CN114023912A - Photoelectronic device based on rare earth oxide - Google Patents
Photoelectronic device based on rare earth oxide Download PDFInfo
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- CN114023912A CN114023912A CN202111312318.XA CN202111312318A CN114023912A CN 114023912 A CN114023912 A CN 114023912A CN 202111312318 A CN202111312318 A CN 202111312318A CN 114023912 A CN114023912 A CN 114023912A
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- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 28
- 238000002347 injection Methods 0.000 claims abstract description 95
- 239000007924 injection Substances 0.000 claims abstract description 95
- 239000000463 material Substances 0.000 claims abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 22
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 22
- 230000005525 hole transport Effects 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 19
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 230000005693 optoelectronics Effects 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- HRQXKKFGTIWTCA-UHFFFAOYSA-L beryllium;2-pyridin-2-ylphenolate Chemical compound [Be+2].[O-]C1=CC=CC=C1C1=CC=CC=N1.[O-]C1=CC=CC=C1C1=CC=CC=N1 HRQXKKFGTIWTCA-UHFFFAOYSA-L 0.000 claims description 11
- 230000007704 transition Effects 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- IWZZBBJTIUYDPZ-DVACKJPTSA-N (z)-4-hydroxypent-3-en-2-one;iridium;2-phenylpyridine Chemical compound [Ir].C\C(O)=C\C(C)=O.[C-]1=CC=CC=C1C1=CC=CC=N1.[C-]1=CC=CC=C1C1=CC=CC=N1 IWZZBBJTIUYDPZ-DVACKJPTSA-N 0.000 claims description 7
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical group C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 claims description 7
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 142
- 238000010586 diagram Methods 0.000 description 17
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052769 Ytterbium Inorganic materials 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 2
- 229940075624 ytterbium oxide Drugs 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/813—Anodes characterised by their shape
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
- H10K50/822—Cathodes characterised by their shape
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a rare earth oxide-based photoelectronic device, which comprises a substrate, an anode, a hole injection layer, a hole transport layer, an electroluminescent unit, an electron transport layer, an electron injection layer and a cathode, wherein the substrate, the anode, the hole injection layer, the hole transport layer, the electroluminescent unit, the electron transport layer, the electron injection layer and the cathode are sequentially arranged from bottom to top; a first connecting end is arranged on the side surface of the anode; the top surface of the cathode is provided with a second connecting end; the first connecting end and the second connecting end are respectively connected with the positive pole and the negative pole of a power supply. According to the invention, the anode, the hole injection layer, the hole transport layer, the electroluminescent unit, the electron transport layer, the electron injection layer and the cathode with fixed thicknesses are arranged, so that the problem that the doping proportion is difficult to determine when rare earth metal powder and rare earth oxide are doped as materials of the electron injection layer in the prior art is solved, and the stability of the photoelectronic device is improved.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a photoelectronic device based on rare earth oxide.
Background
Since the advent of organic light-emitting diodes (OLEDs) in 1987, organic light-emitting diodes (OLEDs) have found wide application in the high performance display and lighting fields due to their advantages of being ultra-thin, low energy consumption, self-emissive, color tunable, wide color gamut, flexible, etc. An OLED device is a thin film device that converts electrical energy into light energy, and the structure of the device includes an anode, a cathode, and an organic light emitting layer and an organic transport layer disposed between two injection electrodes. Electrons and holes are injected from the two electrodes, transported through the organic layer, and finally recombined to emit light in the light emitting layer. Under the drive of an external voltage, electrons reach the organic light-emitting layer through the electron injection layer and the transmission layer, and form excitons with holes passing through the hole injection layer and the transmission layer in the organic light-emitting layer, so that organic light-emitting molecules are in an excited state, the excited state with high energy is recombined through carriers, energy is radiated in the form of emitted photons, and finally, a photoelectric conversion process (the process is called as radiation light emission) is realized.
The lowest-occupied-state molecular orbital (LUMO) level commonly used as an electron transport material is in the vicinity of-3.0 eV, while the work function of a metal cathode in contact therewith is generally greater than-4.0 eV, and therefore, when electrons are directly injected from the metal cathode into the electron transport layer, there is a large energy gap to hinder the injection of electrons, so that the device driving voltage is high, and at the same time, electron holes reaching the light emitting layer are unbalanced, thereby lowering the device efficiency and shortening the device lifetime. The adoption of the n-type doping method can reduce the LUMO energy level of the electron transport material, reduce the energy gap and further promote the injection of electrons from the metal cathode to the electron transport layer. The mechanism of n-type doping is that the dopant transfers electrons to the LUMO level of the electron transport material, thereby achieving charge transfer and increasing the free carrier concentration. This requires that the dopant work function must be below-3.0 eV in order to efficiently transfer electrons to the LUMO level of the electron transporting material. However, the materials with work functions less than-3.0 eV, such as Li, Ca, Yb, etc., have very active chemical properties and are prone to react with other materials, so that the n-type dopants suitable for OLEDs have few species. The most common alkali metals in the prior art are easily oxidized in air, sodium, potassium, cesium and the like can even generate spontaneous combustion, are difficult to store for a long time, and are not convenient for preparation operation. In the prior patent (CN103165825B), cerium oxide or ytterbium oxide is used as an insulating layer of an organic electroluminescent device, in contact with a rare earth metal material layer. The thickness of the insulating layer is limited within the range of 0.5-2nm, however, the rare earth metal material layer is formed by doping rare earth metal powder and rare earth oxide, the doping proportion is difficult to determine, so that the optimal rare earth metal material layer cannot be obtained, and the stability of the photoelectronic device is reduced.
Disclosure of Invention
The invention aims to provide a photoelectronic device based on rare earth oxide, which can improve the stability of the photoelectronic device.
In order to achieve the purpose, the invention provides the following scheme:
a rare earth oxide based optoelectronic device comprising:
the electroluminescent device comprises a substrate, an anode, a hole injection layer, a hole transport layer, an electroluminescent unit, an electron transport layer, an electron injection layer and a cathode which are arranged from bottom to top in sequence;
a first connecting end is arranged on the side surface of the anode; the top surface of the cathode is provided with a second connecting end; the first connecting end and the second connecting end are respectively connected with the positive pole and the negative pole of a power supply.
Alternatively to this, the first and second parts may,
the thickness of the hole injection layer is 10 nm;
the thickness of the hole transport layer is 45 nm;
the thickness of the electroluminescent unit is 15 nm;
the thickness of the electron transport layer is 40nm or 45 nm;
the thickness of the electron injection layer is 0.1-8 nm.
Alternatively to this, the first and second parts may,
the anode is indium tin oxide;
the cathode is aluminum.
Alternatively to this, the first and second parts may,
and a cathode transition layer is arranged between the electron injection layer and the cathode.
Alternatively to this, the first and second parts may,
the cathode transition layer is made of rare earth metal.
Optionally, the thickness of the cathode transition layer is 4 nm.
Alternatively to this, the first and second parts may,
the anode is aluminum;
the cathode is silver or silver-magnesium alloy.
The work function of the electron injection layer is less than 3 eV.
Alternatively to this, the first and second parts may,
the substrate is glass, quartz or sapphire;
the hole injection layer is molybdenum trioxide;
the hole transport layer is TAPC;
the electroluminescent units are Bepp2 and Ir (ppy)2(acac) a mixed material;
the electron transport layer is Bepp 2;
the electron injection layer is a rare earth metal oxide; the work function of the electron injection layer is less than 3 eV.
Optionally, Ir (ppy) in the mixed material2The proportion of (acac) was 8%.
According to the specific embodiment provided by the invention, the invention discloses the following technical effects:
the invention provides a rare earth oxide-based photoelectronic device, which comprises a substrate, an anode, a hole injection layer, a hole transport layer, an electroluminescent unit, an electron transport layer, an electron injection layer and a cathode which are sequentially arranged from bottom to top; a first connecting end is arranged on the side surface of the anode; the top surface of the cathode is provided with a second connecting end; the first connecting end and the second connecting end are respectively connected with the positive pole and the negative pole of a power supply. According to the invention, the anode, the hole injection layer, the hole transport layer, the electroluminescent unit, the electron transport layer, the electron injection layer and the cathode with fixed thicknesses are arranged, so that the problem that the doping proportion is difficult to determine when rare earth metal powder and rare earth oxide are doped as materials of the electron injection layer in the prior art is solved, and the stability of the photoelectronic device is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive labor.
FIG. 1 is a schematic structural diagram of a rare earth oxide based optoelectronic device in an embodiment of the present invention;
FIG. 2 shows Yb in an example of the present invention2O3The structure diagram of the bottom-emitting first OLED device of the electron injection layer is shown;
FIG. 3 shows Yb in an embodiment of the present invention2O3An energy level structure diagram of a bottom-emitting first OLED device being an electron injection layer;
FIG. 4 shows Yb in an embodiment of the present invention2O3A graph of I-V-L test results for a bottom-emitting first OLED device for an electron injection layer; FIG. 4(a) shows Yb in an example of the present invention2O3A first I-V-L test result graph for a bottom-emitting first OLED device for an electron injection layer; FIG. 4(b) shows Yb in an example of the present invention2O3A second I-V-L test result graph for a bottom-emitting first OLED device for the electron injection layer;
FIG. 5 shows a rare earth metal Yb and the corresponding oxide Yb in an embodiment of the present invention2O3A graph of measurement results of (a);
FIG. 5(a) is a graph showing XPS measurements of a rare earth metal Yb and a corresponding oxide Yb2O3 in an example of the present invention; FIG. 5(b) is a graph showing the UPS measurements of a rare earth metal Yb and the corresponding oxide Yb2O3 in an example of the present invention;
FIG. 6 shows Yb in an embodiment of the present invention2O3An energy level diagram for a bottom emitting first OLED device being an electron injecting layer;
FIG. 7 shows Yb in an example of the present invention2O3Schematic structure of first OLED device for top emission of electron injection layer；
FIG. 8 shows Yb in an example of the present invention2O3An energy level structure diagram of a top-emitting first OLED device being an electron injection layer;
FIG. 9 shows Yb in an example of the present invention2O3A graph of I-V-L test results for a top-emitting first OLED device for an electron injection layer; FIG. 9(a) shows Yb in an example of the present invention2O3A first I-V-L test result graph for a top-emitting first OLED device for an electron injection layer; FIG. 9(b) shows Yb in an example of the present invention2O3A second I-V-L test result graph for a top-emitting first OLED device for the electron injection layer;
FIG. 10 shows Yb in an example of the present invention2O3An energy level diagram for a top-emitting first OLED device being an electron injection layer;
FIG. 11 shows Yb in an example of the present invention2O3The structure diagram of the second OLED device is top emission of the electron injection layer;
FIG. 12 shows Yb in an example of the present invention2O3An energy level structure diagram of a top-emitting second OLED device being an electron injection layer;
FIG. 13 shows Yb in an example of the present invention2O3The structure diagram of the bottom-emitting second OLED device of the electron injection layer is shown;
FIG. 14 shows Yb in an example of the present invention2O3The structure diagram of the bottom-emitting second OLED device of the electron injection layer is shown;
FIG. 15 shows Yb in an example of the present invention2O3A graph of I-V-L test results for a bottom-emitting second OLED device for the electron injection layer; FIG. 15(a) shows Yb in an example of the present invention2O3A first I-V-L test result graph for a bottom emitting second OLED device for an electron injection layer; FIG. 15(b) shows Yb in an example of the present invention2O3A second I-V-L test result graph for a bottom-emitting second OLED device for the electron injection layer;
description of the drawings: 100-a substrate; 110-an anode; 120-a hole injection layer; 130-a hole transport layer; 140-electroluminescent cell; 150-electron transport layer; 160-electron injection layer; 170-cathode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention aims to provide a photoelectronic device based on rare earth oxide, which can improve the stability of the photoelectronic device.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Example one
Fig. 1 is a schematic structural diagram of an optoelectronic device based on rare earth oxide in an embodiment of the present invention, and as shown in fig. 1, the present invention provides an optoelectronic device based on rare earth oxide, including:
a substrate 100, an anode 110, a hole injection layer 120, a hole transport layer 130, an electroluminescent unit 140, an electron transport layer 450, an electron injection layer 160, and a cathode 170, which are sequentially disposed from bottom to top;
the side surface of the anode is provided with a first connecting end; the top surface of the cathode is provided with a second connecting end; the first connecting end and the second connecting end are respectively connected with the anode and the cathode of the power supply.
Wherein the content of the first and second substances,
the thickness of the hole injection layer is 10 nm;
the hole transport layer had a thickness of 45 nm;
the thickness of the electroluminescent unit is 15 nm;
the thickness of the electron transport layer is 45 nm;
the thickness of the electron injection layer is 0.1-8 nm; the work function of the electron injection layer is less than 3 eV.
Specifically, the thickness of the electron injection layer is 4 nm;
in particular, the method comprises the following steps of,
the anode is indium tin oxide; the thickness of the anode is 100 nm;
the cathode is aluminum; the cathode thickness was 80 nm.
In particular, the method comprises the following steps of,
the substrate is glass, quartz or sapphire;
the hole injection layer is molybdenum trioxide;
the hole transport layer is TAPC;
electroluminescent units are Bepp2 and Ir (ppy)2(acac) a mixed material;
the electron transport layer is Bepp 2;
the electron injection layer is rare earth metal oxide; the work function of the electron injection layer is less than 3 eV. Specifically, the electron injection layer is an oxide of a rare earth metal, and is one of lanthanum oxide, cerium oxide, samarium oxide, gadolinium oxide, erbium oxide, yttrium oxide, and scandium oxide
In particular, Ir (ppy) in the mixed material2The proportion of (acac) was 8%.
Specifically, FIG. 2 shows Yb in an embodiment of the present invention2O3The structure of the first OLED device with bottom emission of the electron injection layer is schematically shown, wherein Light represents Light and Glass Substrate represents Glass Substrate, as shown in FIG. 2, the invention provides Yb2O3The method for preparing the bottom-emitting first OLED device of the electron injection layer comprises the following steps:
all materials (including organic materials, metal materials and oxide materials) related to the invention use a thermal evaporation process, a substrate is washed by deionized water, acetone, alcohol and other solutions in sequence, and then is transferred to a substrate frame in a vacuum chamber after being flushed by nitrogen, and the substrate frame can realize the rotation and the lifting of the substrate. The organic small molecule material is contained in a clean crucible and is evaporated by a beam source furnace, while the metal electrode material is evaporated by a heating source. The thickness of the material is controlled by a film thickness detector connected to the inside of the vacuum chamber, the deposition of all the materials is completed in the same vacuum evaporation chamber, and the vacuum degree of the vacuum chamberIs superior to 5X 10-5Pa. The evaporation of the material will be deposited in sequence according to the structure and thickness of the device.
The structure of the bottom-emitting first OLED device is shown in figure 2, the substrate is ITO glass, and the hole injection layer MoO is arranged from bottom to top in sequence3(thickness of 10nm), hole transport layer TAPC (thickness of 45nm), and light emitting layer made of phosphorescent host material Bepp2 and green doped material Ir (ppy)2(acac) (the doping proportion of the guest is 8 percent, the thickness is 15nm), the electron transport layer is Bepp2 (the thickness is 45nm), the electron injection layer is ytterbium trioxide, the thickness is 4nm, the metal aluminum is a cathode material, and the thickness is 80 nm. In order to prevent the metal aluminum from being oxidized, an NPB covering layer can be added on the outermost layer. To obtain Yb2O3Bottom emitting first OLED device for electron injection layer in Yb2O3The energy level structure diagram of the first OLED device for bottom emission of the electron injection layer is shown in fig. 3; wherein the ordinate is energy.
For a simpler understanding of the noun abbreviations of the present invention, the abbreviations, full names and functions of the terms appearing in the present invention are detailed in table 1:
TABLE 1 abbreviation, full name and function table of terms
Testing the performance of the device: by measuring the current-voltage-luminance (I-V-L) curve and the luminous efficiency results of the bottom-emitting first OLED device as shown in fig. 4, in fig. 4(a), the abscissa is voltage, the ordinate (left) is luminance, and the ordinate (right) is current density; in fig. 4(b), the abscissa is luminance, the ordinate (left) is current efficiency, and the ordinate (right) is power efficiency; yb compared to OLED devices prepared conventionally using Liq as the electron-injecting layer2O3OLED devices prepared as electron injection layers have the same turn-on voltage (2.6eV) and the sameThe current density.
Testing of the thin film electronic structure: to further illustrate the rare earth metal oxide Yb2O3In the electron injection performance of the OLED device, the composition and the electronic structure of the thin film of the rare earth metal Yb were measured by X-ray photoelectron spectroscopy (XPS).
The rare earth metal Yb easily loses two 6s electrons and one 4f electron in air and exists in a stable +3 valence state. The surface of the commercially available Yb particle is usually covered with a layer of oxide, and the Yb particle can be etched and stripped by Ar ions, so that the oxide layer on the surface is stripped, and the simple substance of the rare earth metal Yb is left. Full spectrum measurement of XPS on thin films (FIG. 5(a), in which the abscissa is binding energy and the ordinate is strength), the peak of the 4d orbital of the rare earth metal Yb was at 182.3eV, Yb2O3The peak of the 4d orbital of (2) was located at 186.5eV, thereby confirming that the surface of the rare earth metal Yb thin film was coated with a layer of oxide (Yb)2O3) And (4) covering.
In order to further analyze the valence electronic structure of rare earth metal and rare earth metal oxide, UPS for measuring Yb metal blocks before and after grinding and polishing is placed in an XPS/UPS test system, and impurities on the surface are removed by a single ion etching method and the test is carried out. FIG. 5(b) is a graph showing a rare earth metal Yb and a corresponding oxide Yb in an example of the present invention2O3A UPS measurement result graph of (a); wherein the abscissa is kinetic energy and the ordinate is intensity, as shown in FIG. 5(b), secondary electron cut-off edges can be obtained from the UPS measurements shown in FIGS. 1-5, and Yb can be calculated2O3The exact value of work function of. The work function of the energy band metal Yb is 2.64eV and the work function of the ytterbium oxide is as low as 2.42eV, so that the energy level structure of the device can be obtained according to the Yb2O3The energy level diagram for the bottom emitting first OLED device being an electron injecting layer is shown in fig. 6. EvacFor vacuum level, LUMO is the lowest occupied state, HOMO is the highest occupied state, φ is the work function, EgIs an energy gap, EfIs the Fermi level, N(E)Is the density of states.
Example two
FIG. 7 shows Yb in an example of the present invention2O3Referring to FIG. 7, the difference between this embodiment and the first embodiment is that Yb is provided in this embodiment2O3In a first OLED device that is top-emitting with an electron injection layer:
the anode is aluminum;
the cathode is silver-magnesium alloy.
In this example, Yb2O3The energy level structure of the first OLED device for top emission of the electron injection layer is as shown in fig. 8; wherein the ordinate is energy.
The preparation method of the device comprises the following steps: under vacuum condition of 5X 10-5Pa, the substrate is glass or silicon wafer, and metal anode layer Al (thickness of 100nm) and hole injection layer MoO are sequentially evaporated from bottom to top by using thermal evaporation equipment3(thickness of 10nm), hole transport layer TAPC (thickness of 45nm), and light-emitting layer made of phosphorescence host material Bepp2 and green doping material Ir (ppy)2(acac) (the doping proportion of the object is 8 percent, the thickness is 15nm), the electron transport layer is Bepp2 (the thickness is 45nm), the electron injection layer is the oxide of the rare earth ytterbium, the thickness is 4nm, the metal aluminum is the cathode material, and the thickness is 80 nm. In order to prevent the metal aluminum from being oxidized, an NPB covering layer can be added on the outermost layer.
Testing the performance of the device: by measuring the current-voltage-luminance (I-V-L) curve and luminous efficiency results (FIG. 9, in FIG. 9(a), the abscissa is voltage, the ordinate (left) is luminance, and the ordinate (right) is current density; in FIG. 9(b), the abscissa is luminance, the ordinate (left) is current efficiency, and the ordinate (right) is power efficiency) of the top-emitting first OLED device, Yb is compared to that of an OLED device conventionally prepared using Liq as an electron injection layer2O3The OLED devices prepared as electron injection layers have the same turn-on voltage and the same current density. In Yb2O3An energy level diagram for the bottom emitting first OLED device for the electron injection layer is shown in figure 10,
EXAMPLE III
FIG. 11 shows Yb in an example of the present invention2O3The structure diagram of the second OLED device is top emission of the electron injection layer; as shown in FIG. 11, the difference between this embodiment and the second embodiment is that Yb is provided in this embodiment2O3In a second OLED device that is top-emitting with an electron injection layer:
the anode is aluminum;
the cathode is silver. The thickness of the cathode is 15 nm;
the thickness of the electron transport layer is 40 nm;
the thickness of the electron injection layer is 8 nm;
the preparation method of the device comprises the following steps: depositing a layer of metal aluminum (Al) with the thickness of 100nm on a glass substrate as an anode, and evaporating a layer of molybdenum trioxide (MoO3) with the thickness of 10nm as a hole injection layer and MoO to improve the hole transmission efficiency3In contact with the film was a hole-transporting layer TAPC of 45nm thickness based on Bepp2 and Ir (ppy)2(acac) is a phosphorescent guest (the doping proportion of the guest is 8 wt%, the thickness is 15nm) as a luminescent layer, Bepp2 is an electron transport layer, the thickness is 40nm, Yb2O3As an electron injection layer, a laminated electrode having a thickness varying from 4nm to 8nm and a cathode made of Ag (15nm) metal was used.
In this example, Yb2O3The energy level structure of the second OLED device for top emission of the electron injection layer is as shown in fig. 12; wherein the ordinate is energy.
Example four
FIG. 13 shows Yb in an example of the present invention2O3The structure diagram of the bottom-emitting second OLED device of the electron injection layer is shown; as shown in fig. 13, the difference between this embodiment and the first embodiment is that, in the bottom-emitting second OLED device provided in this embodiment:
a cathode transition layer is arranged between the electron injection layer and the cathode.
The cathode transition layer is made of rare earth metal. The cathode transition layer can also be a transition metal oxide;
the thickness of the cathode transition layer is 4 nm.
The thickness of the electron transport layer is 40 nm;
in order to improve the hole transport efficiency, the bottom-emitting OLED device prepared in this example uses ITO glass as an anode, and a layer of 10nm molybdenum trioxide (MoO3) thin film is evaporated as a hole injection layer, a hole transport layer TAPC is in contact with the MoO3 thin film, the thickness is 45nm, Bepp2 is used as a host, ir (ppy)2(acac) is used as a phosphorescent guest (the doping ratio of the guest is 8 wt%, the thickness is 15nm) is used as a light-emitting layer, Bepp2 is used as an electron transport layer, the thickness is 40nm, Yb2O3 is used as an electron injection layer, the thickness is 4nm, and the cathode is a laminated electrode composed of rare earth ytterbium Yb (4nm) and metal Al (100 nm).
In Yb2O3The energy level structure diagram of the second OLED device, which is bottom emission of the electron injection layer, is shown in fig. 14, in which the ordinate is energy.
Testing the performance of the device: it can be seen from FIG. 15(a) showing voltage on the abscissa, luminance on the ordinate, and current density on the ordinate, and L-I-V characteristic curve shown in FIG. 15(b) that the bottom-emitting OLED device in which Yb2O3 is the electron injection layer and Liq is the electron injection layer has the same turn-on voltage (2.6V) and the same current density, and also has the same EL spectrum, that Yb2O3 can be used as the electron injection layer in combination with the stacked electrode composed of Yb and Al, and has the same device performance as the conventional single-layer electrode, and also has very good electron injection performance.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. Meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (9)
1. An optoelectronic device based on rare earth oxides, comprising:
the electroluminescent device comprises a substrate, an anode, a hole injection layer, a hole transport layer, an electroluminescent unit, an electron transport layer, an electron injection layer and a cathode which are arranged from bottom to top in sequence;
a first connecting end is arranged on the side surface of the anode; the top surface of the cathode is provided with a second connecting end; the first connecting end and the second connecting end are respectively connected with the positive pole and the negative pole of a power supply.
2. The rare earth oxide-based optoelectronic device according to claim 1,
the thickness of the hole injection layer is 10 nm;
the thickness of the hole transport layer is 45 nm;
the thickness of the electroluminescent unit is 15 nm;
the thickness of the electron transport layer is 40nm or 45 nm;
the thickness of the electron injection layer is 0.1-8 nm.
3. The rare earth oxide-based optoelectronic device according to claim 1,
the anode is indium tin oxide;
the cathode is aluminum.
4. The rare earth oxide-based optoelectronic device according to claim 3,
and a cathode transition layer is arranged between the electron injection layer and the cathode.
5. The rare earth oxide-based optoelectronic device according to claim 4,
the cathode transition layer is made of rare earth metal.
6. A rare earth oxide based optoelectronic device according to claim 5, wherein the thickness of the cathode transition layer is 4 nm.
7. The rare earth oxide-based optoelectronic device according to claim 1,
the anode is aluminum;
the cathode is silver or silver-magnesium alloy.
The work function of the electron injection layer is less than 3 eV.
8. The rare earth oxide-based optoelectronic device according to claim 1,
the substrate is glass, quartz or sapphire;
the hole injection layer is molybdenum trioxide;
the hole transport layer is TAPC;
the electroluminescent units are Bepp2 and Ir (ppy)2(acac) a mixed material;
the electron transport layer is Bepp 2;
the electron injection layer is a rare earth metal oxide; the work function of the electron injection layer is less than 3 eV.
9. The rare earth oxide-based optoelectronic device of claim 8, wherein Ir (ppy) in the mixed material2The proportion of (acac) was 8%.
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