CN117693215A - 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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- 238000000034 method Methods 0.000 claims abstract description 14
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- 239000002096 quantum dot Substances 0.000 claims description 89
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- Electroluminescent Light Sources (AREA)
Abstract
The present disclosure provides a light emitting device comprising an anode, a cathode, a light emitting layer between the anode and the cathode, and a hole function layer between the anode and the light emitting layer, characterized in that the light emitting device further comprises an auxiliary layer between the anode and the hole function layer, the material of the auxiliary layer comprising a doped or undoped metal oxide. The light emitting device in the present disclosure has higher luminous efficiency and longer service life. The disclosure also provides a method for manufacturing the light emitting device and a display device including the light emitting device.
Description
Technical Field
The disclosure relates to the field of display devices, and in particular relates to a light emitting device, a preparation method thereof and a display device.
Background
Light emitting devices such as Organic Light Emitting Diodes (OLEDs) and quantum dot light emitting diodes (QLEDs) have been widely used in display devices in recent years because of their advantages such as high color gamut, solution-fabricability, and flexibility. The functional layers of the existing light-emitting device are usually manufactured by spin coating film formation, printing film formation or other methods. However, the prepared light-emitting device has low light-emitting efficiency and service life, and cannot reach the index of mass production.
Disclosure of Invention
Based on this, it is necessary to provide a light emitting device having higher light emitting efficiency and longer service life.
In addition, there is a need to provide a method of manufacturing a light emitting device.
In addition, it is also necessary to provide a display device.
At least one embodiment of the present disclosure provides a light emitting device including an anode, a cathode, a light emitting layer between the anode and the cathode, and a hole function layer between the anode and the light emitting layer, the light emitting device further including an auxiliary layer between the anode and the hole function layer, a material of the auxiliary layer including at least one of a doped or undoped metal oxide, and a doped or undoped metal oxide sandwiching a metal therebetween.
In at least one embodiment of the present disclosure, in the doped or undoped metal oxide, the metal oxide includes at least one of tin oxide, zinc oxide, magnesium oxide, and titanium oxide, and the doped element includes at least one of indium, fluorine, antimony, aluminum, gallium, and magnesium;
or, the doped or undoped metal oxide comprises at least one of indium doped tin oxide, fluorine doped tin oxide, antimony doped tin oxide, aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide, magnesium doped zinc oxide, aluminum doped magnesium oxide, zinc sulfide and titanium oxide;
And/or, in the doped metal oxide, the mass fraction of the doped element is 20% -50%.
In at least one embodiment of the present disclosure, the auxiliary layer is a laminated structure, and the material of the auxiliary layer further includes a metal, and the specific structure of the auxiliary layer is: doped or undoped metal oxide/metal material/doped or undoped metal oxide, wherein the metal comprises at least one of silver and aluminum;
or, the specific structure of the auxiliary layer comprises at least one of aluminum doped zinc oxide/silver/aluminum doped zinc oxide, aluminum doped zinc oxide/aluminum doped zinc oxide, indium doped tin oxide/silver/indium doped tin oxide, indium doped tin oxide/aluminum/indium doped tin oxide, zinc oxide/silver/zinc oxide, zinc oxide/aluminum/zinc oxide, titanium oxide/silver/titanium oxide and titanium oxide/aluminum/titanium oxide;
and/or the thickness of the auxiliary layer is 1nm-20nm or 1nm-15nm.
In at least one embodiment of the present disclosure, the light emitting device further includes an electron transport layer between the light emitting layer and the cathode;
wherein the material of the electron transport layer comprises ZnO and TiO 2 At least one of (a) and (b);
And/or the thickness of the electron transport layer is 15nm-60nm;
and/or the light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer;
and/or the thickness of the light-emitting layer is 10nm-60nm.
In at least one embodiment of the present disclosure, the quantum dot light emitting layer is a red light quantum dot light emitting layer, a green light quantum dot light emitting layer, or a blue light quantum dot light emitting layer;
the blue light quantum dot luminescent layer comprises at least one of blue light quantum dots with a single structure and blue light quantum dots with a core-shell structure, and the blue light quantum dots with the core-shell structure comprise at least one of CdSe@ZnS blue light quantum dots and ZnCdS@ZnS blue light quantum dots;
the green light quantum dot light emitting layer comprises quantum dots of at least one of the following materials: cdSe/CdZnSe alloy, inP and CuInS 2 、AgInS 2 CdTe, cdSe/Te alloys;
the red light quantum dot luminescent layer comprises quantum dots of at least one of the following materials: pbSe/Te, pbS, inAs, cuInSe 2 、Cd 3 As 2 、Cd 3 P 2 、CdTe、AgInS 2 ；
And/or the material of the organic light emitting layer comprises at least one of 4,4' -bis (N-carbazole) -1,1' -biphenyl, tris [2- (p-tolyl) pyridine-C2, N) iridium (III), 4' -tris (carbazole-9-yl) triphenylamine, tris [2- (p-tolyl) pyridine-C2, N) iridium, biaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials and DBP fluorescent materials, polyacetylene and derivatives thereof, poly-p-benzene and derivatives thereof, polythiophene and derivatives thereof, polyfluorene and derivatives thereof;
And/or the hole functional layer comprises a hole transport layer and/or a hole injection layer, the material of the hole transport layer comprises an organic material with hole transport capability or an inorganic material with hole transport capability, the organic material with hole transport capability comprises 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, N ' - (1, N ' -naphthalene) -1, 4' -biphenyldiamine (NPB), graphene, or graphene-1, 4' -biphenyl (NPB), and at least one of the non-doped graphene materials with hole transport capability 3 、MoO 3 And at least one of CuO, the material of the hole injection layer includes at least one of poly (3, 4-ethylenedioxythiophene) (PEDOT), 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 polyestercarbonate (CuPc), transition metal oxide, and transition metal chalcogenide;
And/or the anode and/or the cathode comprises Al, ag, cu, mo, au, ba, ca, mg, graphite, carbon nanotube, graphene, carbon fiber, ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO, AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO 2 /Ag/TiO 2 TiO 2 /Al/TiO 2 At least one of them.
At least one embodiment of the present disclosure provides a method for manufacturing the light emitting device, including the steps of:
providing an anode substrate, and preparing an auxiliary layer on the anode substrate;
preparing a hole function layer on the auxiliary layer;
preparing a light emitting layer on the hole function layer; and
preparing a cathode on the light-emitting layer to obtain a light-emitting device;
or providing a cathode substrate and preparing a light-emitting layer on the cathode substrate;
preparing a hole function layer on the light emitting layer;
preparing an auxiliary layer on the hole functional layer;
preparing an anode on the auxiliary layer to obtain a light-emitting device;
the material of the auxiliary layer comprises doped or undoped metal oxide and at least one of doped or undoped metal oxide and metal sandwiched between the doped or undoped metal oxide.
In at least one embodiment of the present disclosure, in the doped or undoped metal oxide, the metal oxide includes at least one of tin oxide, zinc oxide, magnesium oxide, and titanium oxide, and the doped element includes at least one of indium, fluorine, antimony, aluminum, gallium, and magnesium;
Or, the doped or undoped metal oxide comprises at least one of indium doped tin oxide, fluorine doped tin oxide, antimony doped tin oxide, aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide, magnesium doped zinc oxide, aluminum doped magnesium oxide, zinc sulfide and titanium oxide;
and/or, in the doped metal oxide, the mass fraction of the doped element is 20% -50%.
In at least one embodiment of the present disclosure, the auxiliary layer is a laminated structure, and the material of the auxiliary layer further includes a metal, and the specific structure of the auxiliary layer is: doped or undoped metal oxide/metal material/doped or undoped metal oxide, wherein the metal comprises at least one of silver and aluminum;
or, the specific structure of the auxiliary layer comprises at least one of aluminum doped zinc oxide/silver/aluminum doped zinc oxide, aluminum doped zinc oxide/aluminum doped zinc oxide, indium doped tin oxide/silver/indium doped tin oxide, indium doped tin oxide/aluminum/indium doped tin oxide, zinc oxide/silver/zinc oxide, zinc oxide/aluminum/zinc oxide, titanium oxide/silver/titanium oxide and titanium oxide/aluminum/titanium oxide;
and/or the thickness of the auxiliary layer is 1nm-20nm or nm-15nm.
In at least one embodiment of the present disclosure, after the light emitting layer is prepared and before the cathode is prepared, the preparation method further includes the steps of:
preparing an electron transport layer on the light emitting layer;
or, before the light emitting layer is prepared on the cathode substrate, the preparation method further comprises the steps of:
an electron transport layer is prepared on the cathode substrate.
In at least one embodiment of the present disclosure, the material of the electron transport layer includes ZnO and TiO 2 At least one of (a) and (b);
and/or the thickness of the electron transport layer is 15nm-60nm;
and/or the light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer;
and/or the thickness of the light-emitting layer is 10nm-60nm.
At least one embodiment of the present disclosure provides a display apparatus including the light emitting device or the light emitting device prepared by the preparation method.
The auxiliary layer is arranged between the anode and the hole injection layer, and the auxiliary layer can reduce the energy level difference between the anode and the hole injection layer, so that the auxiliary layer improves the transmission capability of hole carriers and electron carriers and the recombination rate of the hole carriers and the electron carriers in the light-emitting layer, thereby improving the light-emitting efficiency, the service life and the stability of the light-emitting device.
Drawings
Fig. 1 is a schematic structural view of a light emitting device according to an embodiment of the present disclosure;
fig. 2 is a schematic structural view of a light emitting device according to another embodiment of the present disclosure;
fig. 3 is a flowchart illustrating a method for manufacturing a light emitting device according to an embodiment of the present disclosure;
FIG. 4 is a slice analysis diagram of device one provided by the present disclosure;
FIG. 5 is a slice analysis of device two provided by the present disclosure;
FIG. 6 is a JV diagram of the present disclosure providing three HOD devices;
FIG. 7 is a JV diagram of three EOD devices provided by the present disclosure;
fig. 8 is a life chart of the light emitting devices prepared in examples 1 to 5 and comparative example 1 of the present disclosure decaying to T95;
fig. 9 is an efficiency graph of light emitting devices prepared in examples 1 to 5 and comparative example 1 of the present disclosure;
fig. 10 is a voltage diagram of light emitting devices prepared in examples 1 to 5 and comparative example 1 of the present disclosure;
fig. 11 and 12 are JV diagrams of light emitting devices prepared in examples 1 to 5 and comparative example 1 of the present disclosure.
Reference numerals: 100. 200-a light emitting device; 10-anode; 20-an auxiliary layer; 30-a hole functional layer; 301-a hole injection layer; 302-a hole transport layer; 40-a light emitting layer; 50-an electron transport layer; 60-cathode; 70-capping layer; 80-encapsulation layer.
Detailed Description
In order that the disclosure may be understood, a more complete description of the disclosure will be rendered by reference to the appended drawings. Preferred embodiments of the present disclosure are shown in the drawings. This disclosure may, however, be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description of the disclosure herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, at least one embodiment of the present disclosure provides a light emitting device 100 including an anode 10, an auxiliary layer 20, a hole function layer 30, a light emitting layer 40, an electron transport layer 50, and a cathode 60, which are sequentially stacked.
In one embodiment, the anode 10 comprises Al (aluminum), ag (silver), cu (copper), mo (molybdenum), au (gold), ba (barium), ca (calcium), mg (magnesium), graphite, carbon nanotube, graphene, carbon fiber, ITO (indium doped tin oxide), FTO (fluorine doped tin oxide), ATO (antimony doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped zinc oxide), IZO (indium doped zinc oxide), MZO (magnesium doped zinc oxide), AMO (aluminum doped magnesium oxide), AZO/Ag/AZO (aluminum doped zinc oxide/silver/aluminum doped zinc oxide), AZO/Al/AZO (aluminum doped zinc oxide/aluminum doped zinc oxide), ITO/Ag/ITO (indium doped tin oxide/silver/indium doped tin oxide), ITO/ITO (indium doped tin oxide/aluminum/indium doped tin oxide), znO/Ag/ZnO (zinc oxide/silver/zinc oxide), znO/Al/ZnO (zinc oxide/aluminum/zinc oxide), tiO/Al/ZnO (aluminum/zinc oxide) 2 /Ag/TiO 2 (titanium oxide/silver/titanium oxide) and TiO 2 /Al/TiO 2 At least one of (titanium oxide/aluminum/titanium oxide).
In one embodiment, the anode 10 may have a thickness of 10nm to 100nm. Specifically, the thickness of the anode 10 may be 10nm, 20nm, 30nm, 50nm, 60nm, 80nm, 100nm, etc.
In one embodiment, the material of the auxiliary layer 20 includes doped or undoped metal oxide. In one embodiment, in the doped or undoped metal oxide, the metal oxide includes at least one of tin oxide, zinc oxide, magnesium oxide, and titanium oxide, and the doped element includes at least one of indium, fluorine, antimony, aluminum, gallium, and magnesiumOne of the two. Specifically, the doped or undoped metal oxide includes ITO (indium doped tin oxide), FTO (fluorine doped tin oxide), ATO (antimony doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped zinc oxide), IZO (indium doped zinc oxide), MZO (magnesium doped zinc oxide), AMO (aluminum doped magnesium oxide), zinc oxide (ZnO), zinc sulfide (ZnS), and titanium oxide (TiO) 2 ) At least one of them.
In one embodiment, the mass fraction of the doped element in the doped metal oxide is 20% to 50%. In particular, in the doped metal oxide, the mass fraction of the doped element may be 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc.
In an embodiment, the auxiliary layer 20 is a laminated structure, and the material of the auxiliary layer 20 further includes metal. The specific structure of the auxiliary layer 20 is as follows: doped or undoped metal oxide/metal material/doped or undoped metal oxide.
In one embodiment, the metal comprises at least one of silver and aluminum. Specifically, the specific structure of the auxiliary layer 20 includes AZO/Ag/AZO (aluminum doped zinc oxide/silver/aluminum doped zinc oxide), AZO/Al/AZO (aluminum doped zinc oxide/aluminum doped zinc oxide), ITO/Ag/ITO (indium doped tin oxide/silver/indium doped tin oxide), ITO/Al/ITO (indium doped tin oxide/aluminum/indium doped tin oxide), znO/Ag/ZnO (zinc oxide/silver/zinc oxide), znO/Al/ZnO (zinc oxide/aluminum/zinc oxide), and TiO 2 /Ag/TiO 2 (titanium oxide/silver/titanium oxide) and TiO 2 /Al/TiO 2 At least one of (titanium oxide/aluminum/titanium oxide).
In one embodiment, the thickness of the auxiliary layer 20 is 1nm to 20nm, preferably 1nm to 15nm. Specifically, the thickness of the auxiliary layer 20 may be 1nm, 3nm, 5nm, 7nm, 9nm, 11nm, 13nm, 15nm, 17nm, 19nm, 20nm, etc.
In one embodiment, the hole-functional layer 30 includes a hole-injecting layer 301. The material of the hole injection layer 301 may be selected from materials having hole injection capability. In one embodiment, the material of the hole injection layer 301 includes at least one of poly (3, 4-ethylenedioxythiophene) (PEDOT), 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 polyestercarbonate (CuPc), transition metal oxide, and transition metal chalcogenide.
In one embodiment, the hole injection layer 301 has a thickness of 20nm to 120nm. Specifically, the thickness of the hole injection layer 301 may be 20nm, 40nm, 60nm, 80nm, 100nm, 120nm, and the like.
In an embodiment, the light emitting layer 40 may be an organic light emitting layer or a quantum dot light emitting layer.
In an embodiment, the material of the organic light emitting layer includes at least one of 4,4' -bis (N-carbazole) -1,1' -biphenyl, tris [2- (p-tolyl) pyridine-C2, N) iridium (III), 4',4 "-tris (carbazole-9-yl) triphenylamine, tris [2- (p-tolyl) pyridine-C2, N) iridium, biaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, polyacetylene and derivatives thereof, poly-p-phenylene and derivatives thereof, polythiophene and derivatives thereof, polyfluorene and derivatives thereof.
In an embodiment, the quantum dot light emitting layer is a red light quantum dot light emitting layer, a green light quantum dot light emitting layer, or a blue light quantum dot light emitting layer. Preferably, the quantum dot light emitting layer is a blue light quantum dot light emitting layer.
In one embodiment, the red light quantum dot light emitting layer comprises quantum dots of at least one of the following materials: pbSe/Te, pbS, inAs, cuInSe 2 、Cd 3 As 2 、Cd 3 P 2 、CdTe、AgInS 2 。
In one embodiment, the green light quantum dot light emitting layer comprises quantum dots of at least one of the following materials: cdSe/CdZnSe alloy, inP and CuInS 2 、AgInS 2 CdTe, cdSe/Te alloys.
In an embodiment, the blue light quantum dot light emitting layer includes at least one of blue light quantum dots of a single structure and blue light quantum dots of a core-shell structure. Specifically, the blue light quantum dot of the core-shell structure comprises at least one of CdSe@ZnS blue light quantum dot and ZnCdS@ZnS blue light quantum dot. In one embodiment, the particle size of the CdSe@ZnS blue light quantum dots is 3 nm-6 nm. In one embodiment, the particle size of the ZnCdS@ZnS blue light quantum dots is 8 nm-15 nm. It should be noted that "cdse@zns" means ZnS coated CdSe, and "zncds@zns" means ZnS coated ZnCdS.
In one embodiment, the thickness of the light emitting layer 40 is 10nm-60nm. Specifically, the thickness of the light emitting layer 40 may be 10nm, 15nm, 20nm, 25nm, 30nm, 40nm, 50nm, 60nm, etc.
In one embodiment, the material of the electron transport layer 50 includes zinc oxide (ZnO) and titanium dioxide (TiO 2 ) At least one of them.
In one embodiment, the electron transport layer 50 has a thickness of 15nm to 60nm. Specifically, the thickness of the electron transport layer 50 may be 15nm, 30nm, 45nm, 60nm, etc.
In one embodiment, the material of the cathode 60 includes Al (aluminum), ag (silver), cu (copper), mo (molybdenum), au (gold), ba (barium), ca (calcium), mg (magnesium), graphite, carbon nanotube, graphene, carbon fiber, ITO (indium doped tin oxide), FTO (fluorine doped tin oxide), ATO (antimony doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped zinc oxide), IZO (indium doped zinc oxide), MZO (magnesium doped zinc oxide), AMO (aluminum doped magnesium oxide), AZO/Ag/AZO (aluminum doped zinc oxide/silver/aluminum doped zinc oxide), AZO/Al/AZO (aluminum doped zinc oxide/aluminum doped zinc oxide), ITO/Ag/ITO (indium doped tin oxide/silver/indium doped tin oxide), ITO/Al/ITO (indium doped tin oxide/aluminum/indium doped tin oxide), znO/Ag/ZnO (zinc oxide/silver/zinc oxide), znO/Al/ZnO (zinc oxide/aluminum/zinc oxide), tiO/Al/ZnO (aluminum/zinc oxide/aluminum doped tin oxide) 2 /Ag/TiO 2 (titanium oxide/silver/titanium oxide) and TiO 2 /Al/TiO 2 At least one of (titanium oxide/aluminum/titanium oxide).
In one embodiment, the thickness of the cathode 60 may be 15nm-100nm. Specifically, the thickness of the cathode 60 may be 15nm, 30nm, 40nm, 50nm, 60nm, 80nm, 100nm, etc.
In one embodimentIn an embodiment, the light emitting device 100 further comprises a capping layer 70 (CPL). Wherein the capping layer 70 is positioned on the cathode 60 to help prevent external moisture and oxygen from penetrating into the light emitting device 100. In an embodiment, the capping layer 70 may be an organic layer or an inorganic layer. In one embodiment, the material of the organic layer may include α -NPD, NPB, TPD, m-MTDATA, alq3, cuPc, N4' -tetrakis (biphenyl-4-yl) biphenyl-4, 4' -diamine (TPD 15), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), or the like, epoxy resins or acrylates such as methacrylates, or combinations thereof. In one embodiment, the material of the inorganic layer may include an alkali metal compound such as LiF, an alkali metal compound such as MgF 2 、SiON、SiN x Or SiO y An alkaline earth metal compound, or the like, or a combination thereof.
In an embodiment, the light emitting device 100 further comprises an encapsulation layer 80. Wherein the encapsulation layer 80 is located on the capping layer 70. The encapsulation layer 80 serves to further prevent external moisture and oxygen from penetrating into the light emitting device 100 and to protect the light emitting device 100.
Referring to fig. 2, at least one embodiment of the present disclosure provides a light emitting device 200, wherein the light emitting device 200 in fig. 2 is different from the light emitting device 100 in fig. 1 in that: the hole function layer 30 includes not only the hole injection layer 301 but also a hole transport layer 302, and the hole transport layer 302 is located between the hole injection layer 301 and the light emitting layer 40.
In an embodiment, the material of the hole transport layer 302 is an organic material with hole transport capability or an inorganic material with hole transport capability. In one embodiment, the organic material having hole transporting capability includes 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' -tris (carbazol-9-yl) triphenylamine (TCATA), 4' -bis (9-Carbazol) Biphenyl (CBP), N, N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl -at least one of 4,4' -diamine (NPB), doped graphene, undoped graphene, and C60. In one embodiment, the inorganic material with hole transport capability comprises doped or undoped NiO, WO 3 、MoO 3 And at least one of CuO.
In one embodiment, the hole transport layer 302 has a thickness of 10nm to 100nm. Specifically, the thickness of the hole transport layer 302 may be 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 100nm, and the like.
Referring to fig. 3, at least one embodiment of the present disclosure provides a method for manufacturing the light emitting device, including the following steps:
step S11, providing an anode substrate.
In an embodiment, the anode substrate comprises Al (aluminum), ag (silver), cu (copper), mo (molybdenum), au (gold), ba (barium), ca (calcium), mg (magnesium), graphite, carbon nanotube, graphene, carbon fiber, ITO (indium doped tin oxide), FTO (fluorine doped tin oxide), ATO (antimony doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped zinc oxide), IZO (indium doped zinc oxide), MZO (magnesium doped zinc oxide), AMO (aluminum doped magnesium oxide), AZO/Ag/AZO (aluminum doped zinc oxide/silver/aluminum doped zinc oxide), AZO/Al/AZO (aluminum doped zinc oxide/aluminum doped zinc oxide), ITO/Ag/ITO (indium doped tin oxide/silver/indium doped tin oxide), ITO/ITO (indium doped tin oxide/aluminum/indium doped tin oxide), znO/Ag/ZnO (zinc oxide/silver/zinc oxide), znO/Al/ZnO (zinc oxide/aluminum/zinc oxide), tiO/Al/ZnO (aluminum/zinc oxide) 2 /Ag/TiO 2 (titanium oxide/silver/titanium oxide) and TiO 2 /Al/TiO 2 At least one of (titanium oxide/aluminum/titanium oxide).
In an embodiment, the thickness of the anode substrate may be 10nm-100nm. Specifically, the thickness of the anode substrate may be 10nm, 20nm, 30nm, 50nm, 60nm, 80nm, 100nm, and the like.
Step S12, preparing an auxiliary layer 20 on the anode substrate.
Specifically, the auxiliary layer 20 is prepared on the anode substrate by a sputtering method.
In one embodiment, the material of the auxiliary layer 20Including doped or undoped metal oxides. In an embodiment, in the doped or undoped metal oxide, the metal oxide includes at least one of tin oxide, zinc oxide, magnesium oxide, and titanium oxide, and the doped element includes at least one of indium, fluorine, antimony, aluminum, gallium, and magnesium. Specifically, the doped or undoped metal oxide includes ITO (indium doped tin oxide), FTO (fluorine doped tin oxide), ATO (antimony doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped zinc oxide), IZO (indium doped zinc oxide), MZO (magnesium doped zinc oxide), AMO (aluminum doped magnesium oxide), zinc oxide (ZnO), zinc sulfide (ZnS), and titanium oxide (TiO) 2 ) At least one of them.
In one embodiment, the mass fraction of the doped element in the doped metal oxide is 20% to 50%. In particular, in the doped metal oxide, the mass fraction of the doped element may be 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc.
In an embodiment, the auxiliary layer 20 is a laminated structure, and the material of the auxiliary layer 20 further includes metal. The specific structure of the auxiliary layer 20 is as follows: doped or undoped metal oxide/metal material/doped or undoped metal oxide.
In one embodiment, the metal comprises at least one of silver and aluminum.
Specifically, the specific structure of the auxiliary layer 20 includes AZO/Ag/AZO (aluminum doped zinc oxide/silver/aluminum doped zinc oxide), AZO/Al/AZO (aluminum doped zinc oxide/aluminum doped zinc oxide), ITO/Ag/ITO (indium doped tin oxide/silver/indium doped tin oxide), ITO/Al/ITO (indium doped tin oxide/aluminum/indium doped tin oxide), znO/Ag/ZnO (zinc oxide/silver/zinc oxide), znO/Al/ZnO (zinc oxide/aluminum/zinc oxide), and TiO 2 /Ag/TiO 2 (titanium oxide/silver/titanium oxide) and TiO 2 /Al/TiO 2 At least one of (titanium oxide/aluminum/titanium oxide).
In one embodiment, the thickness of the auxiliary layer 20 is 1nm to 20nm, preferably 1nm to 15nm. Specifically, the thickness of the auxiliary layer 20 may be 1nm, 3nm, 5nm, 7nm, 9nm, 11nm, 13nm, 15nm, 17nm, 19nm, 20nm, etc.
Step S13, preparing a hole function layer 30 on the auxiliary layer 20.
Specifically, the hole function layer 30 may be prepared on the auxiliary layer 20 by spin coating or printing.
In one embodiment, the hole-functional layer 30 includes a hole-injecting layer 301. The material of the hole injection layer 301 may be selected from materials having hole injection capability. In one embodiment, the material of the hole injection layer 301 includes at least one of poly (3, 4-ethylenedioxythiophene) (PEDOT), 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 polyestercarbonate (CuPc), transition metal oxide, and transition metal chalcogenide.
In one embodiment, the hole injection layer 301 has a thickness of 20nm to 120nm. Specifically, the thickness of the hole injection layer 301 may be 20nm, 40nm, 60nm, 80nm, 100nm, 120nm, and the like.
Step S14, preparing a light emitting layer 40 on the hole function layer 30.
Specifically, the light emitting layer 40 may be prepared on the hole function layer 301 by spin coating or printing.
In an embodiment, the light emitting layer 40 may be an organic light emitting layer or a quantum dot light emitting layer.
In an embodiment, the material of the organic light emitting layer includes at least one of 4,4' -bis (N-carbazole) -1,1' -biphenyl, tris [2- (p-tolyl) pyridine-C2, N) iridium (III), 4',4 "-tris (carbazole-9-yl) triphenylamine, tris [2- (p-tolyl) pyridine-C2, N) iridium, biaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, polyacetylene and derivatives thereof, poly-p-phenylene and derivatives thereof, polythiophene and derivatives thereof, polyfluorene and derivatives thereof.
In an embodiment, the quantum dot light emitting layer is a red light quantum dot light emitting layer, a green light quantum dot light emitting layer, or a blue light quantum dot light emitting layer. Preferably, the quantum dot light emitting layer is a blue light quantum dot light emitting layer.
In one embodiment, the red light quantum dot light emitting layer comprises quantum dots of at least one of the following materials: pbSe/Te, pbS, inAs, cuInSe 2 、Cd 3 As 2 、Cd 3 P 2 、CdTe、AgInS 2 。
In one embodiment, the green light quantum dot light emitting layer comprises quantum dots of at least one of the following materials: cdSe/CdZnSe alloy, inP and CuInS 2 、AgInS 2 CdTe, cdSe/Te alloys.
In an embodiment, the blue light quantum dot light emitting layer includes at least one of blue light quantum dots of a single structure and blue light quantum dots of a core-shell structure. Specifically, the blue light quantum dot of the core-shell structure comprises at least one of CdSe@ZnS blue light quantum dot and ZnCdS@ZnS blue light quantum dot. In one embodiment, the particle size of the CdSe@ZnS blue light quantum dots is 3 nm-6 nm. In one embodiment, the particle size of the ZnCdS@ZnS blue light quantum dots is 8 nm-15 nm. It should be noted that "cdse@zns" means ZnS coated CdSe, and "zncds@zns" means ZnS coated ZnCdS.
In one embodiment, the thickness of the light emitting layer 40 is 10nm-60nm. Specifically, the thickness of the light emitting layer 40 may be 10nm, 15nm, 20nm, 25nm, 30nm, 40nm, 50nm, 60nm, etc.
Step S15, preparing an electron transport layer 50 on the light emitting layer 40.
Specifically, the electron transport layer 50 may be prepared on the light emitting layer 40 by spin coating or printing.
In one embodiment, the material of the electron transport layer 50 includes zinc oxide (ZnO) and titanium dioxide (TiO 2 ) At least one of them.
In one embodiment, the electron transport layer 50 has a thickness of 15nm to 60nm. Specifically, the thickness of the electron transport layer 50 may be 15nm, 30nm, 45nm, 60nm, etc.
Step S16, preparing a cathode 60 on the electron transport layer 50.
In one embodiment, the material of the cathode 60 includes Al (aluminum), ag (silver), cu (copper), mo (molybdenum), au (gold), ba (barium), ca (calcium), mg (magnesium), graphite, carbon nanotube, graphene, carbon fiber, ITO (indium doped tin oxide), FTO (fluorine doped tin oxide), ATO (antimony doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped zinc oxide), IZO (indium doped zinc oxide), MZO (magnesium doped zinc oxide), AMO (aluminum doped magnesium oxide), AZO/Ag/AZO (aluminum doped zinc oxide/silver/aluminum doped zinc oxide), AZO/Al/AZO (aluminum doped zinc oxide/aluminum doped zinc oxide), ITO/Ag/ITO (indium doped tin oxide/silver/indium doped tin oxide), ITO/Al/ITO (indium doped tin oxide/aluminum/indium doped tin oxide), znO/Ag/ZnO (zinc oxide/silver/zinc oxide), znO/Al/ZnO (zinc oxide/aluminum/zinc oxide), tiO/Al/ZnO (aluminum/zinc oxide/aluminum doped tin oxide) 2 /Ag/TiO 2 (titanium oxide/silver/titanium oxide) and TiO 2 /Al/TiO 2 At least one of (titanium oxide/aluminum/titanium oxide).
In one embodiment, the thickness of the cathode 60 may be 15nm-100nm. Specifically, the thickness of the cathode 60 may be 15nm, 30nm, 40nm, 50nm, 60nm, 80nm, 100nm, etc.
Step S17, preparing a capping layer 70 (CPL) on the cathode 60.
Wherein the capping layer 70 helps to prevent external moisture and oxygen from penetrating into the light emitting device 100. In an embodiment, the capping layer 70 may be an organic layer or an inorganic layer. In one embodiment, the material of the organic layer may include α -NPD, NPB, TPD, m-MTDATA, alq3, cuPc, N4' -tetrakis (biphenyl-4-yl) biphenyl-4, 4' -diamine (TPD 15), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), or the like, epoxy resins or acrylates such as methacrylates, or combinations thereof. In one embodiment, the material of the inorganic layer may include an alkali metal compound such as LiF, an alkali metal compound such as MgF 2 、SiON、SiN x Or SiO y An alkaline earth metal compound, or the like, or a combination thereof.
Step S18, preparing the encapsulation layer 80 on the capping layer 70, thereby obtaining the light emitting device 100.
Wherein the encapsulation layer 80 serves to further prevent external moisture and oxygen from penetrating into the light emitting device 100 and to protect the light emitting device 100.
In another embodiment, in step S13, the hole-functional layer 30 includes not only the hole-injecting layer 301 but also a hole-transporting layer 302, and the hole-transporting layer 302 is located between the hole-injecting layer 301 and the light-emitting layer 40, so as to obtain the light-emitting device 200.
Specifically, the hole transport layer 302 may be prepared on the hole injection layer 301 by spin coating or printing.
In an embodiment, the material of the hole transport layer 302 is an organic material with hole transport capability or an inorganic material with hole transport capability. In one embodiment, the organic material having hole transporting capability includes at least one 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, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), doped graphene, undoped graphene, and C60. In one embodiment, the inorganic material with hole transport capability comprises doped or undoped NiO, WO 3 、MoO 3 And at least one of CuO.
In one embodiment, the hole transport layer 302 has a thickness of 10nm to 100nm. Specifically, the thickness of the hole transport layer 302 may be 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 100nm, and the like.
At least one embodiment of the present disclosure provides a method for manufacturing the light emitting device, including the steps of:
step S21, providing a cathode substrate.
In one embodiment, the cathode substrate comprises Al (aluminum), ag (silver), cu (copper), mo (molybdenum), au (gold), ba (barium), ca (calcium), mg (magnesium), graphite, carbon nanotubes, graphene, carbon fibers,ITO (indium doped tin oxide), FTO (fluorine doped tin oxide), ATO (antimony doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped zinc oxide), IZO (indium doped zinc oxide), MZO (magnesium doped zinc oxide), AMO (aluminum doped magnesium oxide), AZO/Ag/AZO (aluminum doped zinc oxide/silver/aluminum doped zinc oxide), AZO/Al/AZO (aluminum doped zinc oxide/aluminum doped zinc oxide), ITO/Ag/ITO (indium doped tin oxide/silver/indium doped tin oxide), ITO/Al/ITO (indium doped tin oxide/aluminum/indium doped tin oxide), znO/Ag/ZnO (zinc oxide/silver/zinc oxide), znO/Al/ZnO (zinc oxide/aluminum/zinc oxide), tiO 2 /Ag/TiO 2 (titanium oxide/silver/titanium oxide) and TiO 2 /Al/TiO 2 At least one of (titanium oxide/aluminum/titanium oxide).
In an embodiment, the thickness of the cathode substrate may be 15nm-100nm. Specifically, the thickness of the cathode substrate may be 15nm, 30nm, 40nm, 50nm, 60nm, 80nm, 100nm, etc.
Step S22, preparing an electron transport layer 50 on the cathode substrate.
Specifically, the electron transport layer 50 may be prepared on the cathode substrate by spin coating or printing.
In one embodiment, the material of the electron transport layer 50 includes zinc oxide (ZnO) and titanium dioxide (TiO 2 ) At least one of them.
In one embodiment, the electron transport layer 50 has a thickness of 15nm to 60nm. Specifically, the thickness of the electron transport layer 50 may be 15nm, 30nm, 45nm, 60nm, etc.
Step S23, preparing the light emitting layer 40 on the electron transport layer 50.
Specifically, the light emitting layer 40 may be prepared on the electron transport layer 50 by spin coating or printing.
In an embodiment, the light emitting layer 40 may be an organic light emitting layer or a quantum dot light emitting layer. In an embodiment, the quantum dot light emitting layer is a red light quantum dot light emitting layer, a green light quantum dot light emitting layer, or a blue light quantum dot light emitting layer. Preferably, the quantum dot light emitting layer is a blue light quantum dot light emitting layer.
In an embodiment, the blue light quantum dot light emitting layer includes at least one of blue light quantum dots of a single structure and blue light quantum dots of a core-shell structure. Specifically, the blue light quantum dot of the core-shell structure comprises at least one of CdSe@ZnS blue light quantum dot and ZnCdS@ZnS blue light quantum dot. In one embodiment, the particle size of the CdSe@ZnS blue light quantum dots is 3 nm-6 nm. In one embodiment, the particle size of the ZnCdS@ZnS blue light quantum dots is 8 nm-15 nm. It should be noted that "cdse@zns" means ZnS coated CdSe, and "zncds@zns" means ZnS coated ZnCdS.
In one embodiment, the thickness of the light emitting layer 40 is 10nm-60nm. Specifically, the thickness of the light emitting layer 40 may be 10nm, 15nm, 20nm, 25nm, 30nm, 40nm, 50nm, 60nm, etc.
Step S24, preparing a hole function layer 30 on the light emitting layer 40.
Specifically, the hole function layer 30 may be prepared on the light emitting layer 40 by spin coating or printing.
In one embodiment, the hole-functional layer 30 includes a hole-injecting layer 301. The material of the hole injection layer 301 may be selected from materials having hole injection capability. In one embodiment, the material of the hole injection layer 301 includes at least one of poly (3, 4-ethylenedioxythiophene) (PEDOT), 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 polyestercarbonate (CuPc), transition metal oxide, and transition metal chalcogenide.
In one embodiment, the hole injection layer 301 has a thickness of 20nm to 120nm. Specifically, the thickness of the hole injection layer 301 may be 20nm, 40nm, 60nm, 80nm, 100nm, 120nm, and the like.
Step S25, preparing an auxiliary layer 20 on the hole function layer 30.
Specifically, the auxiliary layer 20 is prepared on the hole function layer 30 by a sputtering method.
In one embodiment, the material of the auxiliary layer 20 includes doped or undoped metal oxideAnd (3) chemical compounds. In an embodiment, in the doped or undoped metal oxide, the metal oxide includes at least one of tin oxide, zinc oxide, magnesium oxide, and titanium oxide, and the doped element includes at least one of indium, fluorine, antimony, aluminum, gallium, and magnesium. Specifically, the doped or undoped metal oxide includes ITO (indium doped tin oxide), FTO (fluorine doped tin oxide), ATO (antimony doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped zinc oxide), IZO (indium doped zinc oxide), MZO (magnesium doped zinc oxide), AMO (aluminum doped magnesium oxide), zinc oxide (ZnO), zinc sulfide (ZnS), and titanium oxide (TiO) 2 ) At least one of them.
In one embodiment, the mass fraction of the doped element in the doped metal oxide is 20% to 50%. In particular, in the doped metal oxide, the mass fraction of the doped element may be 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc.
In an embodiment, the auxiliary layer 20 is a laminated structure, and the material of the auxiliary layer 20 further includes metal. The specific structure of the auxiliary layer 20 is as follows: doped or undoped metal oxide/metal material/doped or undoped metal oxide.
In one embodiment, the metal comprises at least one of silver and aluminum. Specifically, the specific structure of the auxiliary layer 20 includes AZO/Ag/AZO (aluminum doped zinc oxide/silver/aluminum doped zinc oxide), AZO/Al/AZO (aluminum doped zinc oxide/aluminum doped zinc oxide), ITO/Ag/ITO (indium doped tin oxide/silver/indium doped tin oxide), ITO/Al/ITO (indium doped tin oxide/aluminum/indium doped tin oxide), znO/Ag/ZnO (zinc oxide/silver/zinc oxide), znO/Al/ZnO (zinc oxide/aluminum/zinc oxide), and TiO 2 /Ag/TiO 2 (titanium oxide/silver/titanium oxide) and TiO 2 /Al/TiO 2 At least one of (titanium oxide/aluminum/titanium oxide).
In one embodiment, the thickness of the auxiliary layer 20 is 1nm to 20nm, preferably 1nm to 15nm. Specifically, the thickness of the auxiliary layer 20 may be 1nm, 3nm, 5nm, 7nm, 9nm, 11nm, 13nm, 15nm, 17nm, 19nm, 20nm, etc.
Step S26, preparing the anode 10 on the auxiliary layer 20.
In one embodiment, the anode 10 comprises Al (aluminum), ag (silver), cu (copper), mo (molybdenum), au (gold), ba (barium), ca (calcium), mg (magnesium), graphite, carbon nanotube, graphene, carbon fiber, ITO (indium doped tin oxide), FTO (fluorine doped tin oxide), ATO (antimony doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped zinc oxide), IZO (indium doped zinc oxide), MZO (magnesium doped zinc oxide), AMO (aluminum doped magnesium oxide), AZO/Ag/AZO (aluminum doped zinc oxide/silver/aluminum doped zinc oxide), AZO/Al/AZO (aluminum doped zinc oxide/aluminum doped zinc oxide), ITO/Ag/ITO (indium doped tin oxide/silver/indium doped tin oxide), ITO/ITO (indium doped tin oxide/aluminum/indium doped tin oxide), znO/Ag/ZnO (zinc oxide/silver/zinc oxide), znO/Al/ZnO (zinc oxide/aluminum/zinc oxide), tiO/Al/ZnO (aluminum/zinc oxide) 2 /Ag/TiO 2 (titanium oxide/silver/titanium oxide) and TiO 2 /Al/TiO 2 At least one of (titanium oxide/aluminum/titanium oxide).
In one embodiment, the anode 10 may have a thickness of 10nm to 100nm. Specifically, the thickness of the anode 10 may be 10nm, 20nm, 30nm, 50nm, 60nm, 80nm, 100nm, etc.
Step S27, capping layer 70 (CPL) is formed on the side of the cathode substrate remote from the electron transport layer 50.
Wherein the capping layer 70 helps to prevent external moisture and oxygen from penetrating into the light emitting device 100. In an embodiment, the capping layer 70 may be an organic layer or an inorganic layer. In one embodiment, the material of the organic layer may include α -NPD, NPB, TPD, m-MTDATA, alq3, cuPc, N4' -tetrakis (biphenyl-4-yl) biphenyl-4, 4' -diamine (TPD 15), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), or the like, epoxy resins or acrylates such as methacrylates, or combinations thereof. In one embodiment, the material of the inorganic layer may include an alkali metal compound such as LiF, an alkali metal compound such as MgF 2 、SiON、SiN x Or SiO y An alkaline earth metal compound, or the like, or a combination thereof.
Step S28, preparing the encapsulation layer 80 on the capping layer 70, thereby obtaining the light emitting device 100.
Wherein the encapsulation layer 80 serves to further prevent external moisture and oxygen from penetrating into the light emitting device 100 and to protect the light emitting device 100.
In another embodiment, in step S24, the hole-functional layer 30 includes not only the hole-injecting layer 301 but also a hole-transporting layer 302, and the hole-transporting layer 302 is located between the hole-injecting layer 301 and the light-emitting layer 40, so as to obtain the light-emitting device 200.
Specifically, the hole transport layer 302 may be prepared on the light emitting layer 40 by spin coating or printing.
In an embodiment, the material of the hole transport layer 302 is an organic material with hole transport capability or an inorganic material with hole transport capability. In one embodiment, the organic material having hole transporting capability includes at least one 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, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), doped graphene, undoped graphene, and C60. In one embodiment, the inorganic material with hole transport capability comprises doped or undoped NiO, WO 3 、MoO 3 And at least one of CuO.
In one embodiment, the hole transport layer 302 has a thickness of 10nm to 100nm. Specifically, the thickness of the hole transport layer 302 may be 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 100nm, and the like.
At least one embodiment of the present disclosure provides a display apparatus including the light emitting device 100, or the light emitting device 200, or a light emitting device prepared by the preparation method.
The present disclosure is further described below.
Firstly, directly printing a hole injection layer on a printing substrate (namely an anode substrate) to obtain a device I; sputtering an auxiliary layer on the same printing substrate, and printing a hole injection layer on the auxiliary layer to obtain a second device. And observing the morphology of the first device and the morphology of the second device respectively.
The results show that after printing the hole injection layer, the morphology of device one and device two are significantly optimized compared to before printing the hole injection layer.
And (II) performing slice analysis on the first device and the second device respectively.
Referring to fig. 4 and 5, it can be seen that the anode in the second device has a smoother and more uniform thickness and a smoother and clearer interface than that in the first device.
(III) preparing hole injection layer/hole transport layer/blue light quantum dot light emitting layer/MoO on the print substrate without sputtering auxiliary layer, with auxiliary layer of sputtering thickness of 1nm and with auxiliary layer of sputtering thickness of 15nm respectively 3 And/cathode, three HOD devices were obtained. JV data for three HOD devices were tested separately.
Referring to fig. 6, it can be seen that the hole transporting capability of the HOD device sputtered with the auxiliary layer is significantly improved compared to the HOD device without the auxiliary layer.
And (IV) respectively preparing an electron transmission layer/a blue light quantum dot luminous layer/an electron transmission layer/a cathode on the printing substrate without the sputtering auxiliary layer, with the sputtering auxiliary layer with the thickness of 1nm and with the sputtering auxiliary layer with the thickness of 15nm, so as to obtain three EOD devices. JV data for three EOD devices were tested separately.
Referring to fig. 7, it can be seen that the electron transport capability of the EOD device sputtered with the auxiliary layer is significantly improved as compared with the EOD device without the auxiliary layer.
The present disclosure provides the auxiliary layer 20 between the anode 10 and the hole injection layer 301, and since the auxiliary layer 20 can reduce the energy level difference between the anode 10 and the hole injection layer 301, the auxiliary layer 20 improves the transport capacity of hole carriers and electron carriers and also improves the recombination rate of hole carriers and electron carriers in the light emitting layer 40, thereby improving the light emitting efficiency, the service life and the stability of the light emitting device 100.
The present disclosure is described in detail below by way of examples and comparative examples.
Example 1
(1) Preparing a printing substrate (namely an anode substrate), cleaning the printing substrate by using a detergent, isopropanol and deionized water in an ultrasonic cleaner, treating the printing substrate for 2-5 minutes by using a UV-ozone cleaner, enabling the printing substrate not to carry out long-time UV, damaging a hydrophilic layer and a hydrophobic layer of the printing substrate, and then putting the printing substrate into a vacuum dust-free oven to heat the printing substrate to 230 ℃ for baking for 30 minutes.
(2) And transferring the cleaned and baked printing substrate into sputtering equipment for sputtering to obtain an ITO auxiliary layer with the thickness of 1nm, and performing ion bombardment on the printing substrate in the sputtering process to enable the printing substrate to be more even and uniform, so that the auxiliary layer is even and uniform.
(3) Manufacturing a hole injection layer on the ITO auxiliary layer, and printing the hole injection layer by using a Dimatix printing device or a loose RGB large printing device; the VCD conditions used optimal conditions 1000Pa5min+high VCD 2min, and the film post-annealing process was air heating at 230℃for 15-30min.
(4) Manufacturing a hole transport layer on the surface of the hole injection layer, and printing by using a Dimatix printing device or a loose RGB large printing device; the VCD conditions use the optimum conditions 10000Pa5min+high VCD 2min and are N 2 And (3) performing a post annealing process in the environment: heating at 200deg.C for 30min.
(5) Blue quantum dot light emitting layer (BQD) is manufactured on the hole transport layer, and printing is performed by using a Dimatix printing device or a loose RGB large printing device, wherein the VCD condition uses the optimal condition 3Pa5min+high VCD 2min and is N 2 And (3) performing a post annealing process in the environment: heating at 80deg.C for 15min.
(6) Producing an electron transport layer on a blue light emitting layer (BQD), printing using a Dimatix printing device or a loose RGB printing device, and using optimal conditions 10000Pa9min+high VCD 1min for VCD conditions and N 2 And (3) performing a post annealing process in the environment: heating at 100deg.C for 15min.
(7) Device for printingTransferring to a high vacuum evaporator at 10 -5 Under pa pressure, in the range ofIs deposited at a rate of +.>Is coated with a capping layer.
(8) Packaging with a white glass groove cover plate using packaging adhesive, packaging the sample with ultraviolet light cured resin (Pulse Puretone 20-001) to obtain packaging layer, and packaging under N 2 Preserving in the environment.
(9) And heating the packaged device to 140 ℃ and keeping the temperature for 15min to obtain the light-emitting device.
Example 2
Example 2 differs from example 1 in that: in step (2), the thickness of the prepared ITO auxiliary layer was 3nm.
Example 3
Example 3 differs from example 1 in that: in the step (2), the thickness of the prepared ITO auxiliary layer was 5nm.
Example 4
Example 4 differs from example 1 in that: in the step (2), the thickness of the prepared ITO auxiliary layer was 7nm.
Example 5
Example 5 differs from example 1 in that: in the step (2), the thickness of the prepared ITO auxiliary layer was 15nm.
Example 6
Example 6 differs from example 1 in that: in the step (2), the thickness of the prepared ITO auxiliary layer is 15nm; step (4) is omitted.
Example 7
Example 7 differs from example 1 in that: and (3) changing the ITO auxiliary layer in the step (2) into an IZO auxiliary layer.
Example 8
Example 8 differs from example 1 in that: and (3) changing the ITO auxiliary layer in the step (2) into a ZnO/Ag/ZnO auxiliary layer.
Comparative example 1
Comparative example 1 differs from example 1 in that: the ITO auxiliary layer is prepared without sputtering.
Use of 63.7mA/cm 2 The light emitting devices prepared in examples 1 to 5 and comparative example 1 were respectively tested for decay to a lifetime of T95.
Description: examples 1 to 5 and comparative example 1 each prepared 3 light emitting devices, and each corresponding 3 light emitting devices were tested for decay to a lifetime of T95 to ensure accuracy of data. Thus, there are 3 data in the corresponding oxide layer of the same thickness in fig. 8. The drawings are similar and will not be described in detail later.
And (3) injection: LT95@1000nit means that the light emitting device has an initial luminance of 1000cd/m 2 Continuously lit down when the luminance decays to 95% of the initial luminance (here 950cd/m 2 ) Time elapsed.
Referring to fig. 8, the time elapsed for the luminance decay of the light emitters prepared in examples 1-5 to 95% of the initial luminance was longer than the time elapsed for the luminance decay of the light emitting device prepared in comparative example 1 to 95% of the initial luminance, and the time elapsed for the luminance decay of the light emitting device prepared in examples 1-3 to 95% of the initial luminance was longer. This shows that the auxiliary layer can improve the lifetime of the light emitting device, and the thickness of the auxiliary layer can also have a certain effect on the lifetime of the light emitting device.
(II) the light emitting devices prepared in examples 1 to 5 and comparative example 1 were tested for efficiency, voltage and JV data, respectively.
Referring to fig. 9 to 12, it is understood that the light emitting devices prepared in examples 1 to 5 have electrical properties superior to those of the light emitting device prepared in comparative example 1, and that the light emitting device prepared in example 1 (i.e., the auxiliary layer has a thickness of 1 nm) has the optimal electrical properties.
(III) use of 63.7mA/cm 2 The light emitting devices prepared in examples 6 to 8 were respectively tested for lifetime of decay to T95 and efficiency of the light emitting device, and the test results are shown in table 1 below.
Description: examples 6-8 two batches of light emitting devices were prepared separately and the first and second batches of corresponding light emitting devices were tested for decay to a lifetime of T95, respectively, to ensure data accuracy. In addition, the efficiency of the light emitting device was also tested in two batches.
TABLE 1 lifetime of light emitting devices prepared in examples 6 to 8, respectively, decayed to T95 and efficiency of light emitting device
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples represent only a few embodiments of the present disclosure, which are described in more detail and detail, but are not to be construed as limiting the scope of the disclosure. It should be noted that variations and modifications can be made by those skilled in the art without departing from the spirit of the disclosure, which are within the scope of the disclosure. Accordingly, the scope of protection of the present disclosure should be determined by the following claims.
Claims (11)
1. A light emitting device comprising an anode, a cathode, a light emitting layer between the anode and the cathode, and a hole function layer between the anode and the light emitting layer, characterized in that the light emitting device further comprises an auxiliary layer between the anode and the hole function layer, the auxiliary layer comprising a material comprising a doped or undoped metal oxide.
2. The light-emitting device according to claim 1, wherein in the doped or undoped metal oxide, the metal oxide includes at least one of tin oxide, zinc oxide, magnesium oxide, and titanium oxide, and the doped element includes at least one of indium, fluorine, antimony, aluminum, gallium, and magnesium;
or, the doped or undoped metal oxide comprises at least one of indium doped tin oxide, fluorine doped tin oxide, antimony doped tin oxide, aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide, magnesium doped zinc oxide, aluminum doped magnesium oxide, zinc sulfide and titanium oxide;
and/or, in the doped metal oxide, the mass fraction of the doped element is 20% -50%.
3. The light-emitting device according to any one of claims 1 to 2, wherein the auxiliary layer has a laminated structure, and a material of the auxiliary layer further comprises a metal, and the auxiliary layer has a specific structure of: doped or undoped metal oxide/metal material/doped or undoped metal oxide, wherein the metal comprises at least one of silver and aluminum;
or, the specific structure of the auxiliary layer comprises at least one of aluminum doped zinc oxide/silver/aluminum doped zinc oxide, aluminum doped zinc oxide/aluminum doped zinc oxide, indium doped tin oxide/silver/indium doped tin oxide, indium doped tin oxide/aluminum/indium doped tin oxide, zinc oxide/silver/zinc oxide, zinc oxide/aluminum/zinc oxide, titanium oxide/silver/titanium oxide and titanium oxide/aluminum/titanium oxide;
And/or the thickness of the auxiliary layer is 1nm-20nm or 1nm-15nm.
4. A light-emitting device according to any one of claims 1 to 3, further comprising an electron transport layer between the light-emitting layer and the cathode;
wherein the material of the electron transport layer comprises ZnO and TiO 2 At least one of (a) and (b);
and/or the thickness of the electron transport layer is 15nm-60nm;
and/or the light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer;
and/or the thickness of the light-emitting layer is 10nm-60nm.
5. The light-emitting device of claim 4, wherein the quantum dot light-emitting layer is a red light quantum dot light-emitting layer, a green light quantum dot light-emitting layer, or a blue light quantum dot light-emitting layer;
the blue light quantum dot luminescent layer comprises at least one of blue light quantum dots with a single structure and blue light quantum dots with a core-shell structure, and the blue light quantum dots with the core-shell structure comprise at least one of CdSe@ZnS blue light quantum dots and ZnCdS@ZnS blue light quantum dots;
the green light quantum dot light emitting layer comprises quantum dots of at least one of the following materials: cdSe/CdZnSe alloy, inP and CuInS 2 、AgInS 2 CdTe, cdSe/Te alloys;
The red light quantum dot luminescent layer comprises quantum dots of at least one of the following materials: pbSe/Te, pbS, inAs, cuInSe 2 、Cd 3 As 2 、Cd 3 P 2 、CdTe、AgInS 2 ；
And/or the material of the organic light emitting layer comprises at least one of 4,4' -bis (N-carbazole) -1,1' -biphenyl, tris [2- (p-tolyl) pyridine-C2, N) iridium (III), 4' -tris (carbazole-9-yl) triphenylamine, tris [2- (p-tolyl) pyridine-C2, N) iridium, biaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials and DBP fluorescent materials, polyacetylene and derivatives thereof, poly-p-benzene and derivatives thereof, polythiophene and derivatives thereof, polyfluorene and derivatives thereof;
and/or the hole functional layer comprises a hole transport layer and/or a hole injection layer, the material of the hole transport layer comprises an organic material with hole transport capability or an inorganic material with hole transport capability, the organic material with hole transport capability comprises 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 '-tris (carbazole-9-yl) triphenylamine (TCTA), 4' -bis (9-Carbazole) Biphenyl (CBP), N '-diphenyl-N, N' -bis (3-17-room-temperature-end-treated material At least one of 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 and C60, wherein the inorganic material with hole transport capability comprises doped or undoped NiO, WO 3 、MoO 3 And at least one of CuO, the material of the hole injection layer includes at least one of poly (3, 4-ethylenedioxythiophene) (PEDOT), 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 polyestercarbonate (CuPc), transition metal oxide, and transition metal chalcogenide;
and/or the material of the anode and/or the cathode comprises Al, ag, cu, mo, au, ba, ca, mg, graphite, carbon nano tube, graphene, carbon fiber, ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO, AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, znO/Ag/ZnO, znO/Al/ZnO, znS/Ag/ZnS, znS/Al/ZnS, tiO 2 /Ag/TiO 2 TiO 2 /Al/TiO 2 At least one of them.
6. A method of manufacturing a light emitting device, comprising the steps of:
Providing an anode substrate, and preparing an auxiliary layer on the anode substrate;
preparing a hole function layer on the auxiliary layer;
preparing a light emitting layer on the hole function layer; and
preparing a cathode on the light-emitting layer to obtain a light-emitting device;
or providing a cathode substrate and preparing a light-emitting layer on the cathode substrate;
preparing a hole function layer on the light emitting layer;
preparing an auxiliary layer on the hole functional layer;
preparing an anode on the auxiliary layer to obtain a light-emitting device;
wherein the material of the auxiliary layer comprises doped or undoped metal oxide.
7. The method of manufacturing a light-emitting device according to claim 6, wherein in the doped or undoped metal oxide, the metal oxide includes at least one of tin oxide, zinc oxide, magnesium oxide, and titanium oxide, and the doped element includes at least one of indium, fluorine, antimony, aluminum, gallium, and magnesium;
or, the doped or undoped metal oxide comprises at least one of indium doped tin oxide, fluorine doped tin oxide, antimony doped tin oxide, aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide, magnesium doped zinc oxide, aluminum doped magnesium oxide, zinc sulfide and titanium oxide;
And/or, in the doped metal oxide, the mass fraction of the doped element is 20% -50%.
8. The method for manufacturing a light-emitting device according to any one of claims 6 to 7, wherein the auxiliary layer has a laminated structure, and the material of the auxiliary layer further comprises a metal, and the specific structure of the auxiliary layer is: doped or undoped metal oxide/metal material/doped or undoped metal oxide, wherein the metal comprises at least one of silver and aluminum;
or, the specific structure of the auxiliary layer comprises at least one of aluminum doped zinc oxide/silver/aluminum doped zinc oxide, aluminum doped zinc oxide/aluminum doped zinc oxide, indium doped tin oxide/silver/indium doped tin oxide, indium doped tin oxide/aluminum/indium doped tin oxide, zinc oxide/silver/zinc oxide, zinc oxide/aluminum/zinc oxide, titanium oxide/silver/titanium oxide and titanium oxide/aluminum/titanium oxide;
and/or the thickness of the auxiliary layer is 1nm-20nm or nm-15nm.
9. The method for manufacturing a light-emitting device according to any one of claims 6 to 8, wherein after manufacturing the light-emitting layer and before manufacturing the cathode, the manufacturing method further comprises the steps of:
Preparing an electron transport layer on the light emitting layer;
or, before the light emitting layer is prepared on the cathode substrate, the preparation method further comprises the steps of:
an electron transport layer is prepared on the cathode substrate.
10. The method for manufacturing a light-emitting device according to claim 9, wherein the material of the electron transport layer comprises ZnO and TiO 2 At least one of (a) and (b);
and/or the thickness of the electron transport layer is 15nm-60nm;
and/or the light-emitting layer is an organic light-emitting layer or a quantum dot light-emitting layer;
and/or the thickness of the light-emitting layer is 10nm-60nm.
11. A display apparatus comprising the light-emitting device according to any one of claims 1 to 5 or a light-emitting device produced by the production method according to any one of claims 6 to 10.
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