CN117998886A - Light-emitting device, preparation method thereof and display device - Google Patents
Light-emitting device, preparation method thereof and display device Download PDFInfo
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- CN117998886A CN117998886A CN202211385500.2A CN202211385500A CN117998886A CN 117998886 A CN117998886 A CN 117998886A CN 202211385500 A CN202211385500 A CN 202211385500A CN 117998886 A CN117998886 A CN 117998886A
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- Electroluminescent Light Sources (AREA)
Abstract
The application discloses a light emitting device, a preparation method thereof and a display device. According to the preparation method of the light-emitting device, the first substance is arranged on the surface of the cathode, which is far away from the electron transport layer, and the prefabricated device is electrified to form at least one silver channel in the electron transport layer, and electrons in the cathode can be transferred into the light-emitting layer through the silver channel, so that the electron injection efficiency can be effectively improved, and the performances of the light-emitting device, such as the service life, the light-emitting efficiency and the like, are improved.
Description
Technical Field
The application relates to the technical field of display, in particular to a light-emitting device, a preparation method thereof and a display device.
Background
QLED (quantum dot light emitting diode) is a display device currently being widely studied, and its structure generally includes a stacked structure composed of a hole transport layer, a light emitting layer, and an electron transport layer. The QLED light-emitting device has the advantages of excellent light-emitting performance, long service life, simple packaging process and the like, and has wide development prospect.
However, the current QLED device still has the problems of insufficient electron injection caused by larger potential barrier at the interface between the light emitting layer and the electron transport layer, and the oxide nanocrystalline material such as zinc oxide in the electron transport layer has higher work function contact with the quantum dots, so that interfacial charge transport can occur at the interface between the electron transport layer and the light emitting layer, quenching of the quantum dots can also be caused, unbalance of electron and hole injection is caused, and further, the performances such as the light emitting efficiency and the service life of the QLED are reduced.
Disclosure of Invention
In view of the above, the present application provides a light emitting device, a method of manufacturing the same, and a display apparatus, which aim to improve the device performance of the light emitting device.
The embodiment of the application is realized in such a way that a preparation method of a light-emitting device is provided, comprising the following steps: providing a prefabricated device, wherein the prefabricated device comprises an anode, a light-emitting layer, a first electron transport layer and a cathode; disposing a first substance on a surface of the cathode on a side remote from the first electron transport layer, wherein the first substance comprises silver; energizing the preformed device to form at least one silver channel in the first electron transport layer, forming a light emitting device comprising a second electron transport layer; wherein in the second electron transport layer, the silver channel extends from the cathode to the light emitting layer.
Optionally, in some embodiments of the present application, the material of the first electron transport layer is an electron transport material, and the material of the silver channel includes a mixture of silver and the electron transport material; and/or the cathode is a silver electrode; and/or the thickness of the cathode is 80-120nm; and/or the thickness of the electron transport layer is 20-40nm; and/or the ratio of the mass of the first substance to the area of the cathode is 75 to 500 μg/cm 2.
Optionally, in some embodiments of the application, the first substance is selected from at least one of silver tetrafluoroborate, silver pentafluoropropionate, silver heptafluorobutyrate, silver hexafluorophosphate, and silver acrylate; and/or the mass ratio of the silver in the second electron transport layer is 1.5-4%.
Optionally, in some embodiments of the present application, the disposing a first substance on a surface of the cathode on a side away from the electron transport layer includes: and (3) arranging a first substance solution on the surface of the side, away from the electron transport layer, of the cathode through a solution method, and then drying.
Optionally, in some embodiments of the present application, the solvent of the first substance solution is selected from at least one of diethyl ether, benzene, toluene, nitromethane; and/or the concentration of the first substance in the first substance solution ranges from 5 to 20mg/mL; and/or the drying temperature is 60-100 ℃ and the drying time is 10-30min; and/or before said drying, further comprising: standing for 30-240s.
Optionally, in some embodiments of the present application, before the energizing the prefabricated device, the method further includes: packaging the prefabricated device; and/or the energizing voltage is 5-12V.
Alternatively, in some embodiments of the present application, the material of the electron transport layer is selected from inorganic nanocrystalline materials or doped inorganic nanocrystalline materials; the inorganic nanocrystalline material is selected from one or more of zinc oxide, titanium dioxide, tin dioxide, aluminum oxide, calcium oxide, silicon dioxide, gallium oxide, zirconium oxide, nickel oxide and zirconium oxide; the doped inorganic nanocrystalline material comprises the inorganic nanocrystalline material and doping elements, wherein the doping elements are at least one selected from Mg, ca, li, ga, al, co, mn; and/or the material of the light emitting layer is selected from a quantum dot material, the quantum dot material is selected from at least one of single-structure quantum dots, core-shell structure quantum dots, doped or undoped inorganic perovskite type quantum dots, or organic-inorganic hybrid perovskite type quantum dots, the single-structure quantum dots are selected from at least one of group II-VI compounds, group III-V compounds, group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds and group IV simple substances, the group II-VI compounds are selected from at least one of CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、 ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe and CdZnSTe, the group III-V compounds are selected from at least one of InP, inAs, gaP, gaAs, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP, and the group I-III-VI compounds are selected from at least one of CuInS 2、CuInSe2 and AgInS 2; the core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS; the structural general formula of the inorganic perovskite type quantum dot is AMX 3, wherein A is Cs + ion, M is divalent metal cation, at least one of Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、 Cr2+、Mn2+、Co2+、Fe2+、Ge2 +、Yb2+、Eu2+ and X is halogen anion, at least one of Cl -、Br-、I-; the organic-inorganic hybrid perovskite quantum dot has a structural general formula of BMX 3, wherein B is an organic amine cation selected from CH 3(CH2)n-2NH3+ or NH 3(CH2)nNH3 2+, wherein n is more than or equal to 2, M is a divalent metal cation selected from at least one of Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、 Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+, X is a halogen anion selected from at least one of Cl -、Br-、I-; and/or the anode is selected from one or more of a metal electrode, a carbon electrode, a doped or undoped metal oxide electrode and a composite electrode; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the composite electrode is at least one selected from AZO/Ag/AZO、AZO/Al/AZO、 ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、 TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2 and TiO 2/Al/TiO2; and/or the prefabricated device further comprises a hole functional layer, wherein the hole functional layer is arranged between the anode and the light-emitting layer, and comprises a hole injection layer and/or a hole transport layer; when the hole functional layer comprises two layers of the hole injection layer and the hole transport layer, the hole injection layer is arranged close to one side of the anode, and the hole transport layer is arranged close to one side of the light-emitting layer; the material of the hole transport layer is selected from one or more of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4',4 "-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), spiro-NPB, spiro-TPD, doped or undoped NiO, moO 3、WO3、V2O5, P-type gallium nitride, crO 3、 CuO、MoS2、MoSe2、WS3、WSe3, cuS, cun; and/or the material of the hole injection layer is selected from one or more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, copper phthalocyanine, transition metal oxide and transition metal chalcogenide; wherein the transition metal oxide comprises one or more of NiO, moO 2、WO3 and CuO; the metal chalcogenide comprises one or more of MoS 2、MoSe2、WS3、WSe3 and CuS.
Correspondingly, the embodiment of the application also provides a light-emitting device, which comprises a laminated anode, a light-emitting layer, an electron transport layer and a cathode, wherein the electron transport layer comprises at least one silver channel, and the silver channel extends from the cathode to the light-emitting layer.
Optionally, in some embodiments of the present application, the material of the electron transport layer is an electron transport material, and the material of the silver channel is a mixture of silver and the electron transport material; and/or one or more of the silver channels of the at least one silver channel communicates the cathode with the light emitting layer; and/or the contact area between each silver channel and the cathode is 1-9 nm 2; and/or the mass ratio of the silver in the electron transport layer is 1.5-4%.
Optionally, in some embodiments of the application, the cathode is a silver electrode; and/or the thickness of the cathode is 80-120nm; and/or the material of the electron transport layer is selected from inorganic nanocrystalline materials or doped inorganic nanocrystalline materials; the inorganic nanocrystalline material is selected from one or more of zinc oxide, titanium dioxide, tin dioxide, aluminum oxide, calcium oxide, silicon dioxide, gallium oxide, zirconium oxide, nickel oxide and zirconium oxide; the doped inorganic nanocrystalline material comprises the inorganic nanocrystalline material and doping elements, wherein the doping elements are at least one selected from Mg, ca, li, ga, al, co, mn; and/or the thickness of the electron transport layer is 20-40nm; and/or the material of the light emitting layer is selected from a quantum dot material, the quantum dot material is selected from at least one of single-structure quantum dots, core-shell structure quantum dots, doped or undoped inorganic perovskite type quantum dots, or organic-inorganic hybrid perovskite type quantum dots, the single-structure quantum dots are selected from at least one of group II-VI compounds, group III-V compounds, group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds and group IV simple substances, the group II-VI compounds are selected from at least one of CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、 CdZnSeTe and CdZnSTe, the group III-V compounds are selected from at least one of InP, inAs, gaP, gaAs, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP, and the group I-III-VI compounds are selected from at least one of CuInS 2、CuInSe2 and AgInS 2; the core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS; the structural general formula of the inorganic perovskite type quantum dot is AMX 3, wherein A is Cs + ion, M is divalent metal cation, at least one of Pb2+、Sn2+、 Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+ and X is halogen anion, at least one of Cl -、Br-、I-; the organic-inorganic hybrid perovskite quantum dot has a structural general formula of BMX 3, wherein B is an organic amine cation selected from CH 3(CH2)n-2NH3+ or NH 3(CH2)nNH3 2+, wherein n is more than or equal to 2, M is a divalent metal cation selected from at least one of Pb2+、Sn2+、Cu2+、 Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+, X is a halogen anion selected from at least one of Cl -、Br-、I-; and/or the anode is selected from one or more of a metal electrode, a carbon electrode, a doped or undoped metal oxide electrode and a composite electrode; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the composite electrode is at least one selected from AZO/Ag/AZO、 AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、 TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2 and TiO 2/Al/TiO2; and/or the light emitting device further comprises a hole function layer; the hole functional layer comprises a hole injection layer and/or a hole transport layer; when the hole functional layer comprises two layers of the hole injection layer and the hole transport layer, the hole injection layer is arranged close to one side of the anode, and the hole transport layer is arranged close to one side of the light-emitting layer; the material of the hole transport layer is selected from one or more of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4',4 "-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), spiro-NPB, spiro-TPD, doped or undoped NiO, moO 3、WO3、V2O5, P-type gallium nitride, crO 3、CuO、MoS2、MoSe2、WS3、WSe3, cuS, cun; and/or the material of the hole injection layer is selected from one or more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, copper phthalocyanine, transition metal oxide and transition metal chalcogenide; wherein the transition metal oxide comprises one or more of NiO, moO 2、WO3 and CuO; the metal chalcogenide comprises one or more of MoS 2、MoSe2、WS3、WSe3 and CuS.
Correspondingly, the embodiment of the application also provides a display device, which comprises the light-emitting device prepared by the preparation method of the light-emitting device; or the display device comprises the light emitting device described above.
According to the preparation method of the light-emitting device, the first substance is arranged on the surface of the cathode, which is far away from the electron transport layer, and the prefabricated device is electrified to form at least one silver channel in the electron transport layer, and electrons in the cathode can be transferred into the light-emitting layer through the silver channel, so that the electron injection efficiency can be effectively improved. The silver channel in the electron transport layer is connected with the light-emitting layer, so that the energy barrier of the interface of the light-emitting layer and the electron transport layer can be effectively reduced, electrons can enter the light-emitting layer from the electron transport layer, the starting voltage of the light-emitting device is reduced, the injection balance of electrons and holes is improved, and the performances of the light-emitting device such as the service life, the light-emitting efficiency and the like are improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of an embodiment of a method for manufacturing a light emitting device according to the present application;
Fig. 2 is a schematic structural view of an embodiment of a light emitting device according to the present application;
FIGS. 3a and 3b are graphs of operating voltage versus time and current density versus voltage, respectively, for single electron devices (EODs) of comparative examples 1-3;
FIGS. 4a and 4b are graphs of operating voltage versus time and current density versus voltage for single electron devices (EODs) of examples 1-4, respectively;
FIGS. 5a and 5b are graphs of operating voltage versus time and current density versus voltage for single electron devices (EODs) of examples 5-7, respectively;
FIGS. 6a and 6b are graphs of operating voltage versus time and current density versus voltage, respectively, for a single hole device (HOD) of test example 1;
Fig. 7 is a TEM image of the single electron device in example 1.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and description only, and is not intended to limit the application.
In the present application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used to generally refer to the upper and lower positions of the device in actual use or operation, and specifically the orientation of the drawing figures; while "inner" and "outer" are for the outline of the device. In addition, in the description of the present application, the term "comprising" means "including but not limited to".
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1,2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, "and/or" describing the association relationship of the association object means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
Referring to fig. 1, fig. 1 is a schematic flow chart of an embodiment of a method for manufacturing a light emitting device according to the present application, which includes the following steps:
Step S11: providing a prefabricated device, wherein the prefabricated device comprises an anode, a light-emitting layer, a first electron transport layer and a cathode;
Step S12: a first substance is arranged on the surface of one side of the cathode, which is far away from the first electron transport layer, wherein the first substance contains silver ions;
step S13: and electrifying the prefabricated device to form silver channels in the first electron transport layer to obtain the light-emitting device comprising the second electron transport layer.
Wherein in the second electron transport layer, the silver channel extends from the cathode to the light emitting layer.
According to the preparation method of the light-emitting device, the first substance is arranged on the surface of the cathode, which is far away from the first electron transport layer, and the prefabricated device is electrified so that at least one silver channel is formed in the first electron transport layer, and electrons in the cathode can be transferred into the light-emitting layer through the silver channel, so that the electron injection efficiency can be effectively improved.
Further, the silver channel extends from the cathode to the light-emitting layer, can extend to be connected with the light-emitting layer and communicate the cathode with the light-emitting layer, so that the energy barrier of the interface between the light-emitting layer and the electron transport layer can be effectively reduced, electrons can enter the light-emitting layer from the electron transport layer, and the starting voltage of the light-emitting device is reduced. Specifically, the silver channel can promote electron transfer at the interface of the light-emitting layer and the electron transport layer, so that electric excitation composite emission is inhibited, device performance is improved, and the silver channel is used as a high-conductivity path to provide a fast injection channel for electrons, promote fast injection of electrons and improve injection balance of electrons and holes. On the other hand, the silver channel can effectively reduce the energy barrier of the interface between the light-emitting layer and the electron transport layer, and promote the electron transfer into the light-emitting layer, so that the starting voltage of the light-emitting device is reduced. In addition, the silver channel can well promote the action between the cathode and the electron transport layer, and the forward aging action time of the light-emitting device can be greatly shortened.
In the step S11:
The cathode is a silver (Ag) electrode. The thickness of the cathode can be 80-120nm, and can be specifically 80-110nm, 80-100nm, 80-90nm, 90-110nm, 90-100nm and the like.
The material of the light emitting layer is selected from quantum dot materials, the quantum dot materials are selected from at least one of single-structure quantum dots, core-shell structure quantum dots, doped or undoped inorganic perovskite type quantum dots or organic-inorganic hybrid perovskite type quantum dots, the single-structure quantum dots are selected from at least one of II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, II-IV-VI compounds and IV simple substances, the II-VI compounds are selected from at least one of CdSe、CdS、 CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、 ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe and CdZnSTe, the III-V compounds are selected from at least one of InP, inAs, gaP, gaAs, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP, and the I-III-VI compounds are selected from at least one of CuInS 2、CuInSe2 and AgInS 2; the core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS; the structural general formula of the inorganic perovskite type quantum dot is AMX 3, wherein A is Cs + ion, M is divalent metal cation, at least one of Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、 Yb2+、Eu2+ and X is halogen anion, at least one of Cl -、Br-、I-; the organic-inorganic hybrid perovskite quantum dot has a structural general formula of BMX 3, wherein B is an organic amine cation selected from CH 3(CH2)n-2NH3+ or NH 3(CH2)nNH3 2+, wherein n is more than or equal to 2, M is a divalent metal cation selected from at least one of Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+, X is a halogen anion selected from at least one of Cl -、Br-、I-.
In a specific embodiment, the material of the light emitting layer is selected from blue light quantum dot materials. Correspondingly, the light emitting device is a blue light quantum dot light emitting device. In the blue light quantum dot luminescent device, the silver channel is formed in the electron transport layer by the preparation method provided by the application, so that electron injection is promoted, and potential barrier of an interface between the luminescent layer and the electron transport layer is reduced, thereby solving the problems of insufficient electron injection and high starting voltage, improving the injection balance of electrons and holes, and improving the luminescent efficiency, the service life and other performances of the blue light quantum dot luminescent device.
The material of the electron transport layer is selected from inorganic nanocrystalline materials or doped inorganic nanocrystalline materials; the inorganic nanocrystalline material is selected from one or more of zinc oxide, titanium dioxide, tin dioxide, aluminum oxide, calcium oxide, silicon dioxide, gallium oxide, zirconium oxide, nickel oxide and zirconium oxide; the doped inorganic nanocrystalline material comprises the inorganic nanocrystalline material and a doping element, wherein the doping element is selected from at least one of Mg, ca, li, ga, al, co, mn.
The electron transport layer may have a thickness of 20-40nm, specifically 20-35nm, 20-30nm, 20-25nm, 25-40nm, 25-35nm, 25-30nm, 30-40nm, 30-35nm, 35-40nm, etc. The electron transport layer in this thickness range can support the formation of the silver channels therein to provide the light emitting device with good electron transport and injection properties.
The anode is selected from one or more of a metal electrode, a carbon electrode, a doped or undoped metal oxide electrode and a composite electrode; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the composite electrode is at least one selected from AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、 ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、 ZnS/Al/ZnS、TiO2/Ag/TiO2 and TiO 2/Al/TiO2. Wherein "/" represents a laminated structure, for example, the composite electrode AZO/Ag/AZO represents an electrode of a composite structure in which AZO layers, ag layers, and AZO layers are laminated in three layers.
In the step S12:
The first substance is at least one selected from silver tetrafluoroborate, silver pentafluoropropionate, silver heptafluorobutyrate, silver hexafluorophosphate and silver acrylate. The first substance not only can provide silver ions to form a silver channel, but also can generate a certain etching effect on the silver electrode to promote the silver ions to pass through the silver electrode and reach the first electron transport layer.
It will be appreciated that the mass of the first substance disposed on the surface of the cathode may be set according to the size of the area of the surface of the cathode. For example, in one embodiment, the ratio of the mass of the first substance to the area of the cathode is 75 to 500 μg/cm 2, and may be 75～100μg/cm2、 100～200μg/cm2、200～300μg/cm2、300～400μg/cm2、400～500μg/cm2、75～450 μg/cm2、100～350μg/cm2、150～350μg/cm2、250～350μg/cm2 or the like.
In another embodiment, the mass of the first substance disposed on the surface of the cathode may be determined according to the area of the first electron transport layer adjacent to the cathode. Specifically, the ratio of the mass of the first substance to the area of the first electron transport layer is 75 to 500 μg/cm 2, specifically 75～100μg/cm2、100～200μg/cm2、200～300μg/cm2、300～400μg/cm2、400～500 μg/cm2、75～450μg/cm2、100～350μg/cm2、150～350μg/cm2、250～350μg/cm2 or the like.
In the above two embodiments, the mass of the first substance is determined according to the area of the cathode or the first electron transport layer, so that it is possible to provide sufficient first substance on the surface of the cathode.
In one embodiment, the disposing the first substance on a surface of the cathode on a side away from the first electron transport layer specifically includes the following steps: and (3) arranging a first substance solution on the surface of the side, away from the first electron transport layer, of the cathode through a solution method, and then drying.
The solution method may be spin coating, printing, ink jet printing, knife coating, printing, dip-coating, dipping, spraying, roll coating, casting, slit coating, bar coating, or the like.
The concentration of the first substance in the first substance solution may range from 5 to 20mg/mL, specifically from 5 to 15mg/mL, from 5 to 10mg/mL, from 10 to 20mg/mL, from 10 to 15mg/mL, from 15 to 20mg/mL, etc. The concentration range may uniformly spread the first substance on the surface of the first electron transport layer.
The volume of the first substance solution disposed on the surface of the cathode may be set according to the area of the surface of the cathode. For example, in one embodiment, the ratio of the volume of the first substance solution to the area of the cathode is 15 to 25 μl/cm 2, specifically 15～22μL/cm2、18～22 μL/cm2、18～20μL/cm2、15～18μL/cm2、22～25μL/cm2 or the like.
In another embodiment, the volume of the first substance solution disposed on the surface of the cathode may be determined according to the area of the first electron transport layer adjacent to the cathode. Specifically, the ratio of the volume of the first substance solution to the area of the first electron transport layer is 15 to 25. Mu.L/cm 2, specifically 15～22μL/cm2、18～22μL/cm2、18～20μL/cm2、15～18μL/cm2、22～25μ L/cm2 or the like.
In the above two embodiments, the volume of the first substance solution is determined according to the area of the cathode or the first electron transport layer, so that it is possible to provide sufficient first substance on the surface of the cathode.
The solvent of the first substance solution is at least one selected from diethyl ether, benzene, toluene and nitromethane.
The drying temperature is 60-100deg.C, and the drying time is 10-30min. The drying temperature can be 60-90deg.C, 70-100deg.C, 70-90deg.C, 70-80deg.C, etc.; the drying time can be 10-25min, 15-30min, 15-25min, 15-20min, etc. By the drying, the solvent in the first substance solution can be volatilized and removed, and the contact tightness between the first substance and the cathode can be promoted.
Wherein, still include the standing before the drying. The time of the standing is 30 to 240s, specifically, 30 to 200s, 60 to 240s, 80 to 200s, 80 to 150s, 90 to 120s, etc., so that the first substance in the first substance solution is sufficiently contacted with the cathode and permeated into the cathode to form silver channels in the subsequent step.
In one embodiment, the first substance is disposed on a surface of the cathode on a side away from the first electron transport layer, and the method specifically includes the following steps:
And (3) dropwise adding silver tetrafluoroborate-diethyl ether solution on the surface of one side of the cathode far away from the first electron transport layer, standing for 30-240s, spin-drying, heating at 80 ℃ for 30 minutes, and packaging.
In the step S13:
Energizing the prefabricated device to enable the silver ions to pass through the cathode to reach the first electron transport layer, reducing the silver ions into silver atoms, forming silver channels in the first electron transport layer, forming the second electron transport layer containing at least one silver channel, and obtaining the light-emitting device.
It is understood that the material of the first electron transport layer is an electron transport material, and the material of the silver channel in the second electron transport layer may be a mixture including silver and the electron transport material, and the material is the electron transport material except for the silver channel.
And electrifying the prefabricated device, namely connecting the anode and the cathode of the prefabricated device with the anode and the cathode of a power supply respectively, so that the prefabricated device is electrified. In other words, an external voltage is applied to the prefabricated device.
Wherein, the voltage of the electrifying can be 5-12V, and can be specifically 5-10V, 5-8V, 8-12V, 8-10V, 10-12V and the like. The energized voltage may be the same as a voltage range in which the light emitting device normally operates.
Silver ions in the first substance on the surface of the cathode drift in the direction of the anode under current guidance when the prefabricated device is energized. In the first electron transport layer, silver ions (Ag +) are reduced to silver atoms (Ag) after a short distance movement due to a low migration rate of silver ions in inorganic nanocrystalline materials such as ZnO. As the oxidation/reduction process continues, silver atoms continuously accumulate at the interface of the cathode and the first electron transport layer, resulting in an enhanced electric field. Further promoting the silver ions to continue to migrate toward the anode. Along with the continuous migration of silver ions, the silver ions are reduced into silver atoms, and the silver atoms further cause the enhancement of an electric field so as to further promote the migration of the silver ions, so that the channels of the silver atoms in the first electron transport layer are promoted to be continuously increased, and silver channels are formed, namely, the silver channels extend from the cathode to the light emitting layer, and the silver channels can promote the rapid injection and transmission of electrons, improve the light emitting efficiency of the light emitting device, reduce the starting voltage, improve the service life of the light emitting device and other performances. In a specific embodiment, the silver channel is continuously increased until being connected with the interface between the first electron transport layer and the light emitting layer, so that the silver channel connecting the interface between the cathode and the light emitting layer is formed, the rapid injection and transmission of electrons can be further promoted, the light emitting efficiency of the light emitting device is improved, the starting voltage is reduced, and the service life of the light emitting device is prolonged.
In the second electron transport layer including at least one of the silver channels formed, the mass ratio of silver is 1.5 to 4%, specifically may be 1.5 to 3.5%, 2.0 to 3.0%, 2.5 to 3.5%, 3.5 to 4.0%, 2.0 to 4.0%, 3.5 to 4.0%, 1.5 to 2.5%, 1.5 to 3.0%, etc.
After the step S12 and before the step S13, the method further includes packaging the prefabricated device. If the packaging is performed before the step S13, the step S13 is: energizing the packaged prefabricated device. Wherein the encapsulation may refer to conventional encapsulation operations in the art.
In an embodiment, the packaging of the prefabricated device may specifically include: and setting packaging glue on the prefabricated device, and then setting a cover plate on the packaging glue on the prefabricated device and curing.
Wherein, the packaging glue can be packaging materials such as acrylic resin or epoxy resin, and when the packaging glue is ultraviolet curing packaging glue, the corresponding curing can be specifically: curing for 15-30 min under a UV lamp.
In some embodiments, the power-up may be power-up when life testing or burn-in testing the device. When the life test or the aging test is carried out on the initial light-emitting device, silver ions on the surface of the cathode drift towards the anode under the action of voltage and are reduced in the first electron transport layer to form silver channels.
The light emitting device generally needs to be placed for a period of time after preparation is completed, and then a life test is performed, etc., so as to promote forward aging of the light emitting device and improve the life of the light emitting device. The mechanism of forward aging action may be the action between the electron transport material and the cathode. In this embodiment, the silver channel is formed in the first electron transport layer, so that the effect between the cathode and the second electron transport layer can be well promoted, the forward aging time of the light emitting device is greatly shortened, and the service life of the light emitting device is prolonged while the forward aging time of the light emitting device is shortened.
In an embodiment, the material of the light emitting layer is selected from quantum dot materials, and the electron transport material is selected from inorganic nanocrystalline materials or doped inorganic nanocrystalline materials, such as zinc oxide. The inorganic nanocrystalline material (or doped inorganic nanocrystalline material) has higher work function contact with the quantum dot material (especially blue light quantum dot material), and interface charge transport can cause quenching of the quantum dot material, thereby reducing efficiency. And, in the inorganic nanocrystalline material or the doped inorganic nanocrystalline material, oxygen ion defects and oxygen vacancies are more mobile than cations (such as zinc ions, etc.) therein under an external electric field, so that oxygen vacancies will be accumulated at the cathode due to repulsive force of oxygen ions (O 2-) when in the first electron transport layer due to an electric field. Once oxygen vacancies of sufficient concentration accumulate in the vicinity of the cathode, electron injection into the light emitting device is difficult, and the resistance of the light emitting device increases and the turn-on voltage increases.
In the present application, the silver channel is formed in the first electron transport, and silver atoms are also easily doped in the inorganic nanocrystalline material or the doped inorganic nanocrystalline material, for example, silver doping is easily formed in zinc oxide, and doping instead of Zn site is easily formed, so that other intrinsic donor doping (such as oxygen vacancy or interstitial doping) is suppressed. Meanwhile, the formation energy of oxygen vacancies in the silver-doped zinc oxide unit cell is high, resulting in less formation of oxygen vacancies. Therefore, forming the silver channel in the first electron transport can effectively reduce oxygen defects of the first electron transport layer, avoid oxygen holes from gathering near the cathode, reduce an energy barrier of an interface between the light emitting layer and the first electron transport layer, promote electron transfer into the light emitting layer, improve electron injection and transport efficiency, reduce quenching of quantum dot materials, and accordingly improve light emitting efficiency and reduce a starting voltage of the light emitting device.
It can be understood that, when the light emitting device further includes a hole function layer, the step S11 is: a prefabricated device is provided, wherein the prefabricated device is provided with an anode, a hole functional layer, a light emitting layer, a first electron transport layer and a cathode which are stacked.
Further, the hole function layer comprises a hole injection layer and/or a hole transport layer. When the hole function layer comprises two layers of a hole injection layer and a hole transport layer, the hole injection layer is arranged close to one side of the anode, and the hole transport layer is arranged close to one side of the light-emitting layer.
The hole transport layer is made of a material selected from the group consisting of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB), polyvinylcarbazole (PVK), poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) (poly-TPD), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-Phenylenediamine) (PFB), 4',4 "-tris (carbazole-9-yl) triphenylamine (TCATA), 4' -bis (9-Carbazole) Biphenyl (CBP), N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT); PSS), spiro-NPB, spiro-TPD, doped or undoped NiO, moO 3、WO3、V2O5, P-gallium nitride, crO 3、CuO、MoS2、MoSe2、WS3、WSe3, cuS, cuSCN.
The hole injection layer is made of a material with hole injection capability and is selected from one or more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS), 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane (F4-TCNQ), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazabenzophenanthrene (HATCN), copper phthalocyanine (CuPc), transition metal oxide and transition metal chalcogenide; wherein the transition metal oxide comprises one or more of NiO, moO 2、WO3 and CuO; the metal chalcogenide comprises one or more of MoS 2、MoSe2、WS3、WSe3 and CuS.
It is understood that the light emitting device may further include a substrate. In one embodiment, the step S11 is: a prefabricated device is provided that includes a stacked substrate, an anode, a hole-functional layer, a light-emitting layer, a first electron-transporting layer, and a cathode. The light-emitting device obtained by the preparation method of the light-emitting device is a front-mounted light-emitting device.
The substrate may be a rigid substrate or a flexible substrate. The rigid substrate can be ceramic material or various glass materials and the like. The flexible substrate may be a substrate formed of a material such as a polyimide film (PI) and its derivatives, polyethylene naphthalate (PEN), phosphoenolpyruvic acid (PEP), or diphenylene ether resin.
In the preparation method of the light-emitting device provided by the application, the preparation methods of the anode, the hole functional layer, the light-emitting layer, the first electron transport layer, the cathode and other film layers included in the prefabricated device can be realized by adopting conventional technologies in the field, such as a chemical method or a physical method. Wherein, the chemical method comprises chemical vapor deposition, continuous ion layer adsorption and reaction, anodic oxidation, electrolytic deposition and coprecipitation. Physical methods include physical plating methods and solution methods, wherein the physical plating methods include: thermal evaporation plating, electron beam evaporation plating, magnetron sputtering, multi-arc ion plating, physical vapor deposition, atomic layer deposition, pulsed laser deposition, etc.; the solution method may be spin coating, printing, ink jet printing, knife coating, printing, dip-coating, dipping, spray coating, roll coating, casting, slit coating, bar coating, or the like.
It is understood that when the light emitting device further includes an electron injection layer, a hole blocking layer, and/or an interface modification layer, the two preparation methods further include a step of forming the corresponding layer using the chemical or physical method.
The application also relates to a light-emitting device, referring to fig. 2, fig. 2 is a schematic structural diagram of an embodiment of a light-emitting device according to the application. The light emitting device 100 includes a cathode 10, an electron transport layer 20, a light emitting layer 30, and an anode 40, which are stacked. The electron transport layer 20 comprises at least one silver channel 21, which silver channel 21 extends from the cathode 10 towards the light emitting layer 30.
Further, the silver channels 21 may have one end connected to the cathode 10 and the other end connected to the light emitting layer 30. That is, one or more of the silver channels 21 of the at least one silver channel 21 may communicate the cathode with the light emitting layer. It will be appreciated that when the electron transport layer 20 includes a silver channel 21, the silver channel 21 extends from the cathode 10 toward the light emitting layer 30, and may or may not be in communication with the light emitting layer 30. When the electron transport layer 20 includes two or more silver channels 21, all of the silver channels 21 extend from the cathode 10 to the light emitting layer 30, and a part of the silver channels 21 may be in communication with the light emitting layer 30 and a part may not be in communication with the light emitting layer 30.
In this embodiment, the silver channel 21 is included in the electron transport layer 20 of the light emitting device 100, and in operation, electrons in the cathode 10 can be transferred to the light emitting layer 30 through the silver channel 21, so that the electron injection efficiency can be effectively improved. The silver channel 21 in the electron transport layer 20 is connected with the light emitting layer 30, so that an energy barrier of an interface between the light emitting layer 30 and the electron transport layer 20 can be effectively reduced, electrons can enter the light emitting layer 30 from the electron transport layer 20, the starting voltage of the light emitting device 100 is reduced, the balance of electron injection and hole injection of the light emitting device 100 is improved, and the light emitting efficiency, the service life and other performances of the light emitting device 100 are improved.
In one embodiment, the material of the electron transport layer 20 is an electron transport material, and the material of the silver channels 21 is a mixture of silver and the electron transport material. That is, the silver channels 21 are partial regions in the electron transport layer 20, and a plurality of silver channels 21 may be formed at intervals in the electron transport layer 20, and the regions corresponding to the silver channels 21 are each extended from the cathode 10 to the light emitting layer 30.
The shape of the contact surface of each silver channel 21 with the cathode 10 may be a regular shape, such as a circle, a rectangle, a square, etc., or may be an irregular shape, such as a cloud-like shape.
In one embodiment, the contact surface is square in shape, and the side length of the square can be 1-3 nm. In another embodiment, when the contact surface is circular in shape, the diameter of the circular shape may be 1 to 3nm or the like.
In an embodiment, the contact area between each silver channel 21 and the cathode 10 may be 1-9 nm 2, such as 1～8nm2、2～8nm2、2～7nm2、3～7nm2、3～6nm2、4～6nm2、4～5nm2.
In an embodiment, the mass ratio of silver in the electron transport layer 20 is 1.5-4%, specifically 1.5-3.5%, 2.0-3.0%, 2.5-3.5%, 3.5-4.0%, 2.0-4.0%, 3.5-4.0%, 1.5-2.5%, 1.5-3.0%, etc.
In one embodiment, the light emitting device 100 further includes a hole function layer 50. The hole-functional layer 50 includes a hole-injecting layer 51 and/or a hole-transporting layer 52. When the hole function layer 50 includes two layers of the hole injection layer 51 and the hole transport layer 52, the hole injection layer 51 is disposed near the anode side, and the hole transport layer 52 is disposed near the light emitting layer side.
In this embodiment, the cathode 10, the electron transport layer 20, the light emitting layer 30, the anode 40, the hole function layer 50, the silver channel 21, and the like may be referred to the related description in the preparation method of the light emitting device, and the description thereof is omitted herein. The electron transport layer 20 may refer to the related descriptions of the first electron transport layer and the second electron transport layer in the preparation method of the light emitting device, and are not described herein.
In one embodiment, the light emitting device 100 is manufactured by the manufacturing method of the light emitting device described above.
The application also relates to a display device comprising the light emitting device provided by the application. The display device may be any electronic product with a display function, including but not limited to a smart phone, a tablet computer, a notebook computer, a digital camera, a digital video camera, a smart wearable device, a smart weighing electronic scale, a vehicle-mounted display, a television set or an electronic book reader, wherein the smart wearable device may be, for example, a smart bracelet, a smart watch, a Virtual Reality (VR) helmet, etc.
The present application will now be described in more detail by way of the following examples, which are intended to be illustrative of the application and not limiting thereof.
Example 1
The present embodiment provides a full light emitting device and a single electronic device. It is understood that a full light emitting device is a light emitting device having a hole functional layer and an electron functional layer, and a single electron device is a light emitting device without a hole functional layer.
The preparation of the full-luminescent device comprises the following steps:
Step 1: placing the ITO glass substrate into a glass vessel filled with ethanol solution, sequentially ultrasonically cleaning the glass vessel for 20 minutes by using acetone, deionized water and ethanol respectively, and drying the glass vessel by using a nitrogen gun; then, the cleaned ITO glass substrate was placed in an oxygen plasma for further cleaning for 10 minutes, and the surface of the ITO glass substrate was treated with ultraviolet-ozone for 15 minutes.
Step 2: spin-coating PEDOT (polyether-ether-ketone) PSS (PSS) on the cleaned ITO glass substrate in air, wherein the rotating speed is 3500r/min, and the spin-coating time is 30 seconds; after spin coating, placing in air for annealing at 150 ℃ for 30 minutes; after the annealing was completed, the wafer was rapidly transferred to a glove box under nitrogen atmosphere to obtain a hole injection layer having a thickness of 20 nm.
Step 3: spin-coating TFB-chlorobenzene solution with the concentration of 8mg/mL on the hole injection layer, wherein the spin-coating rotating speed is 3500r/min, the time is 30 seconds, and the spin-coating is placed in air for annealing at the annealing temperature of 150 ℃ for 30 minutes after the spin-coating is completed, so that a hole transport layer with the thickness of 30nm is obtained;
Step 4: spin-coating a quantum dot solution on the hole transport layer, wherein the spin-coating rotating speed is 2000rpm, the spin-coating time is 30s, annealing is performed at 60 ℃ in a glove box after the spin-coating is completed, and the annealing time is 5 minutes, so that a light-emitting layer with the thickness of 25nm is obtained; the structure of the blue quantum dots used is as follows: cdZnSe/2 ZnSe/0.05Cd/Cd0.6ZnS 2.
Step 5: spin-coating ZnO-ethanol solution (with the concentration of 30 mg/mL) on the luminescent layer at the rotating speed of 3000r/min, spin-coating for 30 seconds, and annealing to obtain an electron transport layer with the thickness of 30 nm;
step 6: evaporating Ag on the light-emitting layer in the vacuum cavity to obtain a cathode (silver electrode) with the thickness of 100 nm;
Step 7: 100 microliters of silver tetrafluoroborate diethyl ether solution (with the concentration of 15 mg/mL) is dripped on the surface of the silver electrode, and after standing for 30s, spin-drying is performed at a rotating speed of 3000r/min, and heating is performed for 30 minutes at 80 ℃.
Step 8: and packaging to obtain the full-light-emitting device.
Step 9: and immediately powering on the prepared full-luminescent device, and carrying out life test.
The preparation of the single electron device is basically the same as that of the full light emitting device, and the only difference is that: step 2 and step 3 are not performed, and the quantum dot solution is directly spin-coated on the ITO in step 4; finally, a single electronic device (EOD) is obtained through encapsulation. And immediately electrifying the prepared single-electron device, and carrying out electrifying aging test.
When the full-luminescent device and the single-electron device are electrified, silver channels are formed in the electron transport layer.
Example 2
The present embodiment provides a full light emitting device and a single electronic device. The preparation of the full light emitting device and the single electron device of this embodiment is substantially the same as that of embodiment 1, except that: in step 7, the standing time was 60s.
Example 3
The present embodiment provides a full light emitting device and a single electronic device. The preparation of the full light emitting device and the single electron device of this embodiment is substantially the same as that of embodiment 1, except that: in step 7, the standing time was 120s.
Example 4
The present embodiment provides a full light emitting device and a single electronic device. The preparation of the full light emitting device and the single electron device of this embodiment is substantially the same as that of embodiment 1, except that: in step 7, the standing time was 240s.
Example 5
The present embodiment provides a full light emitting device and a single electronic device. The preparation of the full light emitting device and the single electron device of this embodiment is substantially the same as that of embodiment 1, except that: in step 7, the standing time was 90s.
Example 6
The present embodiment provides a full light emitting device and a single electronic device. The preparation of the full light emitting device and the single electron device of this embodiment is substantially the same as that of embodiment 5, except that: the prepared full-luminescent device and the single-electron device are all electrified after being placed for 2 hours.
Example 7
The present embodiment provides a full light emitting device and a single electronic device. The preparation of the full light emitting device and the single electron device of this embodiment is substantially the same as that of embodiment 6, except that: this embodiment is substantially the same as embodiment 5 except that: the prepared full-luminescent device and the single-electron device are all electrified after being placed for 24 hours.
Comparative example 1:
The present comparative example provides a full light emitting device and a single electron device. The preparation of the full light emitting device and the single electron device of this comparative example was substantially the same as in example 1, except that: and (7) directly packaging without performing the step 7.
Comparative example 2:
The present comparative example provides a full light emitting device and a single electron device. The preparation of the full light emitting device and the single electron device of this comparative example was substantially the same as in example 1, except that: step 7, directly packaging without performing the step; and (5) electrifying the prepared full-light-emitting device and the single-electron device after being placed for 24 hours.
Comparative example 3
The present comparative example provides a full light emitting device and a single electron device. The preparation of the full light emitting device and the single electron device of this comparative example was substantially the same as comparative example 2, except that: and (5) electrifying the prepared full-light-emitting device and the single-electron device after being placed for 48 hours.
Detection example 1
The present embodiment provides a single hole device. The single hole device of this example was prepared substantially the same as example 1, except that: and (3) without performing steps 5, 7 and 9, forming a cathode directly on the light-emitting layer without forming an electron transport layer, and packaging to obtain a single hole device (HOD).
Experimental example 1
The single hole devices (HOD) of test example 1 and the single electron devices (EOD) of examples 1 to 7 and comparative examples 1 to 3 were subjected to a power on aging test to obtain an operating voltage-time graph and a current density-voltage graph, see fig. 3a, 3b, 4a, 4b, 5a, 5b, 6a and 6b. Wherein fig. 3a and 3b are an operating voltage-time graph and a current density-voltage graph, respectively, of the single electron devices (EOD) of comparative examples 1-3; FIGS. 4a and 4b are graphs of operating voltage versus time and current density versus voltage for single electron devices (EODs) of examples 1-4, respectively; FIGS. 5a and 5b are graphs of operating voltage versus time and current density versus voltage for single electron devices (EODs) of examples 5-7, respectively; fig. 6 is a graph of operating voltage versus time and a graph of current density versus voltage for the single hole device (HOD) of test example 1. The current densities at the operating voltage (8V) and the operating voltages at steady state for the single electron devices (EOD) of examples 1-7 and comparative examples 1-3 are detailed in table 1.
Experimental example 2
Transmission Electron Microscopy (TEM) testing was performed on the full light emitting device in example 1, referring to fig. 7, and fig. 7 is a TEM image of the single electron device in example 1. In fig. 7, an ITO glass substrate 101, a light-emitting layer 102, an electron transport layer 103, a silver electrode 104, and a silver channel 105 in the electron transport layer 103 are sequentially arranged from bottom to top. It can be seen that, by the method for manufacturing a light emitting device provided by the present application, the silver channel 105 can be formed in the electron transport layer 103, and the silver channel 105 connects the light emitting layer 102 and the silver electrode 104.
Experimental example 3
The full light emitting devices of examples 1-7 and comparative examples 1-3 were subjected to performance tests including External Quantum Efficiency (EQE), on-luminance voltage, and lifetime. The External Quantum Efficiency (EQE) is measured by an EQE optical test instrument, and the service life is the time (converted into 1000 nit brightness) for the brightness of the full-light-emitting device to be reduced to 95% of the initial brightness under the constant current density (2 mA/cm 2). The test results are detailed in table 1 below.
TABLE 1
As can be seen from table 1:
As can be seen from the above experimental test results, the all light emitting devices of examples 1,2 and examples 5 to 7 all have better device lifetime, and may benefit from the reduction of the turn-on voltage of the all light emitting device and the effective improvement of the electron injection of the all light emitting device (derived from the current density and operating voltage data of the EOD device at 8V). Specifically, the reduction of the starting voltage of the full light-emitting device and the effective improvement of electron injection may be due to the formation of a silver channel in the electron transport layer of the full light-emitting device, which can effectively reduce the energy barrier of the interface between the light-emitting layer and the electron transport layer, and facilitate the electrons to enter the light-emitting layer from the electron transport layer, thereby improving the electron injection efficiency and reducing the starting voltage of the light-emitting device.
Compared to the detection of the current density (94.68 mA cm -2) and the operating voltage (4.5V) of the HOD device of example 1 in fig. 6a and 6b, the all-light emitting devices of examples 1, 2 and examples 5-7 may be more balanced in carrier injection due to the formation of silver channels in their electron transport layers, which may effectively reduce the energy barrier at the interface of the light emitting layer and the electron transport layer, facilitating the entry of electrons from the electron transport layer into the light emitting layer.
The carrier injection of the full light emitting devices of example 3 and example 4 is more unbalanced and the lifetime is reduced compared to the HOD device of detection example 1, probably due to the excessive injection of Ag caused by the long residence time of the active agent.
As can be seen from the operation voltage-time graphs of the EOD devices of examples 1 to 7 and comparative examples 1 to 3, the EOD devices of examples 1 to 7 have a rapid drop in initial voltage, which is the formation stage of Ag atom channels, thus resulting in a decrease in operation voltage, and improving electron injection of the full-emission device, thereby greatly improving light emission efficiency and lifetime of the full-emission device.
As can be seen from examples 5-7, the forward aging time of the full-light-emitting device of the present application can be greatly shortened, and the test results related to examples 6 and 7 are similar, which indicates that the best forward aging effect can be achieved after 2 hours of the preparation of the EOD device, the full-light-emitting device and other light-emitting devices. In comparative examples 1 to 3, the light-emitting device was not subjected to the treatment with the activating agent, and the light-emitting device was subjected to the forward aging for more than 24 hours to achieve the optimum effect, indicating that the silver channel was formed in the electron transport layer by the treatment with the activating agent, which can well promote the effect between the cathode and the electron transport layer and shorten the forward aging time of the light-emitting device.
The total light emitting devices of comparative examples 1 to 3 were smaller in both external quantum efficiency EQE and lifetime, and may have poor light emitting efficiency due to imbalance of electron and hole injection in the device caused by insufficient electron injection in the device, and thus the external quantum efficiency EQE was smaller. The unbalance of electron and hole injection also causes excessive holes in the light-emitting layer and the device, and damages the functional layers such as the light-emitting layer, thereby affecting the service life of the device.
It can be seen from the above experimental data that the light emitting device treated with the activating agent for a suitable time can effectively improve electron injection of the light emitting device, thereby reducing the turn-on voltage of the light emitting device and improving the lifetime of the light emitting device. Meanwhile, the forward aging time of the device can be greatly reduced after the active reagent is treated, and the time cost is shortened.
The light emitting device, the preparation method thereof and the display device provided by the embodiment of the application are described in detail, and specific examples are applied to the description of the principle and the implementation mode of the application, and the description of the above examples is only used for helping to understand the method and the core idea of the application; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, the present description should not be construed as limiting the present application.
Claims (11)
1. A method of manufacturing a light emitting device, comprising:
providing a prefabricated device, wherein the prefabricated device comprises an anode, a light-emitting layer, a first electron transport layer and a cathode;
Disposing a first substance on a surface of the cathode on a side remote from the first electron transport layer, wherein the first substance comprises silver;
Energizing the prefabricated device to form at least one silver channel in the first electron transport layer to obtain a light emitting device comprising a second electron transport layer;
wherein in the second electron transport layer, the silver channel extends from the cathode to the light emitting layer.
2. The method of claim 1, wherein,
The material of the first electron transport layer is an electron transport material, and the material of the silver channel comprises a mixture of silver and the electron transport material; and/or
The cathode is a silver electrode; and/or
The thickness of the cathode is 80-120nm; and/or
The thickness of the electron transport layer is 20-40nm; and/or
The ratio of the mass of the first substance to the area of the cathode is 75-500 mug/cm 2.
3. The method according to claim 2, wherein the first substance is at least one selected from the group consisting of silver tetrafluoroborate, silver pentafluoropropionate, silver heptafluorobutyrate, silver hexafluorophosphate, and silver acrylate; and/or
The mass ratio of the silver in the second electron transport layer is 1.5-4%.
4. The method of claim 1, wherein disposing a first substance on a surface of the cathode on a side remote from the first electron transport layer comprises:
And (3) arranging a first substance solution on the surface of the side, away from the first electron transport layer, of the cathode through a solution method, and then drying.
5. The method according to claim 4, wherein,
The solvent of the first substance solution is at least one selected from diethyl ether, benzene, toluene and nitromethane; and/or
The concentration range of the first substance in the first substance solution is 5-20mg/mL; and/or
The drying temperature is 60-100deg.C, and the drying time is 10-30min; and/or
Before the drying, the method further comprises the following steps: standing for 30-240s.
6. The method of manufacturing of claim 1, wherein prior to energizing the prefabricated device, further comprising: packaging the prefabricated device; and/or
The energizing voltage is 5-12V.
7. The method of claim 2, wherein,
The electron transport material is selected from inorganic nanocrystalline materials or doped inorganic nanocrystalline materials; the inorganic nanocrystalline material is selected from one or more of zinc oxide, titanium dioxide, tin dioxide, aluminum oxide, calcium oxide, silicon dioxide, gallium oxide, zirconium oxide, nickel oxide and zirconium oxide; the doped inorganic nanocrystalline material comprises the inorganic nanocrystalline material and doping elements, wherein the doping elements are at least one selected from Mg, ca, li, ga, al, co, mn; and/or
The material of the light emitting layer is selected from quantum dot materials, the quantum dot materials are selected from at least one of single-structure quantum dots, core-shell structure quantum dots, doped or undoped inorganic perovskite type quantum dots or organic-inorganic hybrid perovskite type quantum dots, the single-structure quantum dots are selected from at least one of II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, II-IV-VI compounds and IV simple substances, the II-VI compounds are selected from at least one of CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe and CdZnSTe, the III-V compounds are selected from at least one of InP, inAs, gaP, gaAs, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP, and the I-III-VI compounds are selected from at least one of CuInS 2、CuInSe2 and AgInS 2; the core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS; the structural general formula of the inorganic perovskite type quantum dot is AMX 3, wherein A is Cs + ion, M is divalent metal cation, at least one of Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+ and X is halogen anion, at least one of Cl -、Br-、I-; the organic-inorganic hybrid perovskite quantum dot has a structural general formula of BMX 3, wherein B is an organic amine cation selected from CH 3(CH2)n-2NH3+ or NH 3(CH2)nNH3 2+, wherein n is more than or equal to 2, M is a divalent metal cation selected from at least one of Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+, X is a halogen anion selected from at least one of Cl -、Br-、I-; and/or
The anode is selected from one or more of a metal electrode, a carbon electrode, a doped or undoped metal oxide electrode and a composite electrode; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the composite electrode is at least one selected from AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2 and TiO 2/Al/TiO2; and/or
The prefabricated device further comprises a hole functional layer, wherein the hole functional layer is arranged between the anode and the light-emitting layer, and comprises a hole injection layer and/or a hole transport layer; when the hole functional layer comprises the hole injection layer and the hole transport layer, the hole injection layer is arranged close to one side of the anode, and the hole transport layer is arranged close to one side of the light-emitting layer; wherein the hole transport layer material is selected from one or more of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine), poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-phenylenediamine), 4',4 "-tris (carbazol-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), spiro-NPB, spiro-TPD, doped or undoped NiO, moO 3、WO3、V2O5, P-type gallium nitride, crO 3、CuO、MoS2、MoSe2、WS3、WSe3, cuS, cun; the material of the hole injection layer is selected from one or more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, copper phthalocyanine, transition metal oxide and transition metal chalcogenide; wherein the transition metal oxide comprises one or more of NiO, moO 2、WO3 and CuO; the metal chalcogenide comprises one or more of MoS 2、MoSe2、WS3、WSe3 and CuS.
8. A light emitting device comprising a stack of an anode, a light emitting layer, an electron transporting layer and a cathode, wherein the electron transporting layer comprises at least one silver channel extending from the cathode to the light emitting layer.
9. The light-emitting device according to claim 8, wherein a material of the electron-transporting layer is an electron-transporting material, and a material of the silver channel is a mixture of silver and the electron-transporting material; and/or
One or more of the silver channels of the at least one silver channel communicates the cathode with the light emitting layer; and/or
The contact area of each silver channel and the cathode is 1-9 nm 2; and/or
The mass ratio of the silver in the electron transport layer is 1.5-4%.
10. A light-emitting device according to claim 8, wherein,
The cathode is a silver electrode; and/or
The thickness of the cathode is 80-120nm; and/or
The electron transport material is selected from inorganic nanocrystalline materials or doped inorganic nanocrystalline materials; the inorganic nanocrystalline material is selected from one or more of zinc oxide, titanium dioxide, tin dioxide, aluminum oxide, calcium oxide, silicon dioxide, gallium oxide, zirconium oxide, nickel oxide and zirconium oxide; the doped inorganic nanocrystalline material comprises the inorganic nanocrystalline material and doping elements, wherein the doping elements are at least one selected from Mg, ca, li, ga, al, co, mn; and/or
The thickness of the electron transport layer is 20-40nm; and/or
The material of the light emitting layer is selected from quantum dot materials, the quantum dot materials are selected from at least one of single-structure quantum dots, core-shell structure quantum dots, doped or undoped inorganic perovskite type quantum dots or organic-inorganic hybrid perovskite type quantum dots, the single-structure quantum dots are selected from at least one of II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, II-IV-VI compounds and IV simple substances, the II-VI compounds are selected from at least one of CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe and CdZnSTe, the III-V compounds are selected from at least one of InP, inAs, gaP, gaAs, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP and InAlNP, and the I-III-VI compounds are selected from at least one of CuInS 2、CuInSe2 and AgInS 2; the core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from at least one of CdS, cdTe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znSeS and ZnS; the structural general formula of the inorganic perovskite type quantum dot is AMX 3, wherein A is Cs + ion, M is divalent metal cation, at least one of Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+ and X is halogen anion, at least one of Cl -、Br-、I-; the organic-inorganic hybrid perovskite quantum dot has a structural general formula of BMX 3, wherein B is an organic amine cation selected from CH 3(CH2)n-2NH3+ or NH 3(CH2)nNH3 2+, wherein n is more than or equal to 2, M is a divalent metal cation selected from at least one of Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+, X is a halogen anion selected from at least one of Cl -、Br-、I-; and/or
The anode is selected from one or more of a metal electrode, a carbon electrode, a doped or undoped metal oxide electrode and a composite electrode; wherein the material of the metal electrode is at least one selected from Al, ag, cu, mo, au, ba, ca and Mg; the material of the carbon electrode is at least one selected from graphite, carbon nano tube, graphene and carbon fiber; the material of the doped or undoped metal oxide electrode is at least one selected from ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the composite electrode is at least one selected from AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2 and TiO 2/Al/TiO2; and/or
The light emitting device further includes a hole function layer; the hole functional layer comprises a hole injection layer and/or a hole transport layer; when the hole functional layer comprises the hole injection layer and the hole transport layer, the hole injection layer is arranged close to one side of the anode, and the hole transport layer is arranged close to one side of the light-emitting layer; wherein the material of the hole transport layer is selected from poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), polyvinylcarbazole, poly (N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) and poly (9, 9-dioctylfluorene
-One or more of co-bis-N, N-phenyl-1, 4-phenylenediamine), 4',4 "-tris (carbazol-9-yl) triphenylamine, 4' -bis (9-carbazol) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), spiro-NPB, spiro-TPD, doped or undoped NiO, moO 3、WO3、V2O5, P-gallium nitride, crO 3、CuO、MoS2、MoSe2、WS3、WSe3, cuS, cuSCN; the material of the hole injection layer is selected from one or more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanoquinone-dimethane, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, copper phthalocyanine, transition metal oxide and transition metal chalcogenide; wherein the transition metal oxide comprises one or more of NiO, moO 2、WO3 and CuO; the metal chalcogenide comprises one or more of MoS 2、MoSe2、WS3、WSe3 and CuS.
11. A display device characterized in that the display device comprises a light-emitting device produced by the production method of a light-emitting device according to any one of claims 1 to 7; or the display device comprises a light emitting device according to any one of claims 8-10.
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