CN104882546A - Organic electroluminescent device and preparation method thereof - Google Patents
Organic electroluminescent device and preparation method thereof Download PDFInfo
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- CN104882546A CN104882546A CN201410071902.4A CN201410071902A CN104882546A CN 104882546 A CN104882546 A CN 104882546A CN 201410071902 A CN201410071902 A CN 201410071902A CN 104882546 A CN104882546 A CN 104882546A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 187
- 238000002347 injection Methods 0.000 claims abstract description 134
- 239000007924 injection Substances 0.000 claims abstract description 134
- 239000011799 hole material Substances 0.000 claims abstract description 128
- 239000000758 substrate Substances 0.000 claims abstract description 85
- 230000005525 hole transport Effects 0.000 claims abstract description 62
- 238000001704 evaporation Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000005540 biological transmission Effects 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims description 58
- 238000007738 vacuum evaporation Methods 0.000 claims description 54
- 238000005516 engineering process Methods 0.000 claims description 52
- 230000008020 evaporation Effects 0.000 claims description 50
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 34
- 239000011521 glass Substances 0.000 claims description 33
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 26
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 26
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 18
- 229910052741 iridium Inorganic materials 0.000 claims description 18
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 16
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 16
- 239000004305 biphenyl Substances 0.000 claims description 12
- 239000012776 electronic material Substances 0.000 claims description 12
- YACSIMLPPDISOJ-UHFFFAOYSA-N 4-(4-anilinophenyl)-3-(3-methylphenyl)-n-phenylaniline Chemical compound CC1=CC=CC(C=2C(=CC=C(NC=3C=CC=CC=3)C=2)C=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 YACSIMLPPDISOJ-UHFFFAOYSA-N 0.000 claims description 10
- CECAIMUJVYQLKA-UHFFFAOYSA-N iridium 1-phenylisoquinoline Chemical compound [Ir].C1=CC=CC=C1C1=NC=CC2=CC=CC=C12.C1=CC=CC=C1C1=NC=CC2=CC=CC=C12.C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 CECAIMUJVYQLKA-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- -1 phenylquinolyl Chemical group 0.000 claims description 10
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- RKVIAZWOECXCCM-UHFFFAOYSA-N 2-carbazol-9-yl-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 RKVIAZWOECXCCM-UHFFFAOYSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- PSLMOSLVUSXMDQ-UHFFFAOYSA-N iridium;pentane-2,4-dione Chemical compound [Ir].CC(=O)CC(C)=O PSLMOSLVUSXMDQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 8
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 8
- YSZJKUDBYALHQE-UHFFFAOYSA-N rhenium trioxide Chemical compound O=[Re](=O)=O YSZJKUDBYALHQE-UHFFFAOYSA-N 0.000 claims description 8
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims description 7
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 6
- AYTVLULEEPNWAX-UHFFFAOYSA-N cesium;azide Chemical compound [Cs+].[N-]=[N+]=[N-] AYTVLULEEPNWAX-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- FIKCBJNCIJAAKU-UHFFFAOYSA-N 2-(1-benzothiophen-2-yl)pyridine;iridium(3+);pentane-2,4-dione Chemical compound [Ir+3].CC(=O)CC(C)=O.S1C2=CC=CC=C2C=C1C1=CC=CC=N1.S1C2=CC=CC=C2C=C1C1=CC=CC=N1 FIKCBJNCIJAAKU-UHFFFAOYSA-N 0.000 claims description 4
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 4
- ZVFQEOPUXVPSLB-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-4-phenyl-5-(4-phenylphenyl)-1,2,4-triazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C(N1C=2C=CC=CC=2)=NN=C1C1=CC=C(C=2C=CC=CC=2)C=C1 ZVFQEOPUXVPSLB-UHFFFAOYSA-N 0.000 claims description 4
- GWNJZSGBZMLRBW-UHFFFAOYSA-N 9,10-dinaphthalen-1-ylanthracene Chemical compound C12=CC=CC=C2C(C=2C3=CC=CC=C3C=CC=2)=C(C=CC=C2)C2=C1C1=CC=CC2=CC=CC=C12 GWNJZSGBZMLRBW-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000001771 vacuum deposition Methods 0.000 description 48
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 24
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound 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 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 9
- 229910002785 ReO3 Inorganic materials 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 210000001072 colon Anatomy 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000003599 detergent Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 6
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 4
- 239000003086 colorant Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H10K50/15—Hole transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to an organic electroluminescent device and a preparation method thereof, wherein the organic electroluminescent device comprises an anode conductive substrate, a first hole injection layer, a second hole injection layer, a hole transport layer, a red light emitting layer, an electron transmission layer, an electron injection layer and a cathode layer; wherein the first hole injection layer, the second hole injection layer, the hole transport layer, the red light emitting layer, the electron transmission layer, the electron injection layer and the cathode layer are successively laminated on one surface of the anode conductive substrate. The first hole injection layer and the second hole injection layer are respectively made of mixed hole material which is obtained through doping a p-type material into a hole transport material, thereby effectively improving separation efficiency between holes and electrons at a PN junction interface. According to the organic electroluminescent device, through arranging two hole injection layers which are made of same material, not only are charge separation efficiency and luminous efficiency improved, but also preparing process complexity is reduced through the p-type material which facilitates vacuum evaporating.
Description
Technical Field
The invention relates to the field of organic electroluminescent devices, in particular to an organic electroluminescent device and a preparation method thereof.
Background
Organic electroluminescent devices (OLEDs) have the following unique advantages: (1) the OLED belongs to a diffusion profile light source, and a large-area white light source is not required to be obtained through an additional light guide system like a Light Emitting Diode (LED); (2) due to the diversity of organic light-emitting materials, the OLED lighting can design light with required color according to requirements, and the current small-molecule OLED obtains light with all colors including white light spectrum; (3) OLEDs can be fabricated on a variety of substrates, such as glass, ceramic, metal, plastic, etc., which allows more freedom in designing illumination sources; (4) an OLED lighting panel is manufactured in an OLED display manufacturing mode, so that information can be displayed while lighting is performed; (5) OLEDs can also be used as controllable colors in lighting systems, allowing the user to adjust the light atmosphere according to personal needs.
Due to the advantages, the OLED has become a display technology and a light source with great potential, meets the development trend of mobile communication and information display in the information age and the requirement of a green lighting technology, and is the focus of attention of many researchers at home and abroad at present. However, although scientific researchers in various countries around the world have greatly improved various performance indexes of the OLED by selecting appropriate materials and reasonable device structure designs, the conventional OLED has low light emitting efficiency, and further application thereof is limited.
Disclosure of Invention
The invention aims to provide an organic electroluminescent device, which is used for solving the problem of low luminous efficiency of the traditional organic electroluminescent device in the prior art.
The invention also aims to provide a preparation method of the organic electroluminescent device, which is used for preparing the organic electroluminescent device.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention relates to an organic electroluminescent device, which comprises an anode conductive substrate, a first hole injection layer, a second hole injection layer, a hole transport layer, a red luminous layer, an electron transport layer, an electron injection layer and a cathode layer, wherein the first hole injection layer, the second hole injection layer, the hole transport layer, the red luminous layer, the electron transport layer, the electron injection layer and the cathode layer are sequentially stacked on one surface of the anode conductive substrate,
the first hole injection layer and the second hole injection layer are made of the same material, and both the first hole injection layer and the second hole injection layer are made of a mixed hole material formed by doping a p-type material with a hole transport material; in the mixed hole material, the p-type material accounts for 25-35 wt% of the hole transport material;
the hole transport material is any one of N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), 4',4' '-tris (carbazol-9-yl) triphenylamine (TCTA), 4' -bis (9-Carbazol) Biphenyl (CBP), N '-bis (3-methylphenyl) -N, N' -diphenyl-4, 4 '-biphenyldiamine (TPD) or 1, 1-bis [4- [ N, N' -bis (p-tolyl) amino ] phenyl ] cyclohexane (TAPC);
the p-type material is molybdenum trioxide (MoO)3) Tungsten trioxide (WO)3) Vanadium pentoxide (V)2O5) Or rhenium trioxide (ReO)3) Any one of them.
In an embodiment of the invention, the thicknesses of the first hole injection layer and the second hole injection layer are both 10nm to 15 nm.
In an embodiment of the invention, the material of the hole transport layer is the same as the hole transport material in the mixed hole material; the thickness of the hole transport layer is 30 nm-50 nm.
In an embodiment of the invention, the material of the red light emitting layer is a mixed light emitting material formed by doping a host material with a guest material; in the mixed luminescent material, the guest material accounts for 0.5-2 wt% of the host material;
the host material is any one of 4,4',4' ' -tris (carbazol-9-yl) triphenylamine (TCTA), 9' - (1, 3-phenyl) di-9H-carbazole (mCP), 4' -di (9-Carbazole) Biphenyl (CBP), N ' -di (3-methylphenyl) -N, N ' -diphenyl-4, 4' -biphenyldiamine (TPD), 1-di [4- [ N, N ' -di (p-tolyl) amino ] phenyl ] cyclohexane (TAPC) or 9, 10-bis (1-naphthyl) Anthracene (ADN);
the guest material is di (2-methyl-diphenyl [ f, h ]]Quinoxaline) (acetylacetone) Iridium (Ir (MDQ)2(acac)), bis [2- (phenylquinolinyl) -N, C2]Iridium (III) (PQIr) acetylacetonate, bis [ N-isopropyl-2- (4-fluorophenyl) benzimidazole]Iridium (III) (acetylacetonate) ((fbi)2Ir (acac), bis [2- (2-fluorophenyl) -1, 3-benzothiazole-N, C2]Iridium (III) (acetylacetonate) ((F-BT)2Ir (acac), bis (2-benzothiophen-2-yl-pyridine) (acetylacetone) iridium (III) (Ir (btp)2(acac)) or tris (1-phenyl-isoquinoline) iridium (Ir (piq)3) Any one of the above;
the thickness of the red luminous layer is 10 nm-30 nm.
In an embodiment of the present invention, the electron injection layer is made of a mixed electron material formed by doping an n-type material with an electron transport material; in the mixed electronic material, the n-type material accounts for 25-35 wt% of the mixed electronic material;
the electron transport material is 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 4, 7-diphenyl-1, 10-phenanthroline (BCP), 4-biphenol-bis (2-methyl-8-hydroxyquinoline) aluminum (BAlq), 8-hydroxyquinoline aluminum (Alq)3) Any one of 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ) and 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI);
the n-type material is cesium carbonate (Cs)2CO3) Cesium fluoride (CsF), cesium azide (CsN)3) Lithium carbonate (Li)2CO3) Lithium fluoride (LiF) or lithium oxide (Li)2O) is selected from any one of the following; m is
The material of the electron transport layer is the same as that of the electron transport material in the mixed electron material;
the thickness of the electron injection layer is 20 nm-40 nm;
the thickness of the electron transmission layer is 10 nm-60 nm.
In an embodiment of the invention, the cathode layer is made of any one of metal silver (Ag), aluminum (Al) or gold (Au); the thickness of the cathode layer is 50 nm-200 nm.
In an embodiment of the present invention, the anode conductive substrate includes a substrate and an anode conductive layer, wherein the substrate is made of glass, the anode conductive layer is made of Indium Tin Oxide (ITO), and a thickness of the anode conductive substrate is 100nm to 150 nm.
The invention relates to a preparation method of an organic electroluminescent device, which comprises the following steps:
providing an anode conductive substrate, and cleaning, drying and activating the anode conductive substrate for later use;
sequentially laminating and evaporating a first hole injection layer, a second hole injection layer, a hole transport layer, a red light-emitting layer, an electron transport layer, an electron injection layer and a cathode layer on the surface of the anode conductive substrate by adopting a vacuum evaporation technology; wherein,
the first hole injection layer and the second hole injection layer are made of the same material; the first hole injection layer and the second hole injection layer are both made of a mixed hole material formed by doping a hole transport material with a p-type material; in the mixed hole material, the p-type material accounts for 25-35 wt% of the hole transport material;
the hole transport material is any one of N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), 4',4' '-tris (carbazol-9-yl) triphenylamine (TCTA), 4' -bis (9-Carbazol) Biphenyl (CBP), N '-bis (3-methylphenyl) -N, N' -diphenyl-4, 4 '-biphenyldiamine (TPD) or 1, 1-bis [4- [ N, N' -bis (p-tolyl) amino ] phenyl ] cyclohexane (TAPC);
the p-type material is molybdenum trioxide (MoO)3) Tungsten trioxide (WO)3) Vanadium pentoxide (V)2O5) Or rhenium trioxide (ReO)3) Any one of the above;
and after the preparation steps are completed, the organic electroluminescent device is obtained.
In an embodiment of the invention, the material of the hole transport layer is the same as the hole transport material in the mixed hole material;
the red light-emitting layer is made of a mixed light-emitting material formed by doping a host material with a guest material; in the mixed luminescent material, the guest material accounts for 0.5-2 wt% of the host material;
the host material is any one of 4,4',4' ' -tris (carbazol-9-yl) triphenylamine (TCTA), 9' - (1, 3-phenyl) di-9H-carbazole (mCP), 4' -di (9-Carbazole) Biphenyl (CBP), N ' -di (3-methylphenyl) -N, N ' -diphenyl-4, 4' -biphenyldiamine (TPD), 1-di [4- [ N, N ' -di (p-tolyl) amino ] phenyl ] cyclohexane (TAPC) or 9, 10-bis (1-naphthyl) Anthracene (ADN);
the guest material is di (2-methyl-diphenyl [ f, h ]]Quinoxaline) (acetylacetone) Iridium (Ir (MDQ)2(acac)), bis [2- (phenylquinolinyl) -N, C2]Iridium (III) (PQIr) acetylacetonate, bis [ N-isopropyl-2- (4-fluorophenyl) benzimidazole]Iridium (III) (acetylacetonate) ((fbi)2Ir (acac), bis [2- (2-fluorophenyl) -1, 3-benzothiazole-N, C2]Iridium (III) (acetylacetonate) ((F-BT)2Ir (acac), bis (2-benzothiophen-2-yl-pyridine) (acetylacetone) iridium (III) (Ir (btp)2(acac)) or tris (1-phenyl-isoquinoline) iridium (Ir (piq)3) Any one of the above;
the electron injection layer is made of a mixed electron material formed by doping an n-type material with an electron transport material; in the mixed electronic material, the n-type material accounts for 25-35 wt% of the mixed electronic material;
the electron transport material is 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 4, 7-diphenyl-1, 10-phenanthroline (BCP), 4-biphenol-bis (2-methyl-8-hydroxyquinoline) aluminum (BAlq), 8-hydroxyquinoline aluminum (Alq)3) Any one of 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ) and 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI);
the n-type material is cesium carbonate (Cs)2CO3) Cesium fluoride (CsF), cesium azide (CsN)3) Lithium carbonate (Li)2CO3) Lithium fluoride (LiF) or lithium oxide (Li)2O) is selected from any one of the following;
the material of the electron transport layer is the same as that of the electron transport material in the mixed electron material;
the cathode layer is made of any one of metal silver (Ag), aluminum (Al) or gold (Au);
the anode conductive substrate comprises a substrate and an anode conductive layer, wherein the substrate is made of glass, and the anode conductive layer is made of Indium Tin Oxide (ITO).
In an embodiment of the present invention, the evaporation rate of the vacuum evaporation technique isVacuum degree of 1X 10-5Pa～1×10-3Pa。
Compared with the prior art, the organic electroluminescent device and the preparation method thereof have the following advantages: the materials of the first hole injection layer and the second hole injection layer of the organic electroluminescent device are the same hole transport material doped with a mixed hole material consisting of p-type materials, and the same mixed hole material is more favorable for the transport and injection of holes; the double-layer hole injection layers all adopt the same doping structure, so that the separation efficiency of holes and electrons on a PN junction interface is effectively improved; in addition, the red light-emitting layer is made of a mixed light-emitting material formed by doping a host material with a red light guest material, and the hole transport layer is made of a hole transport material which is the same as the two hole injection layers, so that the light-emitting efficiency of the organic electroluminescent device is further improved. According to the invention, the two hole injection layers made of the same material are arranged, so that the charge separation efficiency and the luminous efficiency are improved, and the complexity of the preparation process is reduced by selecting the p-type material convenient for vacuum evaporation.
Drawings
Fig. 1 is a schematic structural view of an organic electroluminescent device according to the present invention.
Wherein the reference numerals are as follows:
1 organic electroluminescent device
101 anode conductive substrate
101a substrate
101b anodic conductive layer
102 first hole injection layer
103 second hole injection layer
104 hole transport layer
105 red light emitting layer
106 electron transport layer
107 electron injection layer
108 cathode layer
Detailed Description
An organic electroluminescent device and a method for fabricating the same according to the present invention will be further described in detail with reference to fig. 1.
As shown in fig. 1, the organic electroluminescent device 1 includes: the organic light emitting diode comprises an anode conductive substrate 101, and a first hole injection layer 102, a second hole injection layer 103, a hole transport layer 104, a red light emitting layer 105, an electron transport layer 106, an electron injection layer 107 and a cathode layer 108 which are sequentially stacked on one surface of the anode conductive substrate 101, wherein the anode conductive substrate 101 comprises a substrate 101a and an anode conductive layer 101 b.
The following specifically describes the organic electroluminescent device 1 and the method for manufacturing the same according to the present invention with reference to examples 1 to 6, and since the layer structures of the organic electroluminescent devices 1 of examples 1 to 6 are substantially the same, the following specifically describes the organic electroluminescent device 1 with reference to fig. 1:
example 1
As shown in fig. 1, the present inventionThe organic electroluminescent device of the embodiment has the structure that: ITO glass/MoO3:NPB(30:100)/MoO3:NPB(30:100)/NPB/Ir(MDQ)2(acac):TCTA(0.5:100)/Bphen/Cs2CO3Bphen (30:100)/Ag, wherein the colon ": indicates that the former is doped in the latter.
The method for manufacturing the organic electroluminescent device of this embodiment includes the steps of:
(a) pretreatment of the anode conductive substrate 101:
firstly, ITO glass is used as an anode conductive substrate 101, wherein the substrate 101a is made of glass, and the anode conductive layer 101b is made of ITO;
then, sequentially performing liquid detergent cleaning → deionized water cleaning → acetone cleaning → ethanol cleaning on the anode conductive substrate 101, wherein the cleaning is performed by using an ultrasonic cleaning machine, each cleaning is performed by firstly cleaning for 5 minutes, then stopping for 5 minutes, and repeating for 3 times, and after the cleaning is finished, drying by using an oven for standby;
finally, the surface activation treatment is carried out on the clean ITO glass, namely the anode conductive substrate 101, so as to increase the oxygen content of the ITO surface and improve the work function of the ITO surface; obtaining an anode conductive substrate 101 with the thickness of 150nm after the completion;
(b) preparation of the first hole injection layer 102:
under a vacuum of 1X 10-5In a Pa vacuum coating system, a first hole injection layer 102 with a thickness of 12.5nm is prepared on the surface of an anode conductive substrate 101 by adopting a vacuum evaporation technology, and the material is MoO3Doping of mixed hole material formed in NPB, denoted MoO3:NPB，MoO330:100 wt% of NPB, and evaporation rate of
(c) Preparation of the second hole injection layer 103:
under a vacuum of 1X 10-5In the Pa vacuum coating system, a second hole injection layer 103 with the thickness of 12.5nm is prepared on the surface of the first hole injection layer 102 by adopting a vacuum evaporation technology, and the used material is MoO3Doping of mixed hole material formed in NPB, denoted MoO3:NPB，MoO330:100 wt% of NPB, and evaporation rate of
(d) Preparation of hole transport layer 104:
under a vacuum of 1X 10-5In the Pa vacuum coating system, a hole transport layer 104 with a thickness of 40nm is prepared on the surface of the second hole injection layer 103 by vacuum evaporation technology, the material is NPB, and the evaporation speed is
(e) Preparation of red light-emitting layer 105:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a red light-emitting layer 105 with a thickness of 20nm is prepared on the surface of the hole transport layer 104 by vacuum evaporation technology, and the material is Ir (MDQ)2(acac) hybrid light emitting material doped in TCTA, denoted Ir (MDQ)2(acac):TCTA，Ir(MDQ)2(acac) and TCTA in a weight ratio of 0.5:100, using an evaporation rate of
(f) Preparation of the electron transport layer 106:
under a vacuum of 1X 10-5In the Pa vacuum coating system, an electron transport layer 106 with a thickness of 35nm is prepared on the surface of the red luminescent layer 105 by adopting a vacuum evaporation technology, the used material is Bphen, and evaporation is adoptedHair velocity of
(g) Preparation of the electron injection layer 107:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, an electron injection layer 107 with a thickness of 30nm is prepared on the surface of the electron transport layer 106 by adopting a vacuum evaporation technology, and the material is Cs2CO3Mixed electron material doped in Bphen, denoted Cs2CO3:Bphen，Cs2CO3The weight percentage of the active ingredient to Bphen is 30:100, and the evaporation rate is
(h) Preparation of cathode layer 108:
under a vacuum of 1X 10-5In a Pa vacuum coating system, a cathode layer 108 with a thickness of 125nm is prepared on the surface of the electron injection layer 107 by vacuum evaporation technology, the material is Ag, and the evaporation rate is
And after the preparation steps are completed, the organic electroluminescent device 1 is obtained.
Example 2
As shown in fig. 1, the organic electroluminescent device of the present embodiment has the following structure: ITO glass/WO3:TCTA(25:100)/WO3TCTA (25:100)/TCTA/PQIr: mCP (2:100)/BCP/CsF: BCP (25:100)/Al, wherein, the colons indicate that the former is doped in the latter.
The method for manufacturing the organic electroluminescent device of this embodiment includes the steps of:
(a) pretreatment of the anode conductive substrate 101:
firstly, ITO glass is used as an anode conductive substrate 101, wherein the substrate 101a is made of glass, and the anode conductive layer 101b is made of ITO;
then, sequentially performing liquid detergent cleaning → deionized water cleaning → acetone cleaning → ethanol cleaning on the anode conductive substrate 101, wherein the cleaning is performed by using an ultrasonic cleaning machine, each cleaning is performed by firstly cleaning for 5 minutes, then stopping for 5 minutes, and repeating for 3 times, and after the cleaning is finished, drying by using an oven for standby;
finally, the surface activation treatment is carried out on the clean ITO glass, namely the anode conductive substrate 101, so as to increase the oxygen content of the ITO surface and improve the work function of the ITO surface; obtaining an anode conductive substrate 101 with the thickness of 120nm after the completion;
(b) preparation of the first hole injection layer 102:
under vacuum degree of 5X 10-5In a Pa vacuum coating system, a first hole injection layer 102 with a thickness of 10nm is prepared on the surface of an anode conductive substrate 101 by adopting a vacuum evaporation technology, and the material used is WO3Doping of mixed hole materials formed in TCTA, denoted WO3:TCTA，WO3The weight percentage of the TCTA is 25:100, and the evaporation rate is
(c) Preparation of the second hole injection layer 103:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a second hole injection layer 103 with a thickness of 10nm is prepared on the surface of the first hole injection layer 102 by adopting a vacuum evaporation technology, and the used material is WO3Doping of mixed hole materials formed in TCTA, denoted WO3:TCTA，WO3The weight percentage of the TCTA is 25:100, and the evaporation rate is
(d) Preparation of hole transport layer 104:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a hole transport layer 104 with a thickness of 30nm is prepared on the surface of the second hole injection layer 103 by vacuum evaporation technology, the material is TCTA, and the evaporation rate is
(e) Preparation of red light-emitting layer 105:
under vacuum degree of 5X 10-5In the vacuum coating system of Pa, a red luminescent layer 105 with a thickness of 10nm is prepared on the surface of a hole transport layer 104 by vacuum evaporation technology, the material is a mixed luminescent material formed by doping PQIR in mCP, the mixed luminescent material is expressed as PQIR: mCP, the weight percentage of PQIR and mCP is 2:100, and the evaporation speed is 2:100
(f) Preparation of the electron transport layer 106:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, an electron transport layer 106 with a thickness of 10nm is prepared on the surface of the red luminescent layer 105 by vacuum evaporation technology, the material is BCP, and the evaporation speed is
(g) Preparation of the electron injection layer 107:
under vacuum degree of 5X 10-5In the vacuum coating system of Pa, an electron injection layer 107 with a thickness of 20nm is prepared on the surface of the electron transport layer 106 by vacuum evaporation technology, and the material is a mixed electron material formed by doping CsF in BCP, which means thatCsF: BCP, the weight percentage of CsF and BCP is 25:100, and the evaporation rate is
(h) Preparation of cathode layer 108:
under vacuum degree of 5X 10-5In the vacuum coating system of Pa, a cathode layer 108 with a thickness of 50nm is prepared on the surface of the electron injection layer 107 by vacuum evaporation technology, the material is metal Al, and the evaporation speed is
And after the preparation steps are completed, the organic electroluminescent device 1 is obtained.
Example 3
As shown in fig. 1, the organic electroluminescent device of the present embodiment has the following structure: ITO glass/V2O5:CBP(35:100)/V2O5:CBP(35:100)/CBP/(fbi)2Ir(acac):CBP(1:100)/BAlq/CsN3BAlq (35:100)/Au, wherein the colon ": indicates that the former is doped in the latter.
The method for manufacturing the organic electroluminescent device of this embodiment includes the steps of:
(a) pretreatment of the anode conductive substrate 101:
firstly, ITO glass is used as an anode conductive substrate 101, wherein the substrate 101a is made of glass, and the anode conductive layer 101b is made of ITO;
then, sequentially performing liquid detergent cleaning → deionized water cleaning → acetone cleaning → ethanol cleaning on the anode conductive substrate 101, wherein the cleaning is performed by using an ultrasonic cleaning machine, each cleaning is performed by firstly cleaning for 5 minutes, then stopping for 5 minutes, and repeating for 3 times, and after the cleaning is finished, drying by using an oven for standby;
finally, the surface activation treatment is carried out on the clean ITO glass, namely the anode conductive substrate 101, so as to increase the oxygen content of the ITO surface and improve the work function of the ITO surface; obtaining an anode conductive substrate 101 with the thickness of 100nm after the completion;
(b) preparation of the first hole injection layer 102:
under vacuum degree of 5X 10-5In a Pa vacuum coating system, a first hole injection layer 102 with a thickness of 15nm is prepared on the surface of an anode conductive substrate 101 by adopting a vacuum evaporation technology, and the material is V2O5Doping of the mixed hole material formed in the CBP, denoted as V2O5:CBP，V2O535:100 by weight of CBP, using an evaporation rate of
(c) Preparation of the second hole injection layer 103:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a second hole injection layer 103 with a thickness of 15nm is prepared on the surface of the first hole injection layer 102 by vacuum evaporation technology, and the material is V2O5Doping of the mixed hole material formed in the CBP, denoted as V2O5:CBP，V2O535:100 by weight of CBP, using an evaporation rate of
(d) Preparation of hole transport layer 104:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a hole transport layer 104 with a thickness of 50nm is prepared on the surface of the second hole injection layer 103 by vacuum evaporation technology, the material is CBP, and the evaporation speed is
(e) Preparation of red light-emitting layer 105:
under vacuum degree of 5X 10-5In the vacuum coating system of Pa, a red luminescent layer 105 with a thickness of 30nm is prepared on the surface of the hole transport layer 104 by vacuum evaporation technology, and the material is (fbi)2Ir (acac) doped mixed luminescent materials formed in CBP, denoted (fbi)2Ir(acac):CBP，(fbi)2The weight percentage of Ir (acac) and CBP is 1:100, the evaporation rate is
(f) Preparation of the electron transport layer 106:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, an electron transport layer 106 with a thickness of 60nm is prepared on the surface of the red luminescent layer 105 by vacuum evaporation technology, the material is BAlq, and the evaporation rate is
(g) Preparation of the electron injection layer 107:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, an electron injection layer 107 with a thickness of 40nm is prepared on the surface of the electron transmission layer 106 by adopting a vacuum evaporation technology, and the material is CsN3Doping of mixed electronic materials formed in BAlq, denoted CsN3:BAlq，CsN335: 100% by weight of BALq, using an evaporation rate of
(h) Preparation of cathode layer 108:
under vacuum degree of 5X 10-5Pa ofIn the vacuum coating system, a cathode layer 108 with a thickness of 200nm is prepared on the surface of the electron injection layer 107 by vacuum evaporation technology, the material is metal Au, and the evaporation speed is
And after the preparation steps are completed, the organic electroluminescent device 1 is obtained.
Example 4
As shown in fig. 1, the organic electroluminescent device of the present embodiment has the following structure: ITO glass/ReO3:TPD(30:100)/ReO3:TPD(30:100)/TPD/(F-BT)2Ir(acac):TPD(1.5:100)/Alq3/Li2CO3:Alq3(30:100)/Ag, wherein the colon ": indicates that the former is doped in the latter.
The method for manufacturing the organic electroluminescent device of this embodiment includes the steps of:
(a) pretreatment of the anode conductive substrate 101:
firstly, ITO glass is used as an anode conductive substrate 101, wherein the substrate 101a is made of glass, and the anode conductive layer 101b is made of ITO;
then, sequentially performing liquid detergent cleaning → deionized water cleaning → acetone cleaning → ethanol cleaning on the anode conductive substrate 101, wherein the cleaning is performed by using an ultrasonic cleaning machine, each cleaning is performed by firstly cleaning for 5 minutes, then stopping for 5 minutes, and repeating for 3 times, and after the cleaning is finished, drying by using an oven for standby;
finally, the surface activation treatment is carried out on the clean ITO glass, namely the anode conductive substrate 101, so as to increase the oxygen content of the ITO surface and improve the work function of the ITO surface; obtaining an anode conductive substrate 101 with the thickness of 100nm after the completion;
(b) preparation of the first hole injection layer 102:
under vacuum degree of 5X 10-5In a Pa vacuum coating system, a first hole injection layer 102 with a thickness of 13nm is prepared on the surface of an anode conductive substrate 101 by adopting a vacuum evaporation technology, and the material is ReO3Doping of the Mixed hole Material formed in the TPD, denoted ReO3:TPD，ReO3The weight percentage of TPD and TPD is 30:100, and the evaporation rate is
(c) Preparation of the second hole injection layer 103:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a second hole injection layer 103 with a thickness of 13nm is prepared on the surface of the first hole injection layer 102 by adopting a vacuum evaporation technology, and the material is ReO3Doping of the Mixed hole Material formed in the TPD, denoted ReO3:TPD，ReO3The weight percentage of TPD and TPD is 30:100, and the evaporation rate is
(d) Preparation of hole transport layer 104:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a hole transport layer 104 with a thickness of 40nm is prepared on the surface of the second hole injection layer 103 by vacuum evaporation technology, the material is TPD, and the evaporation speed is
(e) Preparation of red light-emitting layer 105:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a red luminescent layer 105 with a thickness of 20nm is prepared on the surface of the hole transport layer 104 by vacuum evaporation technology, and the material is (F-BT)2Ir (acac) doped mixed luminescent materials formed in TPD, denoted as (F-BT)2Ir(acac):TPD，(F-BT)2The weight percentage of Ir (acac) and TPD is 1.5:100, the evaporation rate is
(f) Preparation of the electron transport layer 106:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, an electron transport layer 106 with a thickness of 30nm is prepared on the surface of the red luminescent layer 105 by adopting a vacuum evaporation technology, and the material is Alq3With an evaporation rate of
(g) Preparation of the electron injection layer 107:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, an electron injection layer 107 with a thickness of 30nm is prepared on the surface of the electron transport layer 106 by adopting a vacuum evaporation technology, and the material is Li2CO3Doped in Alq3Mixed electron material formed in (1), represented by Li2CO3:Alq3，Li2CO3With Alq3Is 30:100 by weight percent, and the evaporation rate is
(h) Preparation of cathode layer 108:
under vacuum degree of 5X 10-5In a Pa vacuum coating system, a cathode layer 108 with a thickness of 100nm is prepared on the surface of the electron injection layer 107 by vacuum evaporation technology, the material is Ag, and the evaporation rate is
And after the preparation steps are completed, the organic electroluminescent device 1 is obtained.
Example 5
As shown in fig. 1, the organic electroluminescent device of the present embodiment has the following structure: ITO glass/MoO3:TAPC(25:100)/MoO3:TAPC(25:100)/TAPC/Ir(btp)2(acac) TAPC (1.8:100)/TAZ/LiF TAZ (30:100)/Al, wherein the colon ": indicates that the former is doped in the latter.
The method for manufacturing the organic electroluminescent device of this embodiment includes the steps of:
(a) pretreatment of the anode conductive substrate 101:
firstly, ITO glass is used as an anode conductive substrate 101, wherein the substrate 101a is made of glass, and the anode conductive layer 101b is made of ITO;
then, sequentially performing liquid detergent cleaning → deionized water cleaning → acetone cleaning → ethanol cleaning on the anode conductive substrate 101, wherein the cleaning is performed by using an ultrasonic cleaning machine, each cleaning is performed by firstly cleaning for 5 minutes, then stopping for 5 minutes, and repeating for 3 times, and after the cleaning is finished, drying by using an oven for standby;
finally, the surface activation treatment is carried out on the clean ITO glass, namely the anode conductive substrate 101, so as to increase the oxygen content of the ITO surface and improve the work function of the ITO surface; obtaining an anode conductive substrate 101 with the thickness of 100nm after the completion;
(b) preparation of the first hole injection layer 102:
under vacuum degree of 5X 10-5In a Pa vacuum coating system, a first hole injection layer 102 with a thickness of 10nm is prepared on the surface of an anode conductive substrate 101 by adopting a vacuum evaporation technology, and the material is MoO3Doping of the mixed hole material formed in TAPC, denoted MoO3:TAPC，MoO3Weight of TAPCThe percentage is 25:100, the evaporation rate is
(c) Preparation of the second hole injection layer 103:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a second hole injection layer 103 with the thickness of 10nm is prepared on the surface of the first hole injection layer 102 by adopting a vacuum evaporation technology, and the used material is MoO3Doping of the mixed hole material formed in TAPC, denoted MoO3:TAPC，MoO3The weight percentage of TAPC is 25:100, the evaporation rate is
(d) Preparation of hole transport layer 104:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a hole transport layer 104 with a thickness of 40nm is prepared on the surface of the second hole injection layer 103 by vacuum evaporation technology, the material is TAPC, and the evaporation rate is TAPC
(e) Preparation of red light-emitting layer 105:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a red light-emitting layer 105 with a thickness of 20nm is prepared on the surface of a hole transport layer 104 by adopting a vacuum evaporation technology, and the material is Ir (btp)2(acac) hybrid light emitting material doped in TAPC, denoted Ir (btp)2(acac):TAPC，Ir(btp)2(acac) and TAPC in a weight ratio of 1.8:100, using an evaporation rate of
(f) Preparation of the electron transport layer 106:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, an electron transport layer 106 with a thickness of 50nm is prepared on the surface of the red luminescent layer 105 by vacuum evaporation technology, the material is TAZ, and the evaporation rate is
(g) Preparation of the electron injection layer 107:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, an electron injection layer 107 with a thickness of 30nm is prepared on the surface of an electron transport layer 106 by adopting a vacuum evaporation technology, the material is a mixed electronic material formed by doping LiF in TAZ, the LiF and TAZ are expressed as LiF: TAZ, the weight percentage of LiF to TAZ is 30:100, and the evaporation speed is
(h) Preparation of cathode layer 108:
under vacuum degree of 5X 10-5In the vacuum coating system of Pa, a cathode layer 108 with a thickness of 100nm is prepared on the surface of the electron injection layer 107 by vacuum evaporation technology, the material is metal Al, and the evaporation speed is
And after the preparation steps are completed, the organic electroluminescent device 1 is obtained.
Example 6
As shown in fig. 1, the organic electroluminescent device of the present embodiment has the following structure: ITO glass/WO3:NPB(30:100)/WO3:NPB(30:100)/NPB/Ir(piq)3:ADN(1.4:100)/TPBI/Li2TPBI (30:100)/Al, wherein, the colon:'Indicating that the former is doped in the latter.
The method for manufacturing the organic electroluminescent device of this embodiment includes the steps of:
(a) pretreatment of the anode conductive substrate 101:
firstly, ITO glass is used as an anode conductive substrate 101, wherein the substrate 101a is made of glass, and the anode conductive layer 101b is made of ITO;
then, sequentially performing liquid detergent cleaning → deionized water cleaning → acetone cleaning → ethanol cleaning on the anode conductive substrate 101, wherein the cleaning is performed by using an ultrasonic cleaning machine, each cleaning is performed by firstly cleaning for 5 minutes, then stopping for 5 minutes, and repeating for 3 times, and after the cleaning is finished, drying by using an oven for standby;
finally, the surface activation treatment is carried out on the clean ITO glass, namely the anode conductive substrate 101, so as to increase the oxygen content of the ITO surface and improve the work function of the ITO surface; obtaining an anode conductive substrate 101 with the thickness of 100nm after the completion;
(b) preparation of the first hole injection layer 102:
under a vacuum of 1X 10-3PaIn the vacuum coating system, a first hole injection layer 102 with a thickness of 12nm is prepared on the surface of an anode conductive substrate 101 by adopting a vacuum evaporation technology, and the material used is WO3Doping of mixed hole materials formed in NPB, denoted WO3:NPB，WO330:100 wt% of NPB, and evaporation rate of
(c) Preparation of the second hole injection layer 103:
under a vacuum of 1X 10-3In the vacuum coating system of Pa, a second hole injection layer 103 with the thickness of 12nm is prepared on the surface of the first hole injection layer 102 by adopting a vacuum evaporation technology,the material is WO3Doping of mixed hole materials formed in NPB, denoted WO3:NPB，WO330:100 wt% of NPB, and evaporation rate of
(d) Preparation of hole transport layer 104:
under a vacuum of 1X 10-3In the Pa vacuum coating system, a hole transport layer 104 with a thickness of 40nm is prepared on the surface of the second hole injection layer 103 by vacuum evaporation technology, the material is NPB, and the evaporation speed is
(e) Preparation of red light-emitting layer 105:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a red luminescent layer 105 with the thickness of 20nm is prepared on the surface of the hole transport layer 104 by adopting a vacuum evaporation technology, and the material is Ir (piq)3Mixed luminescent materials doped in ADN, denoted Ir (piq)3:ADN，Ir(piq)3The weight ratio of ADN to ADN is 1.4:100, and the evaporation rate is
(f) Preparation of the electron transport layer 106:
under a vacuum of 1X 10-3In the Pa vacuum coating system, an electron transport layer 106 with a thickness of 30nm is prepared on the surface of the red light-emitting layer 105 by vacuum evaporation technology, the material is TPBI, and the evaporation rate is
(g) Preparation of the electron injection layer 107:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, an electron injection layer 107 with a thickness of 30nm is prepared on the surface of the electron transport layer 106 by adopting a vacuum evaporation technology, and the material is Li2O doping the Mixed electronic Material formed in TPBI, denoted as Li2O:TPBI，Li2The weight percentage of O and TPBI is 30:100, the evaporation rate is
(h) Preparation of cathode layer 108:
under a vacuum of 1X 10-3In the vacuum coating system of Pa, a cathode layer 108 with a thickness of 100nm is prepared on the surface of the electron injection layer 107 by vacuum evaporation technology, the material is metal Al, and the evaporation speed is
And after the preparation steps are completed, the organic electroluminescent device 1 is obtained.
Comparative example 1
The second hole injection layer 103 of the organic electroluminescent devices prepared in examples 1 to 6 was omitted, i.e., the organic electroluminescent device of the present comparative example includes: an anode conductive substrate 101, a first hole injection layer 102, a hole transport layer 104, a light emitting layer 105, an electron transport layer 106, an electron injection layer 107, and a cathode layer 108.
The organic electroluminescent device has the following structure: ITO glass/V2O5:CBP(30:100)/TCTA/Ir(piq)3:ADN(1:100)/BPhen/Li2TPBI (30:100)/Al, wherein the colon ": indicates that the former is doped in the latter.
The method for manufacturing the organic electroluminescent device of this comparative example includes the steps of:
(a) pretreatment of the anode conductive substrate 101:
firstly, ITO glass is used as an anode conductive substrate 101, wherein the substrate 101a is made of glass, and the anode conductive layer 101b is made of ITO;
then, sequentially performing liquid detergent cleaning → deionized water cleaning → acetone cleaning → ethanol cleaning on the anode conductive substrate 101, wherein the cleaning is performed by using an ultrasonic cleaning machine, each cleaning is performed by firstly cleaning for 5 minutes, then stopping for 5 minutes, and repeating for 3 times, and after the cleaning is finished, drying by using an oven for standby;
finally, the surface activation treatment is carried out on the clean ITO glass, namely the anode conductive substrate 101, so as to increase the oxygen content of the ITO surface and improve the work function of the ITO surface; obtaining an anode conductive substrate 101 with the thickness of 100nm after the completion;
(b) preparation of the first hole injection layer 102:
under vacuum degree of 5X 10-5In a Pa vacuum coating system, a first hole injection layer 102 with a thickness of 12nm is prepared on the surface of an anode conductive substrate 101 by adopting a vacuum evaporation technology, and the material is V2O5Doping of the mixed hole material formed in the CBP, denoted as V2O5:CBP，V2O530:100 weight percent of CBP and the evaporation rate is
(c) Preparation of hole transport layer 104:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a hole transport layer 104 with a thickness of 40nm is prepared on the surface of the second hole injection layer 103 by vacuum evaporation technology, the material is TCTA, and the evaporation rate is
(d) Preparation of the light-emitting layer 105:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, a luminescent layer 105 with a thickness of 20nm is prepared on the surface of the hole transport layer 104 by adopting a vacuum evaporation technology, and the material is Ir (piq)3Mixed luminescent materials doped in ADN, denoted Ir (piq)3:ADN，Ir(piq)3The weight ratio of ADN to ADN is 1:100, and the evaporation rate is
(e) Preparation of the electron transport layer 106:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, an electron transport layer 106 with a thickness of 40nm is prepared on the surface of the luminescent layer 105 by vacuum evaporation technology, the material is Bphen, and the evaporation speed is
(f) Preparation of the electron injection layer 107:
under vacuum degree of 5X 10-5In the Pa vacuum coating system, an electron injection layer 107 with a thickness of 30nm is prepared on the surface of the electron transport layer 106 by adopting a vacuum evaporation technology, and the material is Li2O doping the Mixed electronic Material formed in TPBI, denoted as Li2O:TPBI，Li2The weight percentage of O and TPBI is 30:100, the evaporation rate is
(g) Preparation of cathode layer 108:
under vacuum degree of 5X 10-5In the vacuum coating system of Pa, a cathode layer 108 with a thickness of 100nm is prepared on the surface of the electron injection layer 107 by vacuum evaporation technology, the material is metal Al, and the evaporation speed is
The organic electroluminescent devices prepared in examples 1 to 6 and comparative example 1 exhibited luminance of 1000cd/m2The test of luminous efficiency was carried out under the conditions of (1), and the test results are shown in table 1.
TABLE 1
As can be seen from table 1, the light emitting efficiency of the organic electroluminescent device prepared according to the present invention is significantly improved compared to that of comparative example 1, and the light emitting efficiency of example 1 alone is improved by 40%.
In summary, the organic electroluminescent device of the present invention includes an anode conductive substrate, a first hole injection layer, a second hole injection layer, a hole transport layer, a red light emitting layer, an electron transport layer, an electron injection layer, and a cathode layer sequentially stacked on one surface of the anode conductive substrate; the first hole injection layer and the second hole injection layer are both made of a mixed hole material formed by doping p-type materials with the same hole transport material, and the same mixed hole material is more favorable for hole transport and injection; the double-layer hole injection layers all adopt the same doping structure, so that the separation efficiency of holes and electrons on a PN junction interface is effectively improved; in addition, the red light-emitting layer is made of a mixed light-emitting material formed by doping a host material with a red light guest material, and the hole transport layer is made of a hole transport material which is the same as the two hole injection layers, so that the light-emitting efficiency of the organic electroluminescent device is further improved. According to the invention, the two hole injection layers made of the same material are arranged, so that the charge separation efficiency and the luminous efficiency are improved, and the complexity of the preparation process is reduced by selecting the p-type material convenient for vacuum evaporation.
The above-mentioned embodiments are merely preferred examples of the present invention, and not intended to limit the present invention, and those skilled in the art can easily make various changes and modifications according to the main concept and spirit of the present invention, so that the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. An organic electroluminescent device comprising an anode conductive substrate, a first hole injection layer, a second hole injection layer, a hole transport layer, a red light-emitting layer, an electron transport layer, an electron injection layer and a cathode layer laminated in this order on one surface of the anode conductive substrate,
the first hole injection layer and the second hole injection layer are made of the same material, and both the first hole injection layer and the second hole injection layer are made of a mixed hole material formed by doping a p-type material with a hole transport material; in the mixed hole material, the p-type material accounts for 25-35 wt% of the hole transport material;
the hole transport material is any one of N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, 4',4' '-tri (carbazol-9-yl) triphenylamine, 4' -di (9-carbazol) biphenyl, N '-di (3-methylphenyl) -N, N' -diphenyl-4, 4 '-biphenyldiamine or 1, 1-di [4- [ N, N' -di (p-tolyl) amino ] phenyl ] cyclohexane;
the p-type material is any one of molybdenum trioxide, tungsten trioxide, vanadium pentoxide or rhenium trioxide.
2. The organic electroluminescent device according to claim 1, wherein the first hole injection layer and the second hole injection layer each have a thickness of 10nm to 15 nm.
3. The organic electroluminescent device according to claim 2, wherein the hole transport layer is made of the same material as the hole transport material in the mixed hole material; the thickness of the hole transport layer is 30 nm-50 nm.
4. The organic electroluminescent device according to claim 1,
the red light-emitting layer is made of a mixed light-emitting material formed by doping a host material with a guest material; in the mixed luminescent material, the guest material accounts for 0.5-2 wt% of the host material;
the host material is any one of 4,4',4' ' -tris (carbazole-9-yl) triphenylamine, 9' - (1, 3-phenyl) di-9H-carbazole, 4' -di (9-carbazole) biphenyl, N ' -di (3-methylphenyl) -N, N ' -diphenyl-4, 4' -biphenyldiamine, 1-di [4- [ N, N ' -di (p-tolyl) amino ] phenyl ] cyclohexane or 9, 10-bis (1-naphthyl) anthracene;
the guest material is any one of bis (2-methyl-diphenyl [ f, h ] quinoxaline) (acetylacetone) iridium, bis [2- (phenylquinolyl) -N, C2] (acetylacetone) iridium (III), bis [ N-isopropyl-2- (4-fluorophenyl) benzimidazole ] (acetylacetone) iridium (III), bis [2- (2-fluorophenyl) -1, 3-benzothiazole-N, C2] (acetylacetone) iridium (III), bis (2-benzothien-2-yl-pyridine) (acetylacetone) iridium (III) or tris (1-phenyl-isoquinoline) iridium;
the thickness of the red luminous layer is 10 nm-30 nm.
5. The organic electroluminescent device according to claim 1,
the electron injection layer is made of a mixed electron material formed by doping an n-type material with an electron transport material; in the mixed electronic material, the n-type material accounts for 25-35 wt% of the mixed electronic material;
the electron transport material is any one of 4, 7-diphenyl-1, 10-phenanthroline, 4-biphenol-bis (2-methyl-8-hydroxyquinoline) aluminum, 8-hydroxyquinoline aluminum, 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-triazole or 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene;
the n-type material is any one of cesium carbonate, cesium fluoride, cesium azide, lithium carbonate, lithium fluoride or lithium oxide;
the material of the electron transport layer is the same as that of the electron transport material in the mixed electron material;
the thickness of the electron injection layer is 20 nm-40 nm;
the thickness of the electron transmission layer is 10 nm-60 nm.
6. The organic electroluminescent device as claimed in claim 1, wherein the cathode layer is made of any one of silver, aluminum or gold; the thickness of the cathode layer is 50 nm-200 nm.
7. The organic electroluminescent device according to claim 1, wherein the anode conductive substrate comprises a substrate and an anode conductive layer, wherein the substrate is made of glass, the anode conductive layer is made of indium tin oxide, and the thickness of the anode conductive substrate is 100nm to 150 nm.
8. A preparation method of an organic electroluminescent device is characterized by comprising the following steps:
providing an anode conductive substrate, and cleaning, drying and activating the anode conductive substrate for later use;
sequentially laminating and evaporating a first hole injection layer, a second hole injection layer, a hole transport layer, a red light-emitting layer, an electron transport layer, an electron injection layer and a cathode layer on the surface of the anode conductive substrate by adopting a vacuum evaporation technology; wherein,
the first hole injection layer and the second hole injection layer are made of the same material; the first hole injection layer and the second hole injection layer are both made of a mixed hole material formed by doping a hole transport material with a p-type material; in the mixed hole material, the p-type material accounts for 25-35 wt% of the hole transport material;
the hole transport material is any one of N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, 4',4' '-tri (carbazol-9-yl) triphenylamine, 4' -di (9-carbazol) biphenyl, N '-di (3-methylphenyl) -N, N' -diphenyl-4, 4 '-biphenyldiamine or 1, 1-di [4- [ N, N' -di (p-tolyl) amino ] phenyl ] cyclohexane;
the p-type material is any one of molybdenum trioxide, tungsten trioxide, vanadium pentoxide or rhenium trioxide;
and after the preparation steps are completed, the organic electroluminescent device is obtained.
9. The method for producing an organic electroluminescent element according to claim 8,
the material of the hole transport layer is the same as that of the hole transport material in the mixed hole material;
the red light-emitting layer is made of a mixed light-emitting material formed by doping a host material with a guest material; in the mixed luminescent material, the guest material accounts for 0.5-2 wt% of the host material;
the host material is any one of 4,4',4' ' -tris (carbazole-9-yl) triphenylamine, 9' - (1, 3-phenyl) di-9H-carbazole, 4' -di (9-carbazole) biphenyl, N ' -di (3-methylphenyl) -N, N ' -diphenyl-4, 4' -biphenyldiamine, 1-di [4- [ N, N ' -di (p-tolyl) amino ] phenyl ] cyclohexane or 9, 10-bis (1-naphthyl) anthracene;
the guest material is any one of bis (2-methyl-diphenyl [ f, h ] quinoxaline) (acetylacetone) iridium, bis [2- (phenylquinolyl) -N, C2] (acetylacetone) iridium (III), bis [ N-isopropyl-2- (4-fluorophenyl) benzimidazole ] (acetylacetone) iridium (III), bis [2- (2-fluorophenyl) -1, 3-benzothiazole-N, C2] (acetylacetone) iridium (III), bis (2-benzothien-2-yl-pyridine) (acetylacetone) iridium (III) or tris (1-phenyl-isoquinoline) iridium;
the electron injection layer is made of a mixed electron material formed by doping an n-type material with an electron transport material; in the mixed electronic material, the n-type material accounts for 25-35 wt% of the mixed electronic material;
the electron transport material is any one of 4, 7-diphenyl-1, 10-phenanthroline, 4-biphenol-bis (2-methyl-8-hydroxyquinoline) aluminum, 8-hydroxyquinoline aluminum, 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-triazole or 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene;
the n-type material is any one of cesium carbonate, cesium fluoride, cesium azide, lithium carbonate, lithium fluoride or lithium oxide;
the material of the electron transport layer is the same as that of the electron transport material in the mixed electron material;
the cathode layer is made of any one of metal silver, aluminum or gold;
the anode conductive substrate comprises a substrate and an anode conductive layer, wherein the substrate is made of glass, and the anode conductive layer is made of indium tin oxide.
10. According to the rightThe method of claim 8, wherein the evaporation rate of the vacuum evaporation technique isVacuum degree of 1X 10-5Pa～1×10-3Pa。
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