CN102983288B - A kind of blue-green organic electroluminescent device and preparation method thereof - Google Patents
A kind of blue-green organic electroluminescent device and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of blue-green organic electroluminescent device, with two (4, 6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium as blue-green luminous organic material, described luminescent material has high-luminous-efficiency and superior electron transport ability concurrently, to dominate luminescent layer and electronics in hole dominate doping content in luminescent layer by optimizing described luminescent material respectively, limit the scope between luminous zone and ensure that electronics and the hole balanced distribution at recombination region, delay the efficiency decay of device, and then make device under lower operating voltage, obtain the blue-green electroluminescence of high brightness, namely blue-green organic electroluminescent device provided by the invention is while reducing device operating voltages, improve the luminous efficiency of device, brightness and thermal stability.
Description
Technical field
The present invention relates to technical field of organic electroluminescence, particularly relate to a kind of blue-green organic electroluminescent device and preparation method thereof.
Background technology
Organic electroluminescence device is a kind of selfluminous element, and when electric charge is injected into the organic film between hole injecting electrode (anode) and electron injection electrode (negative electrode), electronics and hole combine and bury in oblivion subsequently, thus produce light.Organic electroluminescence device has the characteristics such as low-voltage, high brightness, wide viewing angle, therefore organic electroluminescence device is obtaining swift and violent development in recent years, wherein, blue-green organic electroluminescent device, due to the application prospect in monochrome display, white light modulation etc., has become current study hotspot.
All the time, many research teams both domestic and external set about from materials synthesis and device optimization aspect, make great efforts the combination property of raising blue-green organic electroluminescent device to meeting the needs of industrialization, trivalent complex of iridium is considered as desirable blue-green electroluminescent organic material because having the advantages such as the high and glow color of luminous efficiency is adjustable by academia and industrial circle, such as, the people such as the S.R.Forrest of Princeton university in 2003 adopt can launch the complex of iridium FIrpic of blue green light as electroluminescent organic material, organic electroluminescence device is obtained by the method for doping, it is luminous that this device shows ideal blue-green, but, unbalanced carrier injection cause the efficiency of device and brightness lower, in addition, the operating voltage of device is also higher.
In order to address these problems, 2008, the people such as the FrankySo of good fortune Flo-Rida-Low university of the U.S. obtained the blue-green organic electroluminescent device of sandwich construction by being mixed in preferred material of main part by high efficiency complex of iridium.This device has higher maximum luminous efficiency, but the current density of device is lower, and luminous efficiency promptly decays along with the raising of current density, thus causes the brightness lower operating voltage of device higher.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of blue-green organic electroluminescent device and preparation method thereof, blue-green organic electroluminescent device provided by the invention, while reducing device operating voltages, improves the luminous efficiency of device, brightness and thermal stability.
The invention provides a kind of blue-green organic electroluminescent device, comprising:
Substrate;
There is anode layer over the substrate;
Described anode layer there is hole to dominate luminescent layer, described hole is dominated luminescent layer and is entrained in cavity type organic host material by blue-green luminous organic material and is formed, the mass percent that described blue-green luminous organic material accounts for described cavity type organic host material is 6.0% ~ 16.0%, described blue-green luminous organic material is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium;
Dominating in described hole on luminescent layer has electronics to dominate luminescent layer, described electronics is dominated luminescent layer and is entrained in electron type organic host material by blue-green luminous organic material and is formed, the mass percent that described blue-green luminous organic material accounts for described electron type organic host material is 13.0% ~ 22.0%, described blue-green luminous organic material is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium;
Dominate on luminescent layer at described electronics and have negative electrode.
Preferably, described cavity type organic host material is two (N-carbazole)-1, the 1'-biphenyl, 1 of 4,4'-, 3-bis-carbazole-9-base benzene, 9,9'-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazoles, 1,3,5-tri-(9-carbazyl) benzene, 4,4', 4 "-three (carbazole-9-base) triphenylamines or Isosorbide-5-Nitrae-bis-(tri-phenyl-silane base) biphenyl.
Preferably, the thickness of luminescent layer is dominated in described hole is 3 ~ 10 nanometers.
Preferably, described electron type organic host material is 9,9'-(2,6-pyridine two base two-3, the sub-benzene of 1-) two-9H-carbazole, 1, two (tri-phenyl-silane base) benzene, 2 of 4-, 2 '-bis-(4-(9-carbazyl) phenyl) biphenyl, three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine, 1,3,5-tri-[(3-pyridine)-3-phenyl] benzene, 1, two [3,5-bis-(3-pyridine radicals) phenyl] benzene of 3-or two (triphenyl the is silica-based)-9H-carbazole of 9-(4-t-butyl-phenyl)-3,6-.
Preferably, described electronics dominates the thickness of luminescent layer is 3 ~ 10 nanometers.
Preferably, described anode layer and hole are dominated between luminescent layer and are also comprised hole transmission layer;
Described hole transmission layer is formed by 4,4'-cyclohexyl two [N, N-bis-(4-aminomethyl phenyl) aniline].
Preferably, described electronics is dominated between luminescent layer and negative electrode and is also comprised hole blocking layer;
Described hole blocking layer is formed by two [3,5-bis-(3-pyridine radicals) phenyl] benzene of three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine, 1,3,5-tri-[(3-pyridine)-3-phenyl] benzene or 1,3-.
Preferably, also resilient coating is comprised between described hole blocking layer and negative electrode;
Described resilient coating is formed by lithium fluoride.
Present invention also offers a kind of preparation method of blue-green organic electroluminescent device, comprising:
Substrate forms anode layer;
Described anode layer forms hole and dominates luminescent layer, described hole is dominated luminescent layer and is entrained in cavity type organic host material by blue-green luminous organic material and is formed, the mass percent that described blue-green luminous organic material accounts for described cavity type organic host material is 6.0% ~ 16.0%, described blue-green luminous organic material is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium;
Dominate in described hole and luminescent layer forms electronics dominate luminescent layer, described electronics is dominated luminescent layer and is entrained in electron type organic host material by blue-green luminous organic material and is formed, the mass percent that described blue-green luminous organic material accounts for described electron type organic host material is 13.0% ~ 22.0%, described blue-green luminous organic material is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium;
Dominate on luminescent layer at described electronics and form negative electrode, obtain blue-green organic electroluminescent device.
Preferably, the thickness of luminescent layer is dominated in described hole is 3 ~ 10 nanometers;
The thickness that described electronics dominates luminescent layer is 3 ~ 10 nanometers.
Compared with prior art, the present invention is with two (4, 6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium as blue-green luminous organic material, described luminescent material has high-luminous-efficiency and superior electron transport ability concurrently, to dominate luminescent layer and electronics in hole dominate doping content in luminescent layer by optimizing described luminescent material respectively, namely dominating the mass percent that luminescent material described in luminescent layer accounts for cavity type organic host material in hole is 6.0% ~ 16.0%, dominating at electronics the mass percent that luminescent material described in luminescent layer accounts for described electron type organic host material is 13.0% ~ 22.0%, thus the scope limited between luminous zone ensure that electronics and the hole balanced distribution at recombination region, delay the efficiency decay of device, and then make device under lower operating voltage, obtain the blue-green electroluminescence of high brightness, experimental result shows, a bright voltage of blue-green organic electroluminescent device provided by the invention is 2.8 ~ 3.0 volts, high-high brightness is 33932 ~ 48325cd/m
2, maximum current efficiency is 48.76 ~ 54.27cd/A, and maximum power efficiency is 49.11 ~ 56.59lm/W.
Accompanying drawing explanation
The structural representation of the blue-green organic electroluminescent device that Fig. 1 provides for the embodiment of the present invention;
Current density-voltage-luminosity response the figure of the blue-green organic electroluminescent device that Fig. 2 provides for the embodiment of the present invention 1;
Current density-power efficiency-current efficiency characteristics the curve chart of the blue-green organic electroluminescent device that Fig. 3 provides for the embodiment of the present invention 1;
The electroluminescent spectrum figure of the blue-green organic electroluminescent device that Fig. 4 provides for the embodiment of the present invention 1;
Current density-voltage-luminosity response the figure of the blue-green organic electroluminescent device that Fig. 5 provides for the embodiment of the present invention 2;
Current density-power efficiency-current efficiency characteristics the curve chart of the blue-green organic electroluminescent device that Fig. 6 provides for the embodiment of the present invention 2.
Embodiment
The invention provides a kind of blue-green organic electroluminescent device, comprising:
Substrate;
There is anode layer over the substrate;
Described anode layer there is hole to dominate luminescent layer, described hole is dominated luminescent layer and is entrained in cavity type organic host material by blue-green luminous organic material and is formed, the mass percent that described blue-green luminous organic material accounts for described cavity type organic host material is 6.0% ~ 16.0%, described blue-green luminous organic material is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium;
Dominating in described hole on luminescent layer has electronics to dominate luminescent layer, described electronics is dominated luminescent layer and is entrained in electron type organic host material by blue-green luminous organic material and is formed, the mass percent that described blue-green luminous organic material accounts for described electron type organic host material is 13.0% ~ 22.0%, described blue-green luminous organic material is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium;
Dominate on luminescent layer at described electronics and have negative electrode.
The present invention does not have particular/special requirement to described substrate, can be glass or plastics, is preferably glass.According to the present invention, described anode layer is formed by the material being easy to inject in hole, be preferably conducting metal or conducting metal oxide, include but not limited to nickel, platinum, gold, indium tin oxide (ITO) and indium-zinc oxide (IZO), be more preferably indium tin oxide, the face resistance of described indium tin oxide is 10 ~ 15 ohm; In the present invention, the conducting metal on substrate or conducting metal oxide corrosion are obtained electrode, and the present invention does not have particular/special requirement, as corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long to the shape of the electrode of corrosion and size.
According to the present invention, described hole is dominated luminescent layer and is entrained in cavity type organic host material by blue-green luminous organic material and is formed, and the thickness that luminescent layer is dominated in described hole is preferably 3 ~ 10 nanometers, is more preferably 5 ~ 8 nanometers; The mass percent that described blue-green luminous organic material accounts for described cavity type organic host material is 6.0% ~ 16.0%, is preferably 7.0% ~ 14.0%, is more preferably 8.0% ~ 11.0%; Described blue-green luminous organic material is for having two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium (being called for short FIrpic) of formula (I) structure, and described FIrpic has high luminous efficiency and superior electron transport ability,
formula (I).
Described cavity type organic host material is preferably 4 of formula (II) structure, two (the N-carbazole)-1 of 4'-, 1'-biphenyl (being called for short CBP), 1 of formula (III) structure, 3-bis-carbazole-9-base benzene (being called for short MCP), 9 of formula (IV) structure, 9'-(5-(tri-phenyl-silane base)-1, 3-phenyl) two-9H-carbazoles (being called for short Simcp), 1 of formula (V) structure, 3, 5-tri-(9-carbazyl) benzene (being called for short TCP), 4 of formula (VI) structure, 4', 4 "-three (carbazole-9-base) fluorine-triphenylamine structure (be called for short TCTA) or formula (VII) structure 1, two (tri-phenyl-silane base) biphenyl of 4-(being called for short BSB), be more preferably 1 of formula (III) structure, 1 of 3-bis-carbazole-9-base benzene (be called for short MCP) or formula (V) structure, 3, 5-tri-(9-carbazyl) benzene (being called for short TCP), the material of main part of luminescent layer dominated by cavity type organic material of the present invention using wide energy gap organic material as hole, be conducive to the center being limited in luminescent layer between the recombination region by hole and electronics, thus improve the efficiency of device.
formula (II);
formula (III);
formula (IV);
formula (V);
formula (VI);
formula (VII).
In order to improve the transmittability in hole, intercept the transmission of electronics simultaneously, and then reduce the energy consumption of device, improve the efficiency of device, described anode layer and hole are dominated between luminescent layer and are preferably also comprised hole transmission layer, and the thickness of described hole transmission layer is preferably 30 ~ 50 nanometers; The material of the present invention to hole transmission layer is not particularly limited, and is preferably and is formed by 4, the 4'-cyclohexyl two [N, N-bis-(4-aminomethyl phenyl) aniline] with formula (VIII) structure (being called for short TAPC),
formula (VIII).
According to the present invention, described electronics is dominated luminescent layer and is entrained in electron type organic host material by blue-green luminous organic material and is formed, and the thickness that described electronics dominates luminescent layer is 3 ~ 10 nanometers, is more preferably 5 ~ 8 nanometers; The mass percent that described blue-green luminous organic material accounts for described electron type organic host material is 13.0% ~ 22.0%, is preferably 15.0% ~ 21.0%, is more preferably 17.0% ~ 20.0%; Described blue-green luminous organic material is for having two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium (being called for short FIrpic) of formula (I) structure, and described FIrpic has high luminous efficiency and superior electron transport ability.
Described electron type organic host material is preferably 9 of formula (IX) structure, 9'-(2, 6-pyridine two base two-3, the sub-benzene of 1-) two-9H-carbazole (being called for short 26DCzPPy), 1 of formula (X) structure, two (tri-phenyl-silane base) benzene of 4-(being called for short UGH2), 2 of formula (XI) structure, 2 '-bis-(4-(9-carbazyl) phenyl) biphenyl (being called for short BCBP), three [2 of formula (XII) structure, 4, 6-trimethyl-3-(3-pyridine radicals) phenyl] borine (being called for short 3TPYMB), 1 of formula (XIII) structure, 3, 5-tri-[(3-pyridine)-3-phenyl] benzene (being called for short TmPyPB), 1 of formula (XIV) structure, 3-two [3, 5-bis-(3-pyridine radicals) phenyl] 9-(4-t-butyl-phenyl)-3 of benzene (be called for short BmPyPhB) or formula (XV) structure, two (triphenyl the is silica-based)-9H-carbazole of 6-(being called for short CzSi), be more preferably 9 of formula (IX) structure, 9'-(2, 6-pyridine two base two-3, the sub-benzene of 1-) two-9H-carbazole (being called for short 26DCzPPy), 2 of formula (XI) structure, 2 '-bis-(4-(9-carbazyl) phenyl) biphenyl (being called for short BCBP), 1 of formula (XIII) structure, 3, 1 of 5-tri-[(3-pyridine)-3-phenyl] benzene (be called for short TmPyPB) or formula (XIV), 3-two [3, 5-bis-(3-pyridine radicals) phenyl] benzene (being called for short BmPyPhB), the material of main part of luminescent layer dominated by electron type organic material of the present invention using wide energy gap organic material as electronics, be conducive to the center being limited in luminescent layer between the recombination region by hole and electronics, thus improve the efficiency of device,
formula (IX);
formula (X);
formula (XI);
formula (XII);
formula (XIII);
formula (XIV);
formula (XV).
The present invention is applied to hole and dominates luminescent layer and electronics dominates luminescent layer using wide energy gap organic material as described cavity type organic material and electron type organic material, be conducive to the center being limited in luminescent layer between the recombination region by hole and electronics, make full use of the exciton that electronics and hole-recombination produce, thus obtain high Carrier recombination probability and device efficiency.
According to the present invention, described negative electrode is preferably the metal of low work function, includes but not limited to calcium, barium, aluminium, magnesium and silver, is more preferably metallic aluminium; The thickness of described negative electrode is 90 ~ 150 nanometers, is preferably 100 ~ 120 nanometers.
In order to improve the transmittability of electronics, intercept the transmission in hole simultaneously, and then reduce the energy consumption of device, improve the efficiency of device, described electronics is dominated between luminescent layer and negative electrode and is preferably also comprised hole blocking layer;
The thickness of described hole blocking layer is preferably 30 ~ 50 nanometers, described hole blocking layer is preferably by three [2 of formula (XII) structure, 4, 6-trimethyl-3-(3-pyridine radicals) phenyl] borine (being called for short 3TPYMB), 1 of formula (XIII) structure, 3, 1 of 5-tri-[(3-pyridine)-3-phenyl] benzene (be called for short TmPyPB) or formula (XIV) structure, 3-two [3, 5-bis-(3-pyridine radicals) phenyl] benzene (being called for short BmPyPhB) formation, be more preferably 1 of formula (XIII) structure, 3, 1 of 5-tri-[(3-pyridine)-3-phenyl] benzene (be called for short TmPyPB) or formula (XIV) structure, 3-two [3, 5-bis-(3-pyridine radicals) phenyl] benzene (being called for short BmPyPhB), the material of formation hole blocking layer of the present invention has lower highest occupied molecular orbital and higher triplet energies, can between restriction luminous zone while the scope of activities of confinement exciton effectively, thus ensure that device has higher luminous efficiency and efficiency decay more slowly.
In order to promote the injection efficiency of electronics, and then improving the efficiency of device, between described hole blocking layer and negative electrode, preferably also comprising resilient coating; Described resilient coating is formed by lithium fluoride; Described buffer layer thickness is preferably 0.8 ~ 1.6 nanometer, is more preferably 0.9 ~ 1.3 nanometer.
The luminous zone of device of the present invention is intersected to form mutually by anode and negative electrode, and the size of the present invention to device does not have particular/special requirement, as can be the device of 8 ~ 12 square millimeters for luminous zone area.
Below in conjunction with accompanying drawing, the blue-green organic electroluminescent device that the embodiment of the present invention provides is described, see Fig. 1, the structural representation of the blue-green organic electroluminescent device that Fig. 1 provides for the embodiment of the present invention, as seen from the figure, described organic electroluminescence device by substrate 1, anode layer 2, hole transmission layer 3, luminescent layer 4 is dominated in hole, electronics dominates luminescent layer 5, hole blocking layer 6, resilient coating 7 and negative electrode 8 connect to form successively.
Present invention also offers a kind of preparation method of blue-green organic electroluminescent device, comprising:
Substrate forms anode layer;
Described anode layer forms hole and dominates luminescent layer, described hole is dominated luminescent layer and is entrained in cavity type organic host material by blue-green luminous organic material and is formed, the mass percent that described blue-green luminous organic material accounts for described cavity type organic host material is 6.0% ~ 16.0%, described blue-green luminous organic material is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium;
Dominate in described hole and luminescent layer forms electronics dominate luminescent layer, described electronics is dominated luminescent layer and is entrained in electron type organic host material by blue-green luminous organic material and is formed, the mass percent that described blue-green luminous organic material accounts for described electron type organic host material is 13.0% ~ 22.0%, described blue-green luminous organic material is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium;
Dominate on luminescent layer at described electronics and form negative electrode, obtain blue-green organic electroluminescent device.
According to the present invention, first on substrate, form anode layer, the present invention is not particularly limited described formation method, is preferably method well known to those skilled in the art.The present invention does not have particular/special requirement to described substrate, can be glass or plastics, is preferably glass.According to the present invention, described anode layer is formed by the material being easy to inject in hole, be preferably conducting metal or conducting metal oxide, include but not limited to nickel, platinum, gold, indium tin oxide (ITO) and indium-zinc oxide (IZO), be more preferably indium tin oxide, the face resistance of described indium tin oxide is 10 ~ 15 ohm; In the present invention, the conducting metal on substrate or conducting metal oxide corrosion are obtained electrode, and the present invention does not have particular/special requirement, as corroded into the strip shaped electric poles of 10 mm wides, 30 millimeters long to the shape of the electrode of corrosion and size.
According to the present invention, described anode layer forms hole and dominates luminescent layer, the present invention is not particularly limited described formation method, is preferably method well known to those skilled in the art, includes but not limited to the methods such as vacuum evaporation.According to the present invention, described hole is dominated luminescent layer and is entrained in cavity type organic host material by blue-green luminous organic material and is formed, the evaporation rate of described blue-green luminous organic material is preferably 0.003 ~ 0.022 nm/sec, and the evaporation rate of described cavity type organic host material is preferably 0.05 ~ 0.1 nm/sec; The thickness that luminescent layer is dominated in described hole is preferably 3 ~ 10 nanometers, is more preferably 5 ~ 8 nanometers;
The mass percent that described blue-green luminous organic material accounts for described cavity type organic host material is 6.0% ~ 16.0%, is preferably 7.0% ~ 14.0%, is more preferably 8.0% ~ 11.0%; Described blue-green luminous organic material is for having two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium (being called for short FIrpic) of formula (I) structure, and described FIrpic has high luminous efficiency and superior electron transport ability,
formula (I).
Described cavity type organic host material is preferably 4 of formula (II) structure, two (the N-carbazole)-1 of 4'-, 1'-biphenyl (being called for short CBP), 1 of formula (III) structure, 3-bis-carbazole-9-base benzene (being called for short MCP), 9 of formula (IV) structure, 9'-(5-(tri-phenyl-silane base)-1, 3-phenyl) two-9H-carbazoles (being called for short Simcp), 1 of formula (V) structure, 3, 5-tri-(9-carbazyl) benzene (being called for short TCP), 4 of formula (VI) structure, 4', 4 "-three (carbazole-9-base) fluorine-triphenylamine structure (be called for short TCTA) or formula (VII) structure 1, two (tri-phenyl-silane base) biphenyl of 4-(being called for short BSB), be more preferably 1 of formula (III) structure, 1 of 3-bis-carbazole-9-base benzene (be called for short MCP) or formula (V) structure, 3, 5-tri-(9-carbazyl) benzene (being called for short TCP), the material of main part of luminescent layer dominated by cavity type organic material of the present invention using wide energy gap organic material as hole, be conducive to the center being limited in luminescent layer between the recombination region by hole and electronics, thus improve the efficiency of device.
formula (II);
formula (III);
formula (IV);
formula (V);
formula (VI);
formula (VII).
According to the present invention, before formation luminescent layer, preferably cleaning has the substrate of the first electrode, and carries out ultraviolet, ozone or low-voltage plasma process to the substrate after cleaning.
In order to improve the transmittability in hole, intercept the transmission of electronics simultaneously, and then reduce the energy consumption of device, improve the efficiency of device, preferably on described anode layer, hole transmission layer was formed before luminescent layer is dominated in formation hole, invention is not particularly limited described formation method, is preferably method well known to those skilled in the art, includes but not limited to the methods such as vacuum evaporation.The thickness of described hole transmission layer is preferably 30 ~ 50 nanometers; The material of the present invention to hole transmission layer is not particularly limited, and is preferably and is formed by 4, the 4'-cyclohexyl two [N, N-bis-(4-aminomethyl phenyl) aniline] with formula (VIII) structure (being called for short TAPC),
formula (VIII).
According to the present invention, dominate in described hole and luminescent layer forms electronics dominate luminescent layer, the present invention is not particularly limited described formation method, is preferably method well known to those skilled in the art, includes but not limited to the methods such as vacuum evaporation.According to the present invention, described electronics is dominated luminescent layer and is entrained in electron type organic host material by blue-green luminous organic material and is formed, and the thickness that described electronics dominates luminescent layer is 3 ~ 10 nanometers, is more preferably 5 ~ 8 nanometers; The mass percent that described blue-green luminous organic material accounts for described electron type organic host material is 13.0% ~ 22.0%, is preferably 15.0% ~ 21.0%, is more preferably 17.0% ~ 20.0%; Described blue-green luminous organic material is for having two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium (being called for short FIrpic) of formula (I) structure, and described FIrpic has high luminous efficiency and superior electron transport ability.
Described electron type organic host material is preferably 9 of formula (IX) structure, 9'-(2, 6-pyridine two base two-3, the sub-benzene of 1-) two-9H-carbazole (being called for short 26DCzPPy), 1 of formula (X) structure, two (tri-phenyl-silane base) benzene of 4-(being called for short UGH2), 2 of formula (XI) structure, 2 '-bis-(4-(9-carbazyl) phenyl) biphenyl (being called for short BCBP), three [2 of formula (XII) structure, 4, 6-trimethyl-3-(3-pyridine radicals) phenyl] borine (being called for short 3TPYMB), 1 of formula (XIII) structure, 3, 5-tri-[(3-pyridine)-3-phenyl] benzene (being called for short TmPyPB), 1 of formula (XIV) structure, 3-two [3, 5-bis-(3-pyridine radicals) phenyl] 9-(4-t-butyl-phenyl)-3 of benzene (be called for short BmPyPhB) or formula (XV) structure, two (triphenyl the is silica-based)-9H-carbazole of 6-(being called for short CzSi), be more preferably 9 of formula (IX) structure, 9'-(2, 6-pyridine two base two-3, the sub-benzene of 1-) two-9H-carbazole (being called for short 26DCzPPy), 2 of formula (XI) structure, 2 '-bis-(4-(9-carbazyl) phenyl) biphenyl (being called for short BCBP), 1 of formula (XIII) structure, 3, 1 of 5-tri-[(3-pyridine)-3-phenyl] benzene (be called for short TmPyPB) or formula (XIV), 3-two [3, 5-bis-(3-pyridine radicals) phenyl] benzene (being called for short BmPyPhB), the material of main part of luminescent layer dominated by electron type organic material of the present invention using wide energy gap organic material as electronics, be conducive to the center being limited in luminescent layer between the recombination region by hole and electronics, thus improve the efficiency of device,
formula (IX);
formula (X);
formula (XI);
formula (XII);
formula (XIII);
formula (XIV);
formula (XV).
The present invention is applied to hole and dominates luminescent layer and electronics dominates luminescent layer using wide energy gap organic material as described cavity type organic material and electron type organic material, be conducive to the center being limited in luminescent layer between the recombination region by hole and electronics, make full use of the exciton that electronics and hole-recombination produce, thus obtain high Carrier recombination probability and device efficiency.
According to the present invention, dominate on luminescent layer form negative electrode at described electronics, the present invention is not particularly limited described formation method, is preferably method well known to those skilled in the art, includes but not limited to the methods such as vacuum evaporation.Described negative electrode is preferably the metal of low work function, includes but not limited to calcium, barium, aluminium, magnesium and silver, is more preferably metallic aluminium; The thickness of described negative electrode is 90 ~ 150 nanometers, is preferably 100 ~ 120 nanometers.
In order to improve the transmittability of electronics, intercept the transmission in hole simultaneously, and then reduce the energy consumption of device, improve the efficiency of device, preferably dominated on luminescent layer at described electronics before described negative electrode is formed and form hole blocking layer, the present invention is not particularly limited described formation method, is preferably method well known to those skilled in the art, includes but not limited to the methods such as vacuum evaporation.The thickness of hole blocking layer of the present invention is preferably 30 ~ 50 nanometers, described hole blocking layer is preferably by three [2 of formula (XII) structure, 4, 6-trimethyl-3-(3-pyridine radicals) phenyl] borine (being called for short 3TPYMB), 1 of formula (XIII) structure, 3, 1 of 5-tri-[(3-pyridine)-3-phenyl] benzene (be called for short TmPyPB) or formula (XIV) structure, 3-two [3, 5-bis-(3-pyridine radicals) phenyl] benzene (being called for short BmPyPhB) formation, be more preferably 1 of formula (XIII) structure, 3, 1 of 5-tri-[(3-pyridine)-3-phenyl] benzene (be called for short TmPyPB) or formula (XIV) structure, 3-two [3, 5-bis-(3-pyridine radicals) phenyl] benzene (being called for short BmPyPhB), the material of formation hole blocking layer of the present invention has lower highest occupied molecular orbital and higher triplet energies, can between restriction luminous zone while the scope of activities of confinement exciton effectively, thus ensure that device has higher luminous efficiency and efficiency decay more slowly.
In order to promote the injection efficiency of electronics, and then improve the efficiency of device, preferably on described hole blocking layer, resilient coating was formed before the described negative electrode of formation, the present invention is not particularly limited described formation method, be preferably method well known to those skilled in the art, include but not limited to the methods such as vacuum evaporation.Described resilient coating is formed by lithium fluoride; Described buffer layer thickness is preferably 0.8 ~ 1.6 nanometer, is more preferably 0.9 ~ 1.3 nanometer.
Below in conjunction with accompanying drawing, the preparation method to the organic electroluminescence device that the embodiment of the present invention provides is described, see Fig. 1, the structural representation of the blue-green organic electroluminescent device that Fig. 1 provides for the embodiment of the present invention, its preparation method comprises the following steps: form anode layer 2 on substrate 1; Then clean described substrate and plasma treatment is carried out to it; Anode layer 2 forms hole transmission layer 3 by the mode of vacuum evaporation; Hole transmission layer 3 forms hole by the mode of vacuum evaporation and dominates luminescent layer 4; Dominate in hole and luminescent layer 4 forms electronics by the mode of vacuum evaporation dominate luminescent layer 5, dominate on luminescent layer 5 at electronics and form hole blocking layer 6 by the mode of vacuum evaporation, hole blocking layer 6 forms resilient coating 7 by the mode of vacuum evaporation, resilient coating 7 forms negative electrode 8 by the mode of evaporation, obtains organic electroluminescence device as shown in Figure 1.
Compared with prior art, the present invention is with two (4, 6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium as blue-green luminous organic material, described luminescent material has high-luminous-efficiency and superior electron transport ability concurrently, to dominate luminescent layer and electronics in hole dominate doping content in luminescent layer by optimizing described luminescent material respectively, namely dominating the mass percent that luminescent material described in luminescent layer accounts for cavity type organic host material in hole is 6.0% ~ 16.0%, dominating at electronics the mass percent that luminescent material described in luminescent layer accounts for described electron type organic host material is 13.0% ~ 22.0%, thus the scope limited between luminous zone ensure that electronics and the hole balanced distribution at recombination region, delay the efficiency decay of device, and then make device under lower operating voltage, obtain the blue-green electroluminescence of high brightness.
In order to understand the present invention further, below in conjunction with embodiment, a kind of blue-green organic electroluminescent device provided by the invention and preparation method thereof is described.
Embodiment 1
Using glass as substrate; Form the anode layer of indium tin oxide (ITO) material on a glass substrate, and anode layer chemical corrosion is become the strip shaped electric poles of 10 mm wides, 30 millimeters long, by strip shaped electric poles successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes put into oven for drying, being transferred to organic vapor deposition room after ito anode being carried out to the Low Pressure Oxygen plasma treatment of 10 minutes with the voltage of 400 volts under the atmosphere of 10 handkerchiefs, is 1 ~ 2 × 10 in vacuum degree
-5in the organic vapor deposition room of handkerchief, on the anode layer successively with the hole transmission layer of TAPC evaporation rate in 0.05 nm/sec evaporation 50 nanometer thickness, FIrpic evaporation rate to be adulterated at 0.1 nm/sec evaporation 5 nanometer thickness FIrpic in 0.008 nm/sec and MCP evaporation rate, and luminescent layer is dominated in the hole of MCP, FIrpic evaporation rate dominates luminescent layer and the TmPyPB evaporation rate hole blocking layer in 0.05 nm/sec evaporation 40 nanometer thickness in 0.02 nm/sec and BCBP evaporation rate at the adulterate electronics of BCBP of 0.1 nm/sec evaporation 5 nanometer thickness FIrpic; Then the device do not completed is transferred to metal evaporation room, 4 ~ 6 × 10
-5with the LiF resilient coating of evaporation rate evaporation 1.0 nanometer thickness of 0.005 nm/sec under the vacuum of handkerchief, then by mask on LiF layer with the metal A l electrode of evaporation rate evaporation 100 nanometer thickness of 0.5 nm/sec, obtaining structure is ITO/TAPC/FIrpic (8%): MCP/FIrpic (20%): the blue-green organic electroluminescent device of BCBP/TmPyPB/LiF/Al.
The light-emitting area of described blue-green organic electroluminescent device is 10 square millimeters.
Performance test is carried out to described organic electroluminescence device, result is see Fig. 2, Fig. 3 and Fig. 4, Current density-voltage-luminosity response the figure of the blue-green organic electroluminescent device that Fig. 2 provides for the embodiment of the present invention 1, current density-power efficiency-current efficiency characteristics the curve chart of the blue-green organic electroluminescent device that Fig. 3 provides for the embodiment of the present invention 1, the electroluminescent spectrum figure of the blue-green organic electroluminescent device that Fig. 4 provides for the embodiment of the present invention 1.As seen from the figure, a bright voltage of described blue-green organic electroluminescent device is 2.9 volts, and high-high brightness is 46249cd/m
2, maximum current efficiency is 50.21cd/A, and maximum power efficiency is 50.31lm/W, and under DC power supply drives, display main peak is positioned at the blue green light that 472 nanometer acromions are positioned at 500 nanometers, when brightness is 20000cd/m
2time, the chromaticity coordinates of device is (0.124,0.326).
Embodiment 2
Using glass as substrate; Form the anode layer of indium tin oxide (ITO) material on a glass substrate, and anode layer chemical corrosion is become the strip shaped electric poles of 10 mm wides, 30 millimeters long, by strip shaped electric poles successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes put into oven for drying, being transferred to organic vapor deposition room after ito anode being carried out to the Low Pressure Oxygen plasma treatment of 10 minutes with the voltage of 400 volts under the atmosphere of 10 handkerchiefs, is 1 ~ 2 × 10 in vacuum degree
-5in the organic vapor deposition room of handkerchief, on the anode layer successively with the hole transmission layer of TAPC evaporation rate in 0.05 nm/sec evaporation 40 nanometer thickness, FIrpic evaporation rate to be adulterated at 0.1 nm/sec evaporation 5 nanometer thickness FIrpic in 0.01 nm/sec and MCP evaporation rate, and luminescent layer is dominated in the hole of MCP, FIrpic evaporation rate dominates luminescent layer and the TmPyPB evaporation rate hole blocking layer in 0.05 nm/sec evaporation 40 nanometer thickness in 0.018 nm/sec and TmPyPB evaporation rate at the adulterate electronics of TmPyPB of 0.1 nm/sec evaporation 5 nanometer thickness FIrpic; Then the device do not completed is transferred to metal evaporation room, 4 ~ 6 × 10
-5with the LiF resilient coating of evaporation rate evaporation 1.0 nanometer thickness of 0.005 nm/sec under the vacuum of handkerchief, then by mask on LiF layer with the metal A l electrode of evaporation rate evaporation 100 nanometer thickness of 0.5 nm/sec, obtaining structure is ITO/TAPC/FIrpic (10%): MCP/FIrpic (18%): the blue-green organic electroluminescent device of TmPyPB/TmPyPB/LiF/Al.
The light-emitting area of described blue-green organic electroluminescent device is 10 square millimeters.
Performance test is carried out to described organic electroluminescence device, result is see Fig. 5 and Fig. 6, current density-power efficiency-current efficiency characteristics the curve chart of the blue-green organic electroluminescent device that the Current density-voltage of the blue-green organic electroluminescent device that Fig. 5 provides for the embodiment of the present invention 2-luminosity response figure, Fig. 6 provides for the embodiment of the present invention 2.As seen from the figure, a bright voltage of described blue-green organic electroluminescent device is 2.9 volts, and high-high brightness is 33932cd/m
2, maximum current efficiency is 54.27cd/A, and maximum power efficiency is 56.59lm/W, and under DC power supply drives, display main peak is positioned at the blue green light that 472 nanometer acromions are positioned at 500 nanometers, when brightness is 20000cd/m
2time, the chromaticity coordinates of device is (0.126,0.331).
Embodiment 3
Using glass as substrate; Form the anode layer of indium tin oxide (ITO) material on a glass substrate, and anode layer chemical corrosion is become the strip shaped electric poles of 10 mm wides, 30 millimeters long, by strip shaped electric poles successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes put into oven for drying, being transferred to organic vapor deposition room after ito anode being carried out to the Low Pressure Oxygen plasma treatment of 10 minutes with the voltage of 400 volts under the atmosphere of 10 handkerchiefs, is 1 ~ 2 × 10 in vacuum degree
-5in the organic vapor deposition room of handkerchief, on the anode layer successively with the hole transmission layer of TAPC evaporation rate in 0.05 nm/sec evaporation 50 nanometer thickness, FIrpic evaporation rate to be adulterated at 0.1 nm/sec evaporation 5 nanometer thickness FIrpic in 0.008 nm/sec and TCP evaporation rate, and luminescent layer is dominated in the hole of TCP, FIrpic evaporation rate dominates luminescent layer and the TmPyPB evaporation rate hole blocking layer in 0.05 nm/sec evaporation 40 nanometer thickness in 0.02 nm/sec and 26DCzPPy evaporation rate at the adulterate electronics of 26DCzPPy of 0.1 nm/sec evaporation 5 nanometer thickness FIrpic; Then the device do not completed is transferred to metal evaporation room, 4 ~ 6 × 10
-5with the LiF resilient coating of evaporation rate evaporation 1.0 nanometer thickness of 0.005 nm/sec under the vacuum of handkerchief, then by mask on LiF layer with the metal A l electrode of evaporation rate evaporation 100 nanometer thickness of 0.5 nm/sec, obtaining structure is ITO/TAPC/FIrpic (8%): TCP/FIrpic (20%): the blue-green organic electroluminescent device of 26DCzPPy/TmPyPB/LiF/Al.
The light-emitting area of described blue-green organic electroluminescent device is 10 square millimeters.
Carry out performance test to described organic electroluminescence device, result shows, a bright voltage of described blue-green organic electroluminescent device is 3.0 volts, and high-high brightness is 45622cd/m
2, maximum current efficiency is 49.68cd/A, and maximum power efficiency is 50.03lm/W, and under DC power supply drives, display main peak is positioned at the blue green light that 472 nanometer acromions are positioned at 500 nanometers, when brightness is 20000cd/m
2time, the chromaticity coordinates of device is (0.129,0.337).
Embodiment 4
Using glass as substrate; Form the anode layer of indium tin oxide (ITO) material on a glass substrate, and anode layer chemical corrosion is become the strip shaped electric poles of 10 mm wides, 30 millimeters long, by strip shaped electric poles successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes put into oven for drying, being transferred to organic vapor deposition room after ito anode being carried out to the Low Pressure Oxygen plasma treatment of 10 minutes with the voltage of 400 volts under the atmosphere of 10 handkerchiefs, is 1 ~ 2 × 10 in vacuum degree
-5in the organic vapor deposition room of handkerchief, on the anode layer successively with the hole transmission layer of TAPC evaporation rate in 0.05 nm/sec evaporation 40 nanometer thickness, FIrpic evaporation rate to be adulterated at 0.1 nm/sec evaporation 5 nanometer thickness FIrpic in 0.008 nm/sec and MCP evaporation rate, and luminescent layer is dominated in the hole of MCP, FIrpic evaporation rate dominates luminescent layer and the BmPyPhB evaporation rate hole blocking layer in 0.05 nm/sec evaporation 40 nanometer thickness in 0.02 nm/sec and BCBP evaporation rate at the adulterate electronics of BCBP of 0.1 nm/sec evaporation 5 nanometer thickness FIrpic; Then the device do not completed is transferred to metal evaporation room, 4 ~ 6 × 10
-5with the LiF resilient coating of evaporation rate evaporation 1.0 nanometer thickness of 0.005 nm/sec under the vacuum of handkerchief, then by mask on LiF layer with the metal A l electrode of evaporation rate evaporation 100 nanometer thickness of 0.5 nm/sec, obtaining structure is ITO/TAPC/FIrpic (8%): MCP/FIrpic (20%): the blue-green organic electroluminescent device of BCBP/BmPyPhB/LiF/Al.
The light-emitting area of described blue-green organic electroluminescent device is 10 square millimeters.
Carry out performance test to described organic electroluminescence device, result shows, a bright voltage of described blue-green organic electroluminescent device is 2.9 volts, and high-high brightness is 48325cd/m
2, maximum current efficiency is 48.76cd/A, and maximum power efficiency is 49.11lm/W, and under DC power supply drives, display main peak is positioned at the blue green light that 472 nanometer acromions are positioned at 500 nanometers, when brightness is 20000cd/m
2time, the chromaticity coordinates of device is (0.122,0.320).
Embodiment 5
Using glass as substrate; Form the anode layer of indium tin oxide (ITO) material on a glass substrate, and anode layer chemical corrosion is become the strip shaped electric poles of 10 mm wides, 30 millimeters long, by strip shaped electric poles successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes put into oven for drying, being transferred to organic vapor deposition room after ito anode being carried out to the Low Pressure Oxygen plasma treatment of 10 minutes with the voltage of 400 volts under the atmosphere of 10 handkerchiefs, is 1 ~ 2 × 10 in vacuum degree
-5in the organic vapor deposition room of handkerchief, on the anode layer successively with the hole transmission layer of TAPC evaporation rate in 0.05 nm/sec evaporation 45 nanometer thickness, FIrpic evaporation rate to be adulterated at 0.1 nm/sec evaporation 5 nanometer thickness FIrpic in 0.01 nm/sec and MCP evaporation rate, and luminescent layer is dominated in the hole of MCP, FIrpic evaporation rate dominates luminescent layer and the BmPyPhB evaporation rate hole blocking layer in 0.05 nm/sec evaporation 40 nanometer thickness in 0.018 nm/sec and BmPyPhB evaporation rate at the adulterate electronics of BmPyPhB of 0.1 nm/sec evaporation 5 nanometer thickness FIrpic; Then the device do not completed is transferred to metal evaporation room, 4 ~ 6 × 10
-5with the LiF resilient coating of evaporation rate evaporation 1.0 nanometer thickness of 0.005 nm/sec under the vacuum of handkerchief, then by mask on LiF layer with the metal A l electrode of evaporation rate evaporation 100 nanometer thickness of 0.5 nm/sec, obtaining structure is ITO/TAPC/FIrpic (10%): MCP/FIrpic (18%): the blue-green organic electroluminescent device of BmPyPhB/BmPyPhB/LiF/Al.
The light-emitting area of described blue-green organic electroluminescent device is 10 square millimeters.
Carry out performance test to described organic electroluminescence device, result shows, a bright voltage of described blue-green organic electroluminescent device is 2.8 volts, and high-high brightness is 35876cd/m
2, maximum current efficiency is 53.45cd/A, and maximum power efficiency is 54.72lm/W, and under DC power supply drives, display main peak is positioned at the blue green light that 472 nanometer acromions are positioned at 500 nanometers, when brightness is 20000cd/m
2time, the chromaticity coordinates of device is (0.128,0.327).
Embodiment 6
Using glass as substrate; Form the anode layer of indium tin oxide (ITO) material on a glass substrate, and anode layer chemical corrosion is become the strip shaped electric poles of 10 mm wides, 30 millimeters long, by strip shaped electric poles successively with cleaning fluid, deionized water ultrasonic cleaning 15 minutes put into oven for drying, being transferred to organic vapor deposition room after ito anode being carried out to the Low Pressure Oxygen plasma treatment of 10 minutes with the voltage of 400 volts under the atmosphere of 10 handkerchiefs, is 1 ~ 2 × 10 in vacuum degree
-5in the organic vapor deposition room of handkerchief, on the anode layer successively with the hole transmission layer of TAPC evaporation rate in 0.05 nm/sec evaporation 40 nanometer thickness, FIrpic evaporation rate to be adulterated at 0.1 nm/sec evaporation 4 nanometer thickness FIrpic in 0.01 nm/sec and TCP evaporation rate, and luminescent layer is dominated in the hole of TCP, FIrpic evaporation rate dominates luminescent layer and the BmPyPhB evaporation rate hole blocking layer in 0.05 nm/sec evaporation 40 nanometer thickness in 0.018 nm/sec and BmPyPhB evaporation rate at the adulterate electronics of BmPyPhB of 0.1 nm/sec evaporation 6 nanometer thickness FIrpic; Then the device do not completed is transferred to metal evaporation room, 4 ~ 6 × 10
-5with the LiF resilient coating of evaporation rate evaporation 1.0 nanometer thickness of 0.005 nm/sec under the vacuum of handkerchief, then by mask on LiF layer with the metal A l electrode of evaporation rate evaporation 100 nanometer thickness of 0.5 nm/sec, obtaining structure is ITO/TAPC/FIrpic (10%): TCP/FIrpic (18%): the blue-green organic electroluminescent device of BmPyPhB/BmPyPhB/LiF/Al.
The light-emitting area of described blue-green organic electroluminescent device is 10 square millimeters.
Carry out performance test to described organic electroluminescence device, result shows, a bright voltage of described blue-green organic electroluminescent device is 3.0 volts, and high-high brightness is 36215cd/m
2, maximum current efficiency is 53.08cd/A, and maximum power efficiency is 53.13lm/W, and under DC power supply drives, display main peak is positioned at the blue green light that 472 nanometer acromions are positioned at 500 nanometers, when brightness is 20000cd/m
2time, the chromaticity coordinates of device is (0.130,0.329).
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.
Claims (8)
1. a blue-green organic electroluminescent device, comprising:
Substrate;
There is anode layer over the substrate;
Described anode layer there is hole to dominate luminescent layer, described hole is dominated luminescent layer and is entrained in cavity type organic host material by blue-green luminous organic material and is formed, the mass percent that described blue-green luminous organic material accounts for described cavity type organic host material is 6.0% ~ 11.0%, described blue-green luminous organic material is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium;
Described cavity type organic host material is 4, two (the N-carbazole)-1 of 4'-, 1'-biphenyl, 1,3-bis-carbazole-9-base benzene, 9,9'-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazoles, 1,3,5-tri-(9-carbazyl) benzene, 4,4'; 4 "-three (carbazole-9-base) triphenylamines or Isosorbide-5-Nitrae-bis-(tri-phenyl-silane base) biphenyl;
Dominating in described hole on luminescent layer has electronics to dominate luminescent layer, described electronics is dominated luminescent layer and is entrained in electron type organic host material by blue-green luminous organic material and is formed, the mass percent that described blue-green luminous organic material accounts for described electron type organic host material is 15.0% ~ 22.0%, described blue-green luminous organic material is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium;
Described electron type organic host material is 9,9'-(2,6-pyridine two base two-3, the sub-benzene of 1-) two-9H-carbazole, 1, two (tri-phenyl-silane base) benzene, 2 of 4-, 2 '-bis-(4-(9-carbazyl) phenyl) biphenyl, three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine, 1,3,5-tri-[(3-pyridine)-3-phenyl] benzene, 1,3-two [3,5-bis-(3-pyridine radicals) phenyl] benzene or two (triphenyl the is silica-based)-9H-carbazoles of 9-(4-t-butyl-phenyl)-3,6-;
Dominate on luminescent layer at described electronics and have negative electrode.
2. device according to claim 1, is characterized in that, the thickness that luminescent layer is dominated in described hole is 3 ~ 10 nanometers.
3. device according to claim 1, is characterized in that, the thickness that described electronics dominates luminescent layer is 3 ~ 10 nanometers.
4. device according to claim 1, is characterized in that, described anode layer and hole are dominated between luminescent layer and also comprised hole transmission layer;
Described hole transmission layer is formed by 4,4'-cyclohexyl two [N, N-bis-(4-aminomethyl phenyl) aniline].
5. device according to claim 1, is characterized in that, described electronics is dominated between luminescent layer and negative electrode and also comprised hole blocking layer;
Described hole blocking layer is formed by two [3,5-bis-(3-pyridine radicals) phenyl] benzene of three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine, 1,3,5-tri-[(3-pyridine)-3-phenyl] benzene or 1,3-.
6. device according to claim 5, is characterized in that, also comprises resilient coating between described hole blocking layer and negative electrode;
Described resilient coating is formed by lithium fluoride.
7. a preparation method for blue-green organic electroluminescent device, comprising:
Substrate forms anode layer;
Described anode layer forms hole and dominates luminescent layer, described hole is dominated luminescent layer and is entrained in cavity type organic host material by blue-green luminous organic material and is formed, the mass percent that described blue-green luminous organic material accounts for described cavity type organic host material is 6.0% ~ 11.0%, described blue-green luminous organic material is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium;
Described cavity type organic host material is 4, two (the N-carbazole)-1 of 4'-, 1'-biphenyl, 1,3-bis-carbazole-9-base benzene, 9,9'-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazoles, 1,3,5-tri-(9-carbazyl) benzene, 4,4'; 4 "-three (carbazole-9-base) triphenylamines or Isosorbide-5-Nitrae-bis-(tri-phenyl-silane base) biphenyl;
Dominate in described hole and luminescent layer forms electronics dominate luminescent layer, described electronics is dominated luminescent layer and is entrained in electron type organic host material by blue-green luminous organic material and is formed, the mass percent that described blue-green luminous organic material accounts for described electron type organic host material is 15.0% ~ 22.0%, described blue-green luminous organic material is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic conjunction iridium;
Described electron type organic host material is 9,9'-(2,6-pyridine two base two-3, the sub-benzene of 1-) two-9H-carbazole, 1, two (tri-phenyl-silane base) benzene, 2 of 4-, 2 '-bis-(4-(9-carbazyl) phenyl) biphenyl, three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine, 1,3,5-tri-[(3-pyridine)-3-phenyl] benzene, 1,3-two [3,5-bis-(3-pyridine radicals) phenyl] benzene or two (triphenyl the is silica-based)-9H-carbazoles of 9-(4-t-butyl-phenyl)-3,6-;
Dominate on luminescent layer at described electronics and form negative electrode, obtain blue-green organic electroluminescent device.
8. method according to claim 7, is characterized in that, the thickness that luminescent layer is dominated in described hole is 3 ~ 10 nanometers;
The thickness that described electronics dominates luminescent layer is 3 ~ 10 nanometers.
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