
a ZnO layer is spin-coated on the CdSe/ZnS quantum dot luminescent layer to be used as an electron transmission layer;
then, 200 uL of mercaptopropyltrimethoxysilane ((CH) was taken at a concentration of 50 mM3O)3SiC3H6SH) solution is dripped on the ZnO electron transport layer, and a mercaptopropyl trimethoxy silane layer is spin-coated under the spin-coating condition of 5000 rpm and 30 s;
and finally, evaporating and plating a layer of Ag on the mercaptopropyl trimethoxy silane layer to serve as a cathode, so as to obtain the quantum dot light-emitting diode.
In this example, (CH)3O)3SiC3H6The structural schematic diagram of SH is shown in figure 2, the structural schematic diagram of a functionalized cathode is shown in figure 3, the structural schematic diagram of the prepared quantum dot light-emitting diode is shown in figure 4, and the structural schematic diagram of the quantum dot light-emitting diode is shown in figure 4The light-emitting diode sequentially comprises a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a quantum dot light-emitting layer 5 and a functionalized cathode 6 from bottom to top, wherein the functionalized cathode 6 specifically comprises an electron transport layer 61, a mercaptosilane layer 62 and a cathode 63.
Example 2
A quantum dot light-emitting diode containing a functionalized cathode is prepared by the following steps:
spin-coating a layer of PEDOT on the ITO substrate, wherein the PSS film is used as a hole injection layer;
spin-coating a layer of PVK on a PEDOT (PSS) hole injection layer to be used as a hole transmission layer;
a CdSe/ZnS layer is spin-coated on the PVK hole transport layer to be used as a quantum dot light-emitting layer;
a ZnO layer is spin-coated on the CdSe/ZnS quantum dot luminescent layer to be used as an electron transmission layer;
then, 200 uL of mercaptopropyltrimethoxysilane ((CH) was taken at a concentration of 50 mM3O)3SiC3H6SH) solution is dripped on the ZnO electron transport layer, and a mercaptopropyl trimethoxy silane layer is spin-coated under the spin-coating condition of 5000 rpm and 30 s;
then, a layer of Ag is evaporated on the mercaptopropyl trimethoxy silane layer to be used as a cathode;
and finally, dripping 100 uL (11-mercapto-undecyl) trimethyl ammonium bromide dimethyl sulfoxide (DMSO) solution with the concentration of 20 mM on the Ag cathode layer, spin-coating a layer of (11-mercapto-undecyl) trimethyl ammonium bromide layer under the spin-coating condition of 5000 rpm for 30s, and then drying by using nitrogen to obtain the quantum dot light-emitting diode.
In this embodiment, a structural schematic diagram of (11-mercaptoundecyl) trimethylammonium bromide used in the present embodiment is shown in fig. 5, a structural schematic diagram of a functionalized cathode is shown in fig. 6, and a structural schematic diagram of a prepared quantum dot light emitting diode is shown in fig. 7, where the quantum dot light emitting diode includes, from bottom to top, a substrate 7, an anode 8, a hole injection layer 9, a hole transport layer 10, a quantum dot light emitting layer 11, and a functionalized cathode 12, and the functionalized cathode 12 specifically includes an electron transport layer 121, a mercaptosilane layer 122, a cathode 123, and an alkylammonium halide 124 with-SH.
Example 3
A quantum dot light-emitting diode containing a functionalized cathode is prepared by the following steps:
spin-coating a layer of PEDOT on the ITO substrate, wherein the PSS film is used as a hole injection layer;
spin-coating a TFB layer on a PEDOT/PSS hole injection layer to serve as a hole transport layer;
a layer of CdSe/ZnS is spin-coated on the TFB hole transport layer to be used as a quantum dot light emitting layer;
a ZnO layer is spin-coated on the CdSe/ZnS quantum dot luminescent layer to be used as an electron transmission layer;
then, 200 uL of 60 mM mercaptopropyltriethoxysilane ((C)2H5O)3SiC3H6SH) solution is dripped on the ZnO electron transport layer, and a mercaptopropyl triethoxysilane layer is spin-coated under the spin-coating condition of 5000 rpm and 30 s;
then, a layer of Ag is evaporated on the mercaptopropyltriethoxysilane layer to be used as a cathode;
and finally, dripping 100 uL (11-mercapto undecyl) trimethyl ammonium bromide dimethyl sulfoxide (DMSO) solution with the concentration of 30 mM on the Ag cathode layer, spin-coating a layer of (11-mercapto undecyl) trimethyl ammonium bromide layer at 5000 rpm for 30s, and then drying by using nitrogen to obtain the quantum dot light-emitting diode.
In summary, the invention provides a functionalized cathode, a QLED, a manufacturing method thereof, a light emitting module and a display device. According to the invention, a layer of mercaptosilane is modified between a metal oxide electron transmission layer and a metal electrode (cathode), wherein a silicon-oxygen bond in the mercaptosilane can be connected with an electron transmission layer such as ZnO and the like, and passivates the surface defect of ZnO, while a mercapto group exposed at the other end can be tightly connected with a metal electrode such as Ag and the like through an S-Ag covalent bond, so that on one hand, the mercaptosilane can be used as a tight nucleation center of metal in the deposition process of the metal electrode to gradually grow a uniform and regular metal electrode, on the other hand, the tight connection between the electron transmission layer and the metal electrode can be promoted, the interface stability and the interface property are maintained, the metal electrode is prevented from permeating, corroding, oxidizing or falling off in the electron layer, and the electron injection efficiency and the service life and stability of. Furthermore, the surface of the metal outer electrode (namely the surface of the cathode) is modified by alkyl ammonium halide with sulfydryl, so that interface dipoles are generated on the surface of the metal electrode, the cathode with high work function is converted into the cathode with low work function, ohmic contact is met between the electrode and the electron transmission layer, the electron injection and transmission potential barrier is reduced, and the luminous efficiency and the luminous life of the QLED device are improved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (12)
1. A method for preparing a functionalized cathode containing an electron transport layer is characterized by comprising the following steps: firstly, depositing a layer of mercaptosilane with a silicon-oxygen bond on a metal oxide electron transport layer;
and then, evaporating and plating a layer of metal cathode on the mercaptosilane layer to obtain the functionalized cathode.
2. The method of claim 1, further comprising the steps of: depositing a layer of alkyl ammonium halide with-SH on the cathode.
3. The method for preparing the functionalized cathode containing the electron transport layer according to claim 1, wherein the electron transport layer is made of ZnO or TiO2、WO3、NiO、MoO3、Fe2O3、SnO2、Ta2O3One or more of AlZnO, ZnSnO and InSnO.
4. The method of claim 1, wherein the mercapto silicon is selected from the group consisting of silicon, aluminum, silicon nitrideThe alkane has the formula X3Si(CH2)nSH, wherein X in the formula is one or more of methoxyl, ethoxyl, methoxyethoxy and acetoxyl, and n takes the value of 0-3.
5. The method of claim 4, wherein the mercaptosilane is (CH)3O)3SiC3H6SH、(C2H5O)3SiC3H6One or two of SH.
6. The method for preparing the functionalized cathode containing the electron transport layer according to claim 1, wherein the cathode is made of one or more of Al, Ag, Cu, Mo and Au, and the cathode is in the form of one or more of dense thin film, nanowire, nanosphere, nanorod and nanocone.
7. The method of claim 2, wherein the alkyl ammonium halide with-SH has a formula of HS- (CH)2)m(CH3)3NY, wherein Y is halogen ion and/or acid radical ion, and the halogen ion is F-、Cl-、Br-、I-The acid radical ion is HSO4 -、COO-One or two of the above, wherein the value of m is 0-16.
8. A functionalized cathode comprising an electron transport layer, which is prepared by the method for preparing the functionalized cathode comprising the electron transport layer according to any one of claims 1 to 7.
9. A preparation method of a QLED device is characterized by comprising the following steps:
step A, depositing an anode on a substrate;
step B, depositing a hole injection layer on the anode;
step C, depositing a hole transport layer on the hole injection layer;
d, depositing a quantum dot light-emitting layer on the hole transport layer;
and E, depositing the functionalized cathode containing the electron transport layer according to claim 8 on the quantum dot light-emitting layer to obtain the QLED device.
10. A QLED device prepared by the method of claim 9, comprising in order: a substrate, an anode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, a functionalized cathode comprising an electron transport layer according to claim 8.
11. A lighting module comprising the QLED device of claim 10.
12. A display device comprising the light-emitting module according to claim 11.
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| CN112018250B (en) | 2019-05-31 | 2021-12-17 | 京东方科技集团股份有限公司 | Quantum dot electroluminescent device, manufacturing method thereof and display device |
| CN112289960B (en) * | 2019-07-25 | 2022-08-23 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode and preparation method thereof |
| CN110635057B (en) | 2019-09-26 | 2022-05-03 | 京东方科技集团股份有限公司 | Quantum dot device backboard, manufacturing method thereof and quantum dot device |
| CN112582564B (en) * | 2019-09-27 | 2022-04-08 | Tcl科技集团股份有限公司 | Light emitting device and method of manufacturing the same |
| CN112582565B (en) * | 2019-09-27 | 2022-04-12 | Tcl科技集团股份有限公司 | Light emitting device and method of manufacturing the same |
| CN113054120B (en) * | 2019-12-28 | 2022-05-31 | Tcl科技集团股份有限公司 | Electron blocking film, quantum dot light emitting diode and preparation method thereof |
| CN113972334A (en) * | 2020-07-22 | 2022-01-25 | Tcl科技集团股份有限公司 | Quantum dot light-emitting diode with positive structure and preparation method thereof |
| CN112186118B (en) * | 2020-09-30 | 2023-06-16 | 京东方科技集团股份有限公司 | Quantum dot light emitting device, manufacturing method thereof and display device |
| CN114039000A (en) * | 2020-10-30 | 2022-02-11 | 广东聚华印刷显示技术有限公司 | Electrode, light emitting device, and electronic apparatus |
| CN112750956B (en) * | 2020-12-31 | 2023-05-30 | 义乌清越光电科技有限公司 | Quantum dot light emitting diode, preparation method thereof, display panel and display device |
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