CN103137887B - A kind of electroluminescent device and preparation method thereof - Google Patents
A kind of electroluminescent device and preparation method thereof Download PDFInfo
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- CN103137887B CN103137887B CN201110384885.6A CN201110384885A CN103137887B CN 103137887 B CN103137887 B CN 103137887B CN 201110384885 A CN201110384885 A CN 201110384885A CN 103137887 B CN103137887 B CN 103137887B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 73
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 45
- 239000004411 aluminium Substances 0.000 claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000005540 biological transmission Effects 0.000 claims abstract description 37
- 238000002347 injection Methods 0.000 claims abstract description 37
- 239000007924 injection Substances 0.000 claims abstract description 37
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims abstract description 28
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 28
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000010931 gold Substances 0.000 claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 15
- 239000004332 silver Substances 0.000 claims abstract description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052737 gold Inorganic materials 0.000 claims abstract description 14
- 229910052741 iridium Inorganic materials 0.000 claims description 31
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 30
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 20
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 18
- 230000008020 evaporation Effects 0.000 claims description 17
- 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 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- MQCHTHJRANYSEJ-UHFFFAOYSA-N n-[(2-chlorophenyl)methyl]-1-(3-methylphenyl)benzimidazole-5-carboxamide Chemical compound CC1=CC=CC(N2C3=CC=C(C=C3N=C2)C(=O)NCC=2C(=CC=CC=2)Cl)=C1 MQCHTHJRANYSEJ-UHFFFAOYSA-N 0.000 claims description 14
- ZEOMRHKTIYBETG-UHFFFAOYSA-N 2-phenyl-1,3,4-oxadiazole Chemical compound O1C=NN=C1C1=CC=CC=C1 ZEOMRHKTIYBETG-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 13
- 239000011787 zinc oxide Substances 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 239000000075 oxide glass Substances 0.000 claims description 12
- 238000009832 plasma treatment Methods 0.000 claims description 12
- -1 4,6-difluorophenyl Chemical group 0.000 claims description 11
- 239000004305 biphenyl Substances 0.000 claims description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 10
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000003599 detergent Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical class N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 7
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 229910001887 tin oxide Inorganic materials 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- QHODXIVESWMRGP-UHFFFAOYSA-N NCC=1C=C(C=CC1)C1=C(C=CC(=C1)NC1=CC=CC=C1)C1=CC=C(NC2=CC=CC=C2)C=C1 Chemical compound NCC=1C=C(C=CC1)C1=C(C=CC(=C1)NC1=CC=CC=C1)C1=CC=C(NC2=CC=CC=C2)C=C1 QHODXIVESWMRGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- QWODREODAXFISP-UHFFFAOYSA-N n-[4-(4-anilinophenyl)phenyl]-n-phenylnaphthalen-1-amine Chemical compound C=1C=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=CC=1NC1=CC=CC=C1 QWODREODAXFISP-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 6
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 5
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 132
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 abstract description 68
- 238000005036 potential barrier Methods 0.000 abstract description 13
- 239000012044 organic layer Substances 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 5
- 238000005215 recombination Methods 0.000 abstract description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 19
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 6
- HXWWMGJBPGRWRS-CMDGGOBGSA-N 4- -2-tert-butyl-6- -4h-pyran Chemical compound O1C(C(C)(C)C)=CC(=C(C#N)C#N)C=C1\C=C\C1=CC(C(CCN2CCC3(C)C)(C)C)=C2C3=C1 HXWWMGJBPGRWRS-CMDGGOBGSA-N 0.000 description 5
- 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 4
- 239000002019 doping agent Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 125000006617 triphenylamine group Chemical class 0.000 description 3
- 230000005684 electric field Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 150000004880 oxines Chemical group 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a kind of electroluminescent device and preparation method thereof.This electroluminescent device comprise stack gradually conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron buffer layer and negative electrode, the material of described negative electrode is the metal of doping cesium salt, cesium salt mass percent of adulterating in the cathode is 1% ~ 10%, this cesium salt is cesium carbonate, nitrine caesium or cesium fluoride, and metal is silver, aluminium, platinum or gold.The work function of cesium carbonate, nitrine caesium and cesium fluoride is lower, about 2.0eV.Be doped with the cesium salt of 1% ~ 10% in the metal that silver, aluminium, platinum or this several work function of gold are relatively high after, the total work content of negative electrode can be made to be reduced to about 3.2eV, thus make the potential barrier between negative electrode and organic layer be reduced to about 0.2eV, effectively reduce injection and the transmission potential barrier of electronics, be conducive to injection and the transmission of electronics, the exciton recombination probability of luminescent layer is improved greatly, thus improves luminous efficiency.
Description
[technical field]
The present invention relates to organic electroluminescent LED field, particularly relate to a kind of electroluminescent device and preparation method thereof.
[background technology]
Organic electroluminescent LED (OrganicLight-EmittingDiode), hereinafter referred to as OLED, a kind of Display Technique and light source of great potential, meet the development trend of information age mobile communication and information displaying, and the requirement of green lighting technique, be the focal point of current lot of domestic and foreign researcher.Under its principle of luminosity is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by energy transferring to luminescent material, and excitation electron is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.
In general electroluminescent device, mate with the lumo energy of organic material to make negative electrode, it is low that the work function of General Requirements negative electrode is tried one's best, the lumo energy of organic material is 3.0eV, and the work function of metal is generally about 5.0eV, if work function is too low, then prove that metal easily loses electronics, very active, less stable, therefore, in field of organic electroluminescence, the moderate metal of general work function such as employing Ag or Al etc. is as electrode, on the one hand, the work content value of these materials is lower, for about 4.5eV, character is more stable, but, still the potential barrier of 1.5eV is had between itself and organic material, this potential barrier still plays very large inhibition to the transmission of electronics, thus have impact on the luminous efficiency of electroluminescent device.
[summary of the invention]
Based on this, be necessary the electroluminescent device providing a kind of luminous efficiency higher.
A kind of electroluminescent device, comprise stack gradually conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron buffer layer and negative electrode, the material of described negative electrode is the metal of doping cesium salt, wherein, the doping mass percent of described cesium salt in described negative electrode is 1% ~ 10%, described cesium salt is cesium carbonate, nitrine caesium or cesium fluoride, and described metal is silver, aluminium, platinum or gold.
Preferably, the thickness of described negative electrode is 80 ~ 250 nanometers.
Preferably, described conductive anode substrate is indium tin oxide glass, fluorine doped tin oxide glass, mixes the zinc oxide glass of aluminium or mix the zinc oxide glass of indium.
Preferably, the thickness of described hole injection layer is 20 ~ 80 nanometers, and the material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide.
Preferably, the thickness of described hole transmission layer is 20 ~ 60 nanometers, and the material of described hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine, 4,4 ', 4 "-three (carbazole-9-base) triphenylamines or N, N '-(1-naphthyl)-N; N '-diphenyl-4,4 '-benzidine.
Preferably, the thickness of described luminescent layer is 2 ~ 50 nanometers, and the material of described luminescent layer is selected from (dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, oxine aluminium, two (4,6-difluorophenyl pyridinato-N, C
2) pyridinecarboxylic closes iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) and close iridium and three (2-phenylpyridine) and close at least one in iridium; Or
The material of described luminescent layer is selected from (dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, oxine aluminium, two (4,6-difluorophenyl pyridinato-N, C
2) pyridinecarboxylic conjunction iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium and three (2-phenylpyridine) and close one and 1 in iridium, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4, 4 '-benzidine, 4, 4 ', 4 "-three (carbazole-9-base) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4, 4 '-benzidine, 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1, 3, 4-oxadiazole, oxine aluminium, 4, 7-diphenyl-1, 10-phenanthroline, 1, 2, the mixtures that a kind of or two kinds of doping in 4-triazole derivative and N-aryl benzimidazole are formed, wherein said (dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, oxine aluminium, two (4, 6-difluorophenyl pyridinato-N, C
2) pyridinecarboxylic closes iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) to close the doping mass percent that iridium or three (2-phenylpyridines) close iridium be 1% ~ 20%.
Preferably, the thickness of described electron transfer layer is 40 ~ 80 nanometers, and the material of described electron transfer layer is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine aluminium, 4,7-diphenyl-1,10-phenanthrolines, 1,2,4-triazole derivative or N-aryl benzimidazole.
Preferably, the material of described electron buffer layer is selected from the one in cesium carbonate, nitrine caesium, cesium fluoride and lithium fluoride, or by the one in cesium carbonate, nitrine caesium, cesium fluoride and lithium fluoride and 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine aluminium, 4,7-diphenyl-1,10-phenanthroline, 1,2, a kind of mixture formed that adulterates in 4-triazole derivative and N-aryl benzimidazole, the doping mass percent of wherein said cesium carbonate, nitrine caesium, cesium fluoride or lithium fluoride is 20 ~ 60%;
When the material of described electron buffer layer is a kind of in cesium carbonate, nitrine caesium, cesium fluoride and lithium fluoride, the thickness of described electron buffer layer is 0.5 ~ 5 nanometer;
When the material of described electron buffer layer is one in cesium carbonate, nitrine caesium, cesium fluoride and lithium fluoride and 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine aluminium, 4,7-diphenyl-1,10-phenanthroline, 1, a kind of in 2,4-triazole derivative and N-aryl benzimidazole adulterate the mixture formed time, the thickness of described electron buffer layer is 20 ~ 60 nanometers.
In addition, there is a need to the preparation method that above-mentioned electroluminescent device is provided, comprise the following steps:
Step one: conductive anode substrate is provided;
Step 2: evaporation hole injection layer successively in described conductive anode substrate, hole transmission layer, luminescent layer, electron transfer layer and electron buffer layer;
Step 3: evaporation negative electrode in described electron buffer layer, obtain described electroluminescent device, the material of wherein said negative electrode is the metal of doping cesium salt, the doping mass percent of described cesium salt in described negative electrode is 1% ~ 10%, described cesium salt is cesium carbonate, nitrine caesium or cesium fluoride, and described metal is silver, aluminium, platinum or gold.
Preferably, step one also comprises carries out pre-treatment step to described conductive anode substrate, comprise and described conductive anode substrate used successively liquid detergent, deionized water, acetone, ethanol and isopropyl alcohol supersound washing 15 minutes, then oxygen plasma treatment is carried out, the oxygen plasma treatment time is 2 ~ 15 minutes, and power is 10 ~ 50W.
The material of the negative electrode of above-mentioned electroluminescent device is the metal of doping cesium salt, and cesium salt is cesium carbonate, nitrine caesium or cesium fluoride, and metal is silver, aluminium, platinum or gold.The work function of above-mentioned cesium salt is lower, about 2.0eV.Be doped with the cesium salt of 1% ~ 10% in the metal that silver, aluminium, platinum or this several work function of gold are relatively high after, total work content can be made to be reduced to about 3.2eV, thus make the potential barrier between negative electrode and organic layer be reduced to about 0.2eV, effectively reduce injection and the transmission potential barrier of electronics, be conducive to injection and the transmission of electronics, the exciton recombination probability of luminescent layer is improved greatly, thus improves luminous efficiency.
[accompanying drawing explanation]
Fig. 1 is the structural representation of the electroluminescent device of an execution mode;
Fig. 2 is preparation method's flow chart of the electroluminescent device of an execution mode;
Fig. 3 is the electroluminescent device of embodiment 1 and the brightness of traditional electroluminescent device and the graph of relation of luminous efficiency.
[embodiment]
Below by way of embodiment, above-mentioned electroluminescent device is set forth further.
Refer to Fig. 1, the electroluminescent device 100 of an execution mode, comprise stack gradually conductive anode substrate 110, hole injection layer 120, hole transmission layer 130, luminescent layer 140, electron transfer layer 150, electron buffer layer 160 and negative electrode 170.
Conductive anode substrate 110 can be indium tin oxide glass (ITO), fluorine doped tin oxide glass (FTO), mixes the zinc oxide glass (AZO) of aluminium or mix the zinc oxide glass (IZO) of indium.Indium tin oxide glass (ITO), fluorine doped tin oxide glass (FTO), the zinc oxide glass (AZO) mixing aluminium and the zinc oxide glass (IZO) mixing indium have higher light transmission, meet the requirement of conductive anode substrate 110 as display device.
The material of hole injection layer 120 can be molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).The thickness of hole injection layer 120 is 20 ~ 80 nanometers.In preferred scheme, the material of hole injection layer 120 is molybdenum trioxide (MoO
3), thickness is 40 nanometers.
The material of hole transmission layer 130 can be 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD), 4,4 ', 4 "-three (carbazole-9-base) triphenylamines (TCTA) or N, N '-(1-naphthyl)-N; N '-diphenyl-4,4 '-benzidine (NPB).Hole transmission layer 130 thickness is 20 ~ 60 nanometers.In preferred scheme, the material of hole transmission layer 130 is N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), and thickness is 40 nanometers.
The material of luminescent layer 140 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), oxine aluminium (Alq
3), two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium (FIrpic), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ) 2 (acac)) and three (2-phenylpyridines) and close at least one in iridium (Ir (ppy) 3).
In other embodiments, the material of luminescent layer 140 can be (dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), oxine aluminium (Alq
3), two (4,6-difluorophenyl pyridinato-N, C
2) pyridinecarboxylic conjunction iridium (FIrpic), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium (Ir (MDQ) 2 (acac)) and three (2-phenylpyridines) and close one and 1 in iridium (Ir (ppy) 3), 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4, 4 '-benzidine (TPD), 4, 4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4, 4 '-benzidine (NPB), 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1, 3, 4-oxadiazole (PBD), oxine aluminium (Alq
3), 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, the mixtures that a kind of or two kinds of doping in 4-triazole derivative (TAZ) and N-aryl benzimidazole (TPBi) are formed, wherein (dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), oxine aluminium (Alq
3), two (4,6-difluorophenyl pyridinato-N, C
2) pyridinecarboxylic closes iridium (FIrpic), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ) 2 (acac)) or three (2-phenylpyridines) close iridium (Ir (ppy)
3) doping mass percent be 1% ~ 20%.
In preferred scheme, the material of luminescent layer 140 is oxine aluminium (Alq
3).
The thickness of luminescent layer 140 is 2 ~ 50 nanometers.In preferred scheme, the thickness of luminescent layer 140 is 30 nanometers.
The material of electron transfer layer 150 can be 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), oxine aluminium (Alq
3), 4,7-diphenyl-1,10-phenanthrolines (Bphen), 1,2,4-triazole derivative (TAZ) or N-aryl benzimidazole (TPBi).The thickness of electron transfer layer 150 is 40 ~ 80 nanometers.In preferred scheme, the material of electron transfer layer 150 is 4,7-diphenyl-1,10-phenanthroline (Bphen), and thickness is 60 nanometers.
The material of electron buffer layer 160 is cesium carbonate (Cs
2cO
3), nitrine caesium (CsN
3), cesium fluoride (CsF) or lithium fluoride (LiF).In this embodiment, the thickness of electron buffer layer 160 is 0.5 ~ 5 nanometer.
In other embodiments, the material of electron buffer layer 160 can be cesium carbonate (Cs
2cO
3), nitrine caesium (CsN
3), one in cesium fluoride (CsF) and lithium fluoride (LiF) and 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), oxine aluminium (Alq
3), a kind of mixture formed that adulterates in 4,7-diphenyl-1,10-phenanthrolines (Bphen), 1,2,4-triazole derivative (TAZ) and N-aryl benzimidazole (TPBi), wherein cesium carbonate (Cs
2cO
3), nitrine caesium (CsN
3), the doping mass percent of cesium fluoride (CsF) or lithium fluoride (LiF) is 20% ~ 60%.In this embodiment, the thickness of electron buffer layer 160 is 20 ~ 60 nanometers.In preferred scheme, the material of electron buffer layer 160 is 4,7-diphenyl-1,10-phenanthroline (Bphen) and nitrine caesium (CsN
3) dopant material, nitrine caesium (CsN
3) doping mass percent be 20%, the thickness of electron buffer layer 160 is 40 nanometers.
The material of negative electrode 170 is the metal of doping cesium salt, and the doping mass percent of cesium salt in negative electrode 170 is 1% ~ 10%.Cesium salt is cesium carbonate (Cs
2cO
3), nitrine caesium (CsN
3) or cesium fluoride (CsF), metal is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).
Generally, the negative electrode of the normal metal making electroluminescent device adopting work function low is to improve the injection efficiency of electronics.If but work function is too low, then metal is very active, easily loses electronics, less stable.Therefore, in field of organic electroluminescence, generally adopt metal that silver (Ag), aluminium (Al), platinum (Pt) or the gold work function such as (Au) are moderate as electrode.The work content value of this several metal is lower, and be about-4.5eV, character is more stable.But still have larger potential barrier between its with organic material, this potential barrier still plays very large inhibition to the transmission of electronics.
The cesium salt that diligent function ratio is lower, as cesium carbonate (Cs
2cO
3), nitrine caesium (CsN
3) or cesium fluoride (CsF) be doped in silver (Ag), aluminium (Al), platinum (Pt) or the relatively high metal of gold (Au) this several work function, total work content can be made to be reduced to about 3.2eV, the potential barrier between negative electrode and organic layer is made to be reduced to about about 0.2eV, the injection of effective reduction electronics and transmission potential barrier, be conducive to injection and the transmission of electronics, the exciton recombination probability of luminescent layer is improved greatly, thus improves luminous efficiency.
In preferred scheme, the thickness of negative electrode 170 is 80 ~ 250 nanometers.
The material of the negative electrode 170 of above-mentioned electroluminescent device 100 is the metal of doping cesium salt, and the doping mass percent of cesium salt in negative electrode 170 is 1% ~ 10%.Cesium salt is cesium carbonate (Cs
2cO
3), nitrine caesium (CsN
3) or cesium fluoride (CsF), metal is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).The work function of above-mentioned several cesium salt is lower, about 2.0eV.The work function of silver (Ag), aluminium (Al), platinum (Pt) and golden (Au) is relatively high, after being doped with the cesium salt of 1% ~ 10% in the metal that this work function is relatively high, total work content can be made to be reduced to about 3.2eV, thus make the potential barrier between negative electrode and organic layer be reduced to about 0.2eV, effectively reduce injection and the transmission potential barrier of electronics, be conducive to injection and the transmission of electronics, the exciton recombination probability of luminescent layer is improved greatly, thus improves luminous efficiency.
Refer to Fig. 2, a kind of preparation method of electroluminescent device, comprises the following steps:
Step S110: conductive anode substrate is provided.
Conductive anode substrate can be indium tin oxide glass (ITO), fluorine doped tin oxide glass (FTO), mixes the zinc oxide glass (AZO) of aluminium or mix the zinc oxide glass (IZO) of indium.
Step S110 also comprises and washing and oxygen plasma pre-treatment step conductive anode substrate.Washing methods for using liquid detergent, deionized water, acetone, ethanol and isopropyl alcohol supersound washing 15 minutes successively, to remove the organic pollution of conductive anode substrate surface.Clean up and carry out oxygen plasma treatment to conductive anode substrate afterwards, the oxygen plasma treatment time is 2 ~ 15 minutes, and power is 10 ~ 50W.The work function that oxygen plasma treatment can improve conductive anode substrate is carried out to conductive anode substrate, thus injection base, hole gesture can be reduced, hole injection efficiency is provided.
Step S120: evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron buffer layer successively in the conductive anode substrate of step S110.
The thickness of hole injection layer is 20 ~ 80 nanometers, and the thickness of hole transmission layer is 20 ~ 60 nanometers, and the thickness of luminescent layer is 2 ~ 50 nanometers, and the thickness of electron transfer layer is 40 ~ 80 nanometers, and the thickness of electron buffer layer is 0.5 ~ 5 nanometer or 20 ~ 60 nanometers.
Step S130: evaporation negative electrode in the electron buffer layer of step S120, obtains described electroluminescent device.
The material of negative electrode is the metal of doping cesium salt, and wherein, cesium salt doping mass percent is in the cathode 1% ~ 10%.Cesium salt is cesium carbonate (Cs
2cO
3), nitrine caesium (CsN
3) or cesium fluoride (CsF), metal is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).
The thickness of negative electrode is 80 ~ 250 nanometers.
The preparation method of above-mentioned electroluminescent device, adopt the metallic cathode steaming legal system altogether and adulterate for cesium salt, the evaporating temperature of cesium salt and metal electrode relatively, is easier to realize common steaming, is easy to suitability for industrialized production.
It is below specific embodiment.
Embodiment 1
First indium tin oxide glass (ITO) is used liquid detergent, deionized water, acetone, ethanol successively, each ultrasonic 15 minutes of isopropyl alcohol, remove the organic pollution on ITO surface, clean up and carry out oxygen plasma treatment 2 minutes to it afterwards, power is 50W; On ITO, evaporation prepares evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron buffer layer successively, and then evaporation negative electrode in electron buffer layer, obtains electroluminescent device.
The material of negative electrode is doping cesium carbonate (Cs
2cO
3) silver (Ag), wherein cesium carbonate (Cs
2cO
3) doping mass percent is in the cathode 5%.The thickness of negative electrode is 150 nanometers.
The material of hole injection layer is molybdenum trioxide (MoO
3), thickness is 40 nanometers.
The material of hole transmission layer is N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), and thickness is 40 nanometers.
The material of luminescent layer is oxine aluminium (Alq
3), thickness is 30 nanometers.
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), and thickness is 60 nanometers.
The material of electron buffer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen) and nitrine caesium (CsN
3) adulterate the mixture formed, wherein nitrine caesium (CsN
3) doping mass percent be 20%, the thickness of electron buffer layer is 5 nanometers.
The structure of prepared organic assembly luminescent device is:
ITO/MoO
3/NPB/Alq
3/Bphen/Bphen:CsN
3/Ag:Cs
2CO
3
Refer to Fig. 3, Fig. 3 is electroluminescent device and traditional electroluminescent device: the ITO/MoO of embodiment 1
3/ NPB/Alq
3/ Bphen/ (CsN
3: Bphen) brightness of/Ag and the relation of luminous efficiency.At different brightnesses, large all than traditional electroluminescent device of the electroluminescent device luminous efficiency of embodiment 1, maximum luminous efficiency is 15.4lm/W, and traditional electroluminescent device be only 12.1lm/W, this illustrates cesium salt (Cs
2cO
3) doping greatly reduce potential barrier between negative electrode and organic layer, be more conducive to injection and the transmission of electronics, the exciton recombination probability of luminescent layer improved greatly, improves luminous efficiency.
Embodiment 2
First the zinc oxide glass (IZO) mixing indium is used liquid detergent, deionized water, acetone, ethanol successively, each ultrasonic 15 minutes of isopropyl alcohol, remove the organic pollution on IZO surface, clean up and carry out oxygen plasma treatment 5 minutes to it afterwards, power is 35W; On IZO, evaporation prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron buffer layer successively, and then evaporation negative electrode in electron buffer layer, obtains electroluminescent device.
The material of negative electrode is the aluminium (Al) of doping cesium fluoride (CsF), and the mass percent that wherein cesium fluoride (CsF) adulterates in the cathode is 1%.The thickness of negative electrode is 250 nanometers.
The material of hole injection layer is tungstic acid (WO
3), thickness is 20 nanometers.
The material of hole transmission layer is 4,4 ', 4, and "-three (carbazole-9-base) triphenylamine (TCTA), thickness is 60 nanometers.The material of luminescent layer is 4,4 ', 4 "-three (carbazole-9-base) triphenylamines (TCTA) and two (4,6-difluorophenyl pyridinato-N; C2) pyridinecarboxylic close the dopant material that iridium (FIrpic) adulterates, and wherein the doping mass percent of FIrpic is 1%.The thickness of luminescent layer is 20 nanometers.
The material of electron transfer layer is oxine aluminium (Alq
3), thickness is 50 nanometers.
The material of electron buffer layer is nitrine caesium (CsN
3), thickness is 5 nanometers.
The structure of prepared organic assembly luminescent device is:
IZO/WO
3/TCTA/TCTA:Firpic/Alq
3/CsN
3/Al:CsF
Embodiment 3
First the zinc oxide glass (AZO) mixing aluminium is used liquid detergent, deionized water, acetone, ethanol successively, each ultrasonic 15 minutes of isopropyl alcohol, remove the organic pollution on AZO surface, clean up and carry out oxygen plasma treatment 15 minutes to it afterwards, power is 10W; On AZO, evaporation prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron buffer layer successively, and the metallic cathode of then evaporation cesium salt doping in electron buffer layer, obtains electroluminescent device.
The material of negative electrode is doping nitrine caesium (CsN
3) gold (Au), wherein nitrine caesium (CsN
3) doping mass percent is in the cathode 10%.The thickness of negative electrode is 80 nanometers.
The material of hole injection layer is vanadic oxide (V
2o
5), thickness is 20 nanometers.
The material of hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane (TAPC), and thickness is 20 nanometers.
The material of luminescent layer is that N-aryl benzimidazole (TPBi) and three (2-phenylpyridine) closes iridium (Ir (ppy)
3) dopant material, wherein Ir (ppy)
3doping mass percent be 10%.The thickness of luminescent layer is 10 nanometers.
The material of electron transfer layer is N-aryl benzimidazole (TPBi), and thickness is 80 nanometers.
The material of electron buffer layer is cesium carbonate (CsCO
3), thickness is 2 nanometers.
The structure of prepared organic assembly luminescent device is:
AZO/V
2O
5/TAPC/TPBi:(Ir(ppy)
3/TPBi/CsCO
3/Au:CsN
3
Embodiment 4
First fluorine doped tin oxide glass (FTO) is used liquid detergent, deionized water, acetone, ethanol successively, each ultrasonic 15 minutes of isopropyl alcohol, remove the organic pollution on FTO surface, clean up and carry out oxygen plasma treatment 5 minutes to it afterwards, power is 35W; On FTO, evaporation prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron buffer layer successively, and the metallic cathode of then evaporation cesium salt doping in electron buffer layer, obtains electroluminescent device.
The material of negative electrode is the platinum (Pt) of doping cesium fluoride (CsF), and wherein cesium fluoride (CsF) doping mass percent is in the cathode 7%.The thickness of negative electrode is 100 nanometers.
The material of hole injection layer is tungstic acid (WO
3), thickness is 20 nanometers.
The material of hole transmission layer is 4,4 ', 4, and "-three (carbazole-9-base) triphenylamine (TCTA), thickness is 60 nanometers.
The material of luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), and the thickness of luminescent layer is 50 nanometers.
The material of electron transfer layer is 1,2,4-triazole derivative (TAZ), and thickness is 60 nanometers.
The material of electron buffer layer is lithium fluoride (LiF), and thickness is 0.7 nanometer.
The structure of prepared organic assembly luminescent device is:
FTO/WO
3/TCTA/DCJTB/TAZ/LiF/Pt:CsF
Embodiment 5
First the zinc oxide glass (ITO) mixing indium is used liquid detergent, deionized water, acetone, ethanol successively, each ultrasonic 15 minutes of isopropyl alcohol, remove the organic pollution on ITO surface, clean up and carry out oxygen plasma treatment 10 minutes to it afterwards, power is 25W; Evaporation prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron buffer layer successively, and the metallic cathode of then evaporation cesium salt doping in electron buffer layer, obtains electroluminescent device.
The material of negative electrode is doping cesium carbonate (Cs
2cO
3) aluminium (Al), wherein cesium carbonate (Cs
2cO
3) doping mass percent is in the cathode 8%.The thickness of negative electrode is 150 nanometers.
The material of hole injection layer is tungstic acid (WO
3), thickness is 20 nanometers.
The material of hole transmission layer is 4,4 ', 4, and "-three (carbazole-9-base) triphenylamine (TCTA), thickness is 60 nanometers.
The material of luminescent layer is 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA) and two (2-methyl-diphenyl [f; h] quinoxaline) (acetylacetone,2,4-pentanedione) closes the dopant material of iridium (Ir (MDQ) 2 (acac)); wherein the doping mass percent of Ir (MDQ) 2 (acac) is 2%, and the thickness of luminescent layer is 50 nanometers.
The material of electron transfer layer is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), and thickness is 60 nanometers.
The material of electron buffer layer is lithium fluoride (LiF), and thickness is 0.5 nanometer.
The structure of prepared organic assembly luminescent device is:
ITO/WO
3/TCTA/TCTA:Ir(MDQ)2(acac)/PBD/LiF/Al:Cs
2CO
3
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (7)
1. an electroluminescent device, comprise stack gradually conductive anode substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron buffer layer and negative electrode, it is characterized in that, the material of described negative electrode is the metal of doping cesium salt, wherein, the doping mass percent of described cesium salt in described negative electrode is 1% ~ 10%, and described cesium salt is cesium carbonate or nitrine caesium, and described metal is silver, aluminium, platinum or gold;
The thickness of described negative electrode is 80 ~ 250 nanometers;
The material of described electron buffer layer is selected from by the one in cesium carbonate and nitrine caesium and 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, 4,7-diphenyl-1,10-phenanthroline, 1, a kind of mixture formed that adulterates in 2,4-triazole derivative and N-aryl benzimidazole, the doping mass percent of wherein said cesium carbonate or nitrine caesium is 20 ~ 60%;
The thickness of described electron buffer layer is 20 ~ 60 nanometers;
The thickness of described electron transfer layer is 40 ~ 80 nanometers, and the material of described electron transfer layer is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine aluminium, 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole.
2. electroluminescent device according to claim 1, is characterized in that, described conductive anode substrate is indium tin oxide glass, fluorine doped tin oxide glass, mix the zinc oxide glass of aluminium or mix the zinc oxide glass of indium.
3. electroluminescent device according to claim 1, is characterized in that, the thickness of described hole injection layer is 20 ~ 80 nanometers, and the material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide.
4. electroluminescent device according to claim 1, it is characterized in that, the thickness of described hole transmission layer is 20 ~ 60 nanometers, the material of described hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine, 4,4'; 4 "-three (carbazole-9-base) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine.
5. electroluminescent device according to claim 1, it is characterized in that, the thickness of described luminescent layer is 2 ~ 50 nanometers, the material of described luminescent layer is selected from (dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, oxine aluminium, two (4,6-difluorophenyl pyridinato-N, C
2) pyridinecarboxylic closes iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) and close iridium and three (2-phenylpyridine) and close at least one in iridium; Or
The material of described luminescent layer is selected from (dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, oxine aluminium, two (4,6-difluorophenyl pyridinato-N, C
2) pyridinecarboxylic conjunction iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium and three (2-phenylpyridine) and close one and 1 in iridium, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4, 4 '-benzidine, 4, 4', 4 "-three (carbazole-9-base) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4, 4 '-benzidine, 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1, 3, 4-oxadiazole, oxine aluminium, 4, 7-diphenyl-1, 10-phenanthroline, 1, 2, the mixtures that a kind of or two kinds of doping in 4-triazole derivative and N-aryl benzimidazole are formed, wherein said (dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, oxine aluminium, two (4, 6-difluorophenyl pyridinato-N, C
2) pyridinecarboxylic closes iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) to close the doping mass percent that iridium or three (2-phenylpyridines) close iridium be 1% ~ 20%.
6. a preparation method for electroluminescent device, is characterized in that, comprises the following steps:
Step one: conductive anode substrate is provided;
Step 2: evaporation hole injection layer successively in described conductive anode substrate, hole transmission layer, luminescent layer, electron transfer layer and electron buffer layer;
Step 3: evaporation negative electrode in described electron buffer layer, obtain described electroluminescent device, the material of wherein said negative electrode is the metal of doping cesium salt, the doping mass percent of described cesium salt in described negative electrode is 1% ~ 10%, described cesium salt is cesium carbonate or nitrine caesium, and described metal is silver, aluminium, platinum or gold;
The thickness of described negative electrode is 80 ~ 250 nanometers;
The material of described electron buffer layer is selected from by the one in cesium carbonate and nitrine caesium and 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, 4,7-diphenyl-1,10-phenanthroline, 1, a kind of mixture formed that adulterates in 2,4-triazole derivative and N-aryl benzimidazole, the doping mass percent of wherein said cesium carbonate or nitrine caesium is 20 ~ 60%;
The thickness of described electron buffer layer is 20 ~ 60 nanometers;
The thickness of described electron transfer layer is 40 ~ 80 nanometers, and the material of described electron transfer layer is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1,3,4-oxadiazole, oxine aluminium, 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole.
7. the preparation method of electroluminescent device according to claim 6, it is characterized in that, step one also comprises carries out pre-treatment step to described conductive anode substrate, comprise and described conductive anode substrate used successively liquid detergent, deionized water, acetone, ethanol and isopropyl alcohol supersound washing 15 minutes, then oxygen plasma treatment is carried out, the oxygen plasma treatment time is 2 ~ 15 minutes, and power is 10 ~ 50W.
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| CN1937279A (en) * | 2006-10-30 | 2007-03-28 | 清华大学 | Method for preparingorganic electroluminescent device electronic injection layer |
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| CN1937279A (en) * | 2006-10-30 | 2007-03-28 | 清华大学 | Method for preparingorganic electroluminescent device electronic injection layer |
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