CN104518130A - Transparent organic electroluminescent device and preparation method thereof - Google Patents

Transparent organic electroluminescent device and preparation method thereof Download PDF

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Publication number
CN104518130A
CN104518130A CN201310449353.5A CN201310449353A CN104518130A CN 104518130 A CN104518130 A CN 104518130A CN 201310449353 A CN201310449353 A CN 201310449353A CN 104518130 A CN104518130 A CN 104518130A
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layer
germane
transparent
electroluminescent device
organic electroluminescent
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周明杰
钟铁涛
王平
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/816—Multilayers, e.g. transparent multilayers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass

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  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention provides a transparent organic electroluminescent device comprising a glass substrate, and a transparent anode, a hole injection layer, a hole transmission layer, a green luminescent layer, an electron transmission layer, an electron injection layer and a transparent cathode which are arranged on the glass substrate in a laminating way in turn. The transparent anode comprises a hydroxy germane organic matter layer and a metal layer. Material of the hydroxyl germane organic matter layer is at least one type of (3-hydroxy propyl) trimethoxy germane, (3-hydroxy ethyl) trimethoxy germane, (3-hydroxy methyl) trimethoxy germane and O, O, O-trimethyl-hydroxy germane. Material of the metal layer is at least one type of a magnesium silver alloy, a lithium aluminum alloy, barium and calcium. According to the transparent organic electroluminescent device, light emergent efficiency of the anode surface is over 45% than light emergent efficiency of the cathode surface so that luminescent performance is excellent. The invention also provides a preparation method of the transparent organic electroluminescent device.

Description

A kind of transparent organic electroluminescent device and preparation method thereof
Technical field
The invention belongs to field of organic electroluminescence, be specifically related to a kind of transparent organic electroluminescent device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) has the advantage of some uniquenesses: (1) OLED belongs to diffused area source, does not need to obtain large-area white light source by extra light-conducting system as light-emitting diode (LED); (2) due to the diversity of luminous organic material, OLED illumination can the light of design color as required; (3) OLED can at multiple substrate as glass, pottery, metal, plastic or other material make, freer when this makes design lighting source; (4) adopt the mode making OLED display to make OLED illumination panel, information can be shown while illumination; (5) OLED also can be used as controlled look in the illumination system, allows user to regulate light atmosphere according to individual demand.
Transparent organic electroluminescent device (TOLED) is the one of OLED, it not only can simultaneously from anode and negative electrode lighting at two sides, and the penetrability had to a certain degree, can the background at display frame rear, be applicable to building and vehicle window, shopper window and glasses etc., be with a wide range of applications.Compared with common OLED, the maximum difference of TOLED is that the negative electrode of device and anode all will adopt the conductive film with high permeability.If general TOLED adopts metal as anode, ITO is as negative electrode, but the poor adhesive force of metal anode and substrate of glass, and metal level light transmission is not as good as ITO, and the light extraction efficiency of device anode surface, well below cathode plane, causes Consumer's Experience very poor; And metal anode/organic material layer interface exists higher hole injection barrier, there is higher electron injection potential barrier in ITO negative electrode/organic material layer interface, causes the performance of device poor especially.Therefore, how equalizing device two-sided light extraction efficiency and how to improve the injection of charge carrier in TOLED, become the key issue of TOLED development.
Summary of the invention
Based on the problems referred to above, the invention provides a kind of transparent organic electroluminescent device, adopt hole injection layer and the electron injecting layer with double-deck transparent anode and improvement, solve the problem that the two-sided light extraction efficiency of transparent organic electroluminescent device is greatly different, carrier injection is difficult, this device anode surface light extraction efficiency reaches more than 45% of cathode plane light extraction efficiency, good luminescence property.Present invention also offers a kind of preparation method of transparent organic electroluminescent device.
For achieving the above object, the invention provides following technical scheme.
First aspect, the invention provides a kind of transparent organic electroluminescent device, comprise substrate of glass and the transparent anode be cascading on the glass substrate, hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, electron injecting layer and transparent cathode;
Described transparent anode comprises be cascading hydroxyl germane organic matter layer on the glass substrate and metal level; The material of described hydroxyl germane organic matter layer is (3-hydroxypropyl) trimethoxy germane, (3-hydroxyethyl) trimethoxy germane, (3-hydroxymethyl) trimethoxy germane and O, at least one in O, O-trimethyl-hydroxyl germane; The material of described metal level is at least one in magnesium silver alloy (Mg:Ag), lithium-aluminium alloy (Li:Al), barium (Ba) and calcium (Ca);
Described transparent cathode material is indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO).
The organic structural formula of described hydroxyl germane is:
Preferably, the thickness of described hydroxyl germane organic matter layer is 2nm ~ 4nm.
Preferably, the thickness of described metal level is 10nm ~ 20nm.
Preferably, in described magnesium silver alloy, magnesium, silver-colored mass ratio are 8:1 ~ 13:1, and in described lithium-aluminium alloy, the mass fraction of lithium is 0.5% ~ 1%; More preferably, the alloy (Mg:Ag(10:1) that described magnesium silver alloy is magnesium, silver-colored mass ratio is 10:1), described lithium-aluminium alloy to be the mass fraction of lithium be 0.6% alloy (Li:Al (0.6%Li)).
In hydroxyl germane organic substance-OH can with in white glass substrate-SiOH group passes through-O-Si is covalently cross-linked, wherein-OX group is first hydrolyzed formation-GeOH group, then-Me-O-Ge-covalent bond is formed with metal (or oxide), a kind of structure of similar germanate glass is defined between such substrate of glass and metal level, the structure of this similar germanate glass is as transition zone, not only there is good visible light permeability, be conducive to the raising of transparent anode face light extraction efficiency, adhesive force and the oxidation resistance of metal level can also be strengthened, be conducive to the prolongation of device lifetime.
Preferably, the thickness of described transparent cathode is 100nm ~ 150nm.
Preferably, the material of described hole injection layer comprises hole mobile material and is entrained in the hole-injecting material in described hole mobile material, and the doping mass fraction of described hole-injecting material is 25% ~ 35%; ; Described hole-injecting material is MoO 3, WO 3, V 2o 5and ReO 3in one, described hole mobile material is N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA), 4,4 '-two (9-carbazole) biphenyl (CBP), N; N '-two (3-aminomethyl phenyl)-N; the one in N '-diphenyl-4,4 '-benzidine (TPD), 1,1-bis-[4-[N; N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), the thickness of hole injection layer is 10nm ~ 15nm.
MoO in hole injection layer 3, WO 3, V 2o 5or ReO 3, can as the resilient coating between anode metal layer and hole mobile material, MoO 3, WO 3, V 2o 5or ReO 3uniform Doped in hole mobile material, makes transparent anode and organic material interface and hole injection layer inside form ohmic contact site, can reduce its hole injection barrier, thus reduce the operating voltage of device; And described hole injection layer adopts hole mobile material as host material, not only can improve the transmittability of injected hole, and as the gradient composition transition zone of anode metal layer and hole transmission layer, interface can be reduced and go out light loss, be conducive to the raising of anode surface light extraction efficiency.
Preferably, the material of described electron injecting layer comprises electron transport material and is entrained in the alkali metal sulfates in described electron transport material, and lithium salts or cesium salt, the doping mass fraction of described alkali metal sulfates is 6% ~ 25%, and the doping mass fraction of described lithium salts or cesium salt is 25% ~ 35%; Described alkali metal sulfates is Li 2sO 4, Na 2sO 4, K 2sO 4, Rb 2sO 4and Cs 2sO 4in any one, described lithium salts is LiF, LiN 3and Li 3any one in N, described cesium salt is CsF, CsN 3, Cs 3any one in N, described electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, the one in 2,4-triazole (TAZ), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI); The thickness of described electron injecting layer is 15nm ~ 45nm.
The while of in electron injecting layer, doped sulfuric acid salt and lithium cesium salt, improve the concentration of free carrier in electron transport material, thus add the conductivity of electron injecting layer, improves the electron transport property of device; And the electron injection potential barrier that can reduce between ITO negative electrode and electron transfer layer, is conducive to entering of electronics, improves the Electron Injection Characteristics of device, make more electronics enter luminescent layer and hole-recombination; But lithium cesium salt easily decomposes in evaporate process, the metal cation discharged, too high doping content can make metal cation enter luminous zone, causes Exciton quenching, affects exciton compound, causes device performance to decline; Although and sulfate is not so good as lithium cesium salt, Heat stability is good in raising Electron Injection Characteristics, conductivity is strong, mixes altogether, greatly can improve the electron transport property of device with lithium cesium salt.Adopt electron transport material as host material, not only can improve and inject the transmittability of electronics, and as the gradient composition transition zone of ITO negative electrode and electron transfer layer, interface can be reduced and go out light loss; As sacrifice layer, the destruction that the organic material in electron transfer layer, luminescent layer sputters from ITO can be made simultaneously.
Preferably, the material of described hole transmission layer is N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA), 4,4 '-two (9-carbazole) biphenyl (CBP), N; N '-two (3-aminomethyl phenyl)-N; the one in N '-diphenyl-4,4 '-benzidine (TPD), 1,1-bis-[4-[N; N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), thickness is 30nm ~ 50nm.
Preferably, described green light emitting layer is made up of green glow material of main part and green glow guest materials, and the doping mass fraction of described green glow guest materials is 2% ~ 10%, and green emitting layer thickness is 10nm ~ 30nm.
Preferably, described green glow material of main part is 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA), 9; 9 '-(1; 3-phenyl) two-9H-carbazole (mCP), 4; 4 '-two (9-carbazole) biphenyl (CBP), N; N '-two (3-aminomethyl phenyl)-N; N '-diphenyl-4,4 '-benzidine (TPD) or 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 9,10-two (1-naphthyl) anthracenes (ADN); Described green glow guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2(acac)) or three [2-(p-methylphenyl) pyridines] close iridium (Ir (mppy) 3).
Preferably, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), 1,3, one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), thickness is 10nm ~ 60nm.
On the other hand, the invention provides a kind of preparation method of transparent organic electroluminescent device, comprise the steps:
(1) substrate of glass is provided;
(2) prepare transparent anode on the glass substrate, described transparent anode comprises hydroxyl germane organic matter layer and metal level; First the mode made by spin coating prepares hydroxyl germane organic matter layer on the glass substrate, the material of described hydroxyl germane organic matter layer is (3-hydroxypropyl) trimethoxy germane, (3-hydroxyethyl) trimethoxy germane, (3-hydroxymethyl) trimethoxy germane and O, O, at least one in O-trimethyl-hydroxyl germane, rotating speed is 2000rpm ~ 5000rpm; Then on described hydroxyl germane organic matter layer, adopt the mode of vacuum evaporation to make metal level, the material of described metal level is at least one in magnesium silver alloy (Mg:Ag), lithium-aluminium alloy (Li:Al), barium (Ba) and calcium (Ca), and evaporation rate is vacuum degree is 1 × 10 -5pa ~ 1 × 10 -3pa;
(3) on described metal level, the mode of vacuum evaporation is adopted to prepare hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively; First prepare hole injection layer, evaporation rate is and then prepare hole transmission layer, evaporation rate is then be green light emitting layer, evaporation rate is prepare electron transfer layer again, evaporation rate is be finally electron injecting layer, evaporation rate is
(4) finally on described electron injecting layer, magnetron sputtering prepares transparent cathode, obtains transparent organic electroluminescent device; Described transparent cathode material is indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO), and the accelerating voltage of magnetron sputtering controls at 300V ~ 800V, and magnetic flux density is 50G ~ 200G, and power density is 10W/cm 2~ 40W/cm 2, background vacuum is 1 × 10 -5pa ~ 1 × 10 -3pa.
Preferably, the thickness of described hydroxyl germane organic matter layer is 2nm ~ 4nm.
Preferably, the thickness of described metal level is 10nm ~ 20nm.
Preferably, in described magnesium silver alloy, magnesium, silver-colored mass ratio are 8:1 ~ 13:1, and in described lithium-aluminium alloy, the mass fraction of lithium is 0.5% ~ 1%; More preferably, the alloy (Mg:Ag(10:1) that described magnesium silver alloy is magnesium, silver-colored mass ratio is 10:1), described lithium-aluminium alloy to be the mass fraction of lithium be 0.6% alloy (Li:Al (0.6%Li)).
Preferably, the thickness of described transparent cathode is 100nm ~ 150nm.
Preferably, the material of described hole injection layer comprises hole mobile material and is entrained in the hole-injecting material in described hole mobile material, and the doping mass fraction of described hole-injecting material is 25% ~ 35%; Described hole-injecting material is MoO 3, WO 3, V 2o 5and ReO 3in one, described hole mobile material is N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA), 4,4 '-two (9-carbazole) biphenyl (CBP), N; N '-two (3-aminomethyl phenyl)-N; the one in N '-diphenyl-4,4 '-benzidine (TPD), 1,1-bis-[4-[N; N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), the thickness of hole injection layer is 10nm ~ 15nm.
Preferably, the material of described electron injecting layer comprises electron transport material and is entrained in the alkali metal sulfates in described electron transport material, and lithium salts or cesium salt, the doping mass fraction of described alkali metal sulfates is 6% ~ 25%, and the doping mass fraction of described lithium salts or cesium salt is 25% ~ 35%; Described alkali metal sulfates is Li 2sO 4, Na 2sO 4, K 2sO 4, Rb 2sO 4and Cs 2sO 4in any one, described lithium salts is LiF, LiN 3and Li 3any one in N, described cesium salt is CsF, CsN 3, Cs 3any one in N, described electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, the one in 2,4-triazole (TAZ), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI); The thickness of described electron injecting layer is 15nm ~ 45nm.
Preferably, the material of described hole transmission layer is N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA), 4,4 '-two (9-carbazole) biphenyl (CBP), N; N '-two (3-aminomethyl phenyl)-N; the one in N '-diphenyl-4,4 '-benzidine (TPD), 1,1-bis-[4-[N; N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), the thickness of described hole transmission layer is 30nm ~ 50nm.
Preferably, described green light emitting layer is made up of green glow material of main part and green glow guest materials, and the doping mass fraction of described green glow guest materials is 2% ~ 10%, and green emitting layer thickness is 10nm ~ 30nm.
Preferably, described green glow material of main part is 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA), 9; 9 '-(1; 3-phenyl) two-9H-carbazole (mCP), 4; 4 '-two (9-carbazole) biphenyl (CBP), N; N '-two (3-aminomethyl phenyl)-N; N '-diphenyl-4,4 '-benzidine (TPD) or 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 9,10-two (1-naphthyl) anthracenes (ADN); Described green glow guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2(acac)) or three [2-(p-methylphenyl) pyridines] close iridium (Ir (mppy) 3).
Preferably, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), 1,3, one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), thickness is 10nm ~ 60nm.
Compared with existing organic electroluminescence device, beneficial effect of the present invention comprises following aspect:
(1) employing has double-deck transparent anode, and near substrate of glass is hydroxyl germane organic matter layer, and near hole injection layer is metal level; Hydroxyl germane organic matter layer has the structure of similar germanate glass, has good visible light permeability, is conducive to the raising of transparent anode face light extraction efficiency, makes the anode surface light extraction efficiency of device reach more than 45% of cathode plane light extraction efficiency; And the setting of hydroxyl germane organic matter layer, make the Adhesion enhancement of substrate of glass and anode metal interlayer, the oxidation resistance of metal level strengthens, thus is conducive to the raising of device lifetime;
(2) hole injection layer adopts hole mobile material doping hole-injecting material, greatly reduces hole injection barrier; And hole mobile material is as host material, not only can improve the transmittability of injected hole, hole injection layer/hole transport bed boundary bright dipping loss can also be reduced, be conducive to the raising of anode surface light extraction efficiency;
(3) electron injecting layer material adopts electron transport material doped sulfuric acid salt, and the composite material of doping lithium salts or cesium salt formation, both can improve carrier concentration, improve the electron injection performance of device, and can effectively avoid again the lithium cesium salt list of high concentration to adulterate the Exciton quenching brought; And adopt electron transport material as host material, not only can improve the transmittability injecting electronics, electron transfer layer/electron injection bed boundary bright dipping loss can also be reduced, be conducive to the raising of cathode plane light extraction efficiency;
(4) electron injecting layer material adopts electron transport material as sacrifice layer, can also make the destruction that the organic material in electron transfer layer, luminescent layer sputters from ITO as host material;
(5) simple, the technological parameter controllable precise of preparation method's operation of described transparent organic electroluminescent device, thickness is adjustable, is applicable to large-scale industrial production.
Accompanying drawing explanation
The structural representation of a kind of transparent organic electroluminescent device that Fig. 1 provides for an embodiment.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The structural representation of a kind of transparent organic electroluminescent device that Fig. 1 provides for an embodiment.As shown in Figure 1, this transparent organic electroluminescent device has been cascading substrate of glass 10, transparent anode 20, hole injection layer 30, hole transmission layer 40, green light emitting layer 50, electron transfer layer 60 and transparent cathode 70 from lower to upper.Wherein, described transparent anode 20 comprises be cascading hydroxyl germane organic matter layer 21 in substrate of glass 10 and metal level 22.
Embodiment 1: a kind of preparation of transparent organic electroluminescent device; Device architecture is substrate of glass/(3-hydroxypropyl) trimethoxy germane/Mg:Ag(10:1)/NPB:MoO 3/ NPB/TCTA:Ir (ppy) 3/ Bphen/Bphen:LiF:Li 2sO 4/ ITO.Its preparation method is as follows:
(1) substrate of glass is provided: get one piece of white glass, successively through liquid detergent cleaning, washed with de-ionized water, acetone cleaning, ethanol purge, this operates in supersonic wave cleaning machine and carries out, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying.
(2) transparent anode is prepared on the glass substrate, transparent anode comprises be cascading hydroxyl germane organic matter layer on the glass substrate and metal level, described hydroxyl germane organic matter layer material is (3-hydroxypropyl) trimethoxy germane, employing spin coating makes, rotating speed 2000rpm, thickness 4nm; Described hydroxyl germane organic matter layer prepares metal level, and described metal layer material is Mg:Ag(10:1), adopt the mode of vacuum evaporation to make, vacuum degree 1 × 10 -5pa, evaporation rate thickness 15nm.
(3) on described metal level, the mode of vacuum evaporation is adopted to prepare hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively; The material of hole injection layer comprises NPB and is entrained in the MoO in NPB 3(be expressed as NPB:MoO 3), MoO 3doping mass fraction be 30%, thickness is 12.5nm, and evaporation rate is the material of hole transmission layer is NPB, evaporation rate evaporation thickness 40nm; The material of green light emitting layer comprises material of main part TCTA and guest materials Ir (ppy) 3(be expressed as TCTA:Ir (ppy) 3), Ir (ppy) 3doping mass fraction be 6%, evaporation rate is evaporation thickness 20nm; The material of electron transfer layer is Bphen, evaporation rate evaporation thickness 35nm; The material of electron injecting layer comprises Bphen and is entrained in LiF and Li in Bphen 2sO 4(be expressed as Bphen:LiF:Li 2sO 4), Li 2sO 4doping mass fraction is 15%, LiF doping mass fraction is 30%, evaporation rate evaporation thickness 35nm; The vacuum degree that above-mentioned vacuum evaporation adopts is 1 × 10 -5pa.
(4) on described electron injecting layer, magnetron sputtering prepares transparent cathode, obtains transparent organic electroluminescent device; Cathode material is ITO, and the accelerating voltage of magnetron sputtering is 800V, and magnetic flux density is 200G, and power density is 40W/cm 2, background vacuum 1 × 10 -5pa, thickness 150nm.
Embodiment 2: a kind of preparation of transparent organic electroluminescent device; Device architecture is substrate of glass/(3-hydroxyethyl) trimethoxy germane/Li:Al (0.6%Li)/TCTA:WO 3/ TCTA/mCP:Ir (ppy) 2(acac)/BCP/BCP:LiN 3: Na 2sO 4/ ITO.Its preparation method is as follows:
(1) substrate of glass is provided: get one piece of white glass, successively through liquid detergent cleaning, washed with de-ionized water, acetone cleaning, ethanol purge, this operates in supersonic wave cleaning machine and carries out, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying.
(2) transparent anode is prepared on the glass substrate, transparent anode comprises be cascading hydroxyl germane organic matter layer on the glass substrate and metal level, described hydroxyl germane organic matter layer material is (3-hydroxyethyl) trimethoxy germane, employing spin coating makes, rotating speed 5000rpm, thickness 2nm; Described hydroxyl germane organic matter layer prepares metal level, and described metal layer material is Li:Al (0.6%Li), adopts the mode of vacuum evaporation to make, vacuum degree 1 × 10 -4pa, evaporation rate thickness 10nm.
(3) on described metal level, the mode of vacuum evaporation is adopted to prepare hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively; The material of hole injection layer comprises TCTA and is entrained in the WO in TCTA 3(be expressed as TCTA:WO 3), WO 3doping mass fraction be 25%, thickness is 10nm, and evaporation rate is the material of hole transmission layer is TCTA, evaporation rate evaporation thickness 30nm; The material of green light emitting layer comprises material of main part mCP and guest materials Ir (ppy) 2(acac) (mCP:Ir (ppy) is expressed as 2(acac)), Ir (ppy) 2(acac) doping mass fraction is 2%, and evaporation rate is evaporation thickness 10nm; The material of electron transfer layer is BCP, and evaporation rate is evaporation thickness 10nm; The material of electron injecting layer comprises BCP and is entrained in the LiN in BCP 3and Na 2sO 4(be expressed as BCP:LiN 3: Na 2sO 4), Na 2sO 4doping mass fraction is 25%, LiN 3doping mass fraction 25%, evaporation rate evaporation thickness 45nm; The vacuum degree that above-mentioned vacuum evaporation adopts is 5 × 10 -5pa.
(4) on described electron injecting layer, magnetron sputtering prepares transparent cathode, obtains transparent organic electroluminescent device; Cathode material is ITO, and the accelerating voltage of magnetron sputtering is 300V, and magnetic flux density is 50G, and power density is 10W/cm 2, background vacuum 1 × 10 -5pa, thickness 120nm.
Embodiment 3: a kind of preparation of transparent organic electroluminescent device; Device architecture is substrate of glass/(3-hydroxymethyl) trimethoxy germane/Ba/CBP:V 2o 5/ CBP/CBP:Ir (mpp y) 3/ BAlq/BAlq:Li 3n:K 2sO 4/ ITO.Its preparation method is as follows:
(1) substrate of glass is provided: get one piece of white glass, successively through liquid detergent cleaning, washed with de-ionized water, acetone cleaning, ethanol purge, this operates in supersonic wave cleaning machine and carries out, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying.
(2) transparent anode is prepared on the glass substrate, transparent anode comprises be cascading hydroxyl germane organic matter layer on the glass substrate and metal level, described hydroxyl germane organic matter layer material is (3-hydroxymethyl) trimethoxy germane, employing spin coating makes, rotating speed 2000rpm, thickness 4nm; Described hydroxyl germane organic matter layer prepares metal level, and described metal layer material is Ba, adopts the mode of vacuum evaporation to make, vacuum degree 1 × 10 -5pa, evaporation rate thickness 20nm.
(3) on described metal level, the mode of vacuum evaporation is adopted to prepare hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively; The material of hole injection layer comprises CPB and is entrained in the V in CPB 2o 5(be expressed as CBP:V 2o 5), V 2o 5doping mass fraction 35%, thickness 15nm, evaporation rate the material of hole transmission layer is CBP, evaporation rate evaporation thickness 50nm; The material of green light emitting layer comprises material of main part CPB and guest materials Ir (mppy) 3(be expressed as CBP:Ir (mppy) 3), Ir (mppy) 3doping mass fraction be 10%, evaporation rate evaporation thickness 30nm; The material of electron transfer layer is BAlq, evaporation rate evaporation thickness 60nm; The material of electron injecting layer comprises BAlq and is entrained in the Li in BAlq 3n and K 2sO 4(be expressed as BAlq:Li 3n:K 2sO 4), K 2sO 4doping mass fraction is 6%, Li 3n adulterates mass fraction 35%, evaporation rate evaporation thickness 15nm; The vacuum degree that above-mentioned vacuum evaporation adopts is 5 × 10 -5pa.
(4) on described electron injecting layer, magnetron sputtering prepares transparent cathode, obtains transparent organic electroluminescent device; Cathode material is ITO, and the accelerating voltage of magnetron sputtering is 400V, and magnetic flux density is 60G, and power density is 20W/cm 2, background vacuum 1 × 10 -5pa, thickness 120nm.
Embodiment 4: a kind of preparation of transparent organic electroluminescent device; Device architecture is substrate of glass/O, O, O-trimethyl-hydroxyl germane/Ca/TPD:ReO 3/ TPD/TPD:Ir (ppy) 3/ Alq 3/ Alq 3: CsF:Rb 2sO 4/ ITO.Its preparation method is as follows:
(1) substrate of glass is provided: get one piece of white glass, successively through liquid detergent cleaning, washed with de-ionized water, acetone cleaning, ethanol purge, this operates in supersonic wave cleaning machine and carries out, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying.
(2) prepare transparent anode on the glass substrate, transparent anode comprises be cascading hydroxyl germane organic matter layer on the glass substrate and metal level, and described hydroxyl germane organic matter layer material is O, O, O-trimethyl-hydroxyl germane, adopts spin coating to make, rotating speed 3000rpm, thickness 3nm; Described hydroxyl germane organic matter layer prepares metal level, and described metal layer material is Ca, adopts the mode of vacuum evaporation to make, vacuum degree 1 × 10 -5pa, evaporation rate thickness 12nm.
(3) on described metal level, the mode of vacuum evaporation is adopted to prepare hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively; The material of hole injection layer comprises TPD and is entrained in the ReO in TPD 3(be expressed as TPD:ReO 3), ReO 3doping mass fraction 30%, thickness 13nm, evaporation rate the material of hole transmission layer is TPD, evaporation rate evaporation thickness 40nm; The material of green light emitting layer comprises material of main part TPD and guest materials Ir (ppy) 3(be expressed as TPD:Ir (ppy) 3), Ir (ppy) 3doping mass fraction be 5%, evaporation rate evaporation thickness 20nm; The material of electron transfer layer is Alq 3, evaporation rate evaporation thickness 30nm; The material of electron injecting layer comprises Alq 3and be entrained in Alq 3in CsF and Rb 2sO 4(be expressed as Alq 3: CsF:Rb 2sO 4)), Rb 2sO 4doping mass fraction is 10%, CsF doping mass fraction 30%, evaporation rate evaporation thickness 30nm; The vacuum degree that above-mentioned vacuum evaporation adopts is 5 × 10 -5pa.
(4) on described electron injecting layer, magnetron sputtering prepares transparent cathode, obtains transparent organic electroluminescent device; Cathode material is ITO, and the accelerating voltage of magnetron sputtering is 500V, and magnetic flux density is 80G, and power density is 25W/cm 2, background vacuum 1 × 10 -4pa, thickness 130nm.
Embodiment 5: a kind of preparation of transparent organic electroluminescent device; Device architecture is substrate of glass/O, O, O-trimethyl-hydroxyl germane/Mg:Ag(10:1)/TAPC:MoO 3/ TAPC/TAPC:Ir (ppy) 2(acac)/TAZ/TAZ:CsN 3: Cs 2sO 4/ ITO.Its preparation method is as follows:
(1) substrate of glass is provided: get one piece of white glass, successively through liquid detergent cleaning, washed with de-ionized water, acetone cleaning, ethanol purge, this operates in supersonic wave cleaning machine and carries out, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying.
(2) transparent anode is prepared on the glass substrate, transparent anode comprises be cascading hydroxyl germane organic matter layer on the glass substrate and metal level, described hydroxyl germane organic matter layer material is O, O, O-trimethyl-hydroxyl germane, employing spin coating makes, rotating speed 4500rpm, thickness 2.5nm; Described hydroxyl germane organic matter layer prepares metal level, and described metal layer material is Mg:Ag(10:1), adopt the mode of vacuum evaporation to make, vacuum degree 1 × 10 -5pa, evaporation rate thickness 18nm.
(3) on described metal level, the mode of vacuum evaporation is adopted to prepare hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively; The material of hole injection layer comprises TAPC and is entrained in the MoO in TAPC 3(be expressed as TAPC:MoO 3), MoO 3doping mass fraction be 25%, thickness is 10nm, and evaporation rate is the material of hole transmission layer is TAPC, evaporation rate evaporation thickness 40nm; The material of green light emitting layer comprises material of main part TAPC and guest materials Ir (ppy) 2(acac) (TAPC:Ir (ppy) is expressed as 2(acac)), Ir (ppy) 2(acac) doping mass fraction is 7%, evaporation rate evaporation thickness 20nm; The material of electron transfer layer is TAZ, evaporation rate evaporation thickness 50nm; The material of electron injecting layer comprises TAZ and is entrained in the CsN in TAZ 3and Cs 2sO 4(be expressed as TAZ:CsN 3: Cs 2sO 4)), Cs 2sO 4doping mass fraction is 10%, CsN 3doping mass fraction 30%, evaporation rate evaporation thickness 30nm; The vacuum degree that above-mentioned vacuum evaporation adopts is 5 × 10 -5pa.
(4) on described electron injecting layer, magnetron sputtering prepares transparent cathode, obtains transparent organic electroluminescent device; Cathode material is ITO, and the accelerating voltage of magnetron sputtering is 600V, and magnetic flux density is 100G, and power density is 30W/cm 2, background vacuum 1 × 10 -5pa, thickness 140nm.
Embodiment 6: a kind of preparation of transparent organic electroluminescent device; Device architecture is substrate of glass/O, O, O-trimethyl-hydroxyl germane/Li:Al (0.6%Li)/NPB:WO 3/ NPB/ADN:Ir (mppy) 3/ TPBI/TPBI:Cs 3n:Cs 2sO 4/ ITO.Its preparation method is as follows:
(1) substrate of glass is provided: get one piece of white glass, successively through liquid detergent cleaning, washed with de-ionized water, acetone cleaning, ethanol purge, this operates in supersonic wave cleaning machine and carries out, each washing adopts cleaning 5 minutes, stop 5 minutes, repeat the method for 3 times respectively, and then stand-by by oven for drying.
(2) transparent anode is prepared on the glass substrate, transparent anode comprises be cascading hydroxyl germane organic matter layer on the glass substrate and metal level, described hydroxyl germane organic matter layer material is O, O, O-trimethyl-hydroxyl germane, employing spin coating makes, rotating speed 3500rpm, thickness 3.5nm; Described hydroxyl germane organic matter layer prepares metal level, and described metal layer material is Li:Al (0.6%Li), adopts the mode of vacuum evaporation to make, vacuum degree 1 × 10 -3pa, evaporation rate thickness 13nm.
(3) on described metal level, the mode of vacuum evaporation is adopted to prepare hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively; The material of hole injection layer comprises NPB and is entrained in the WO in NPB 3(be expressed as NPB:WO 3), WO 3doping mass fraction 30%, thickness 12nm, evaporation rate the material of hole transmission layer is NPB, evaporation rate evaporation thickness 40nm; The material of green light emitting layer comprises material of main part ADN and guest materials Ir (mppy) 3(be expressed as ADN:Ir (mppy) 3), Ir (mppy) 3doping mass fraction be 6%, evaporation rate evaporation thickness 20nm; The material of electron transfer layer is TPBI, evaporation rate evaporation thickness 30nm; The material of electron injecting layer comprises TPBI and is entrained in the Cs in TPBI 3n and Cs 2sO 4(be expressed as TPBI:Cs 3n:Cs 2sO 4), Cs 2sO 4doping mass fraction is 10%, Cs 3n adulterates mass fraction 30%, evaporation rate evaporation thickness 30nm; The vacuum degree that above-mentioned vacuum evaporation adopts is 1 × 10 -3pa.
(4) on described electron injecting layer, magnetron sputtering prepares transparent cathode, obtains transparent organic electroluminescent device; Cathode material is ITO, and the accelerating voltage of magnetron sputtering is 700V, and magnetic flux density is 180G, and power density is 40W/cm 2, background vacuum 1 × 10 -3pa Pa, thickness 100nm.
Effect example
In order to fully demonstrate beneficial effect of the present invention, measure the transparent organic electroluminescent device of embodiment 1 ~ 6 preparation at 1000cd/m 2lumen efficiency values under brightness.Table 1 is the lumen efficiency values of the transparent organic electroluminescent device that the embodiment of the present invention provides.
The lumen efficiency values of the transparent organic electroluminescent device that table 1 embodiment of the present invention provides
As shown in Table 1, the anode surface light extraction efficiency of transparent organic electroluminescent device prepared by embodiment 1 ~ 6 all reaches more than 45% of cathode plane light extraction efficiency, the main structure owing to hydroxyl germane organic matter layer with similar germanate glass, there is good visible light permeability, be conducive to the raising of transparent anode face light extraction efficiency, make the anode surface light extraction efficiency of device reach more than 45% of cathode plane light extraction efficiency.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. a transparent organic electroluminescent device, comprise substrate of glass and the transparent anode be cascading on the glass substrate, hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, electron injecting layer and transparent cathode, it is characterized in that
Described transparent anode comprises be cascading hydroxyl germane organic matter layer on the glass substrate and metal level; The material of described hydroxyl germane organic matter layer is (3-hydroxypropyl) trimethoxy germane, (3-hydroxyethyl) trimethoxy germane, (3-hydroxymethyl) trimethoxy germane and O, at least one in O, O-trimethyl-hydroxyl germane; The material of described metal level is at least one in magnesium silver alloy, lithium-aluminium alloy, barium and calcium;
Described transparent cathode material is indium tin oxide, aluminium zinc oxide or indium-zinc oxide.
2. transparent organic electroluminescent device according to claim 1, is characterized in that, the thickness of described hydroxyl germane organic matter layer is 2nm ~ 4nm.
3. transparent organic electroluminescent device according to claim 1, is characterized in that, described metal layer thickness is 10nm ~ 20nm.
4. transparent organic electroluminescent device according to claim 1, is characterized in that, the thickness of described transparent cathode is 100nm ~ 150nm.
5. transparent organic electroluminescent device according to claim 1, it is characterized in that, the material of described hole injection layer comprises hole mobile material and is entrained in the hole-injecting material in described hole mobile material, and the doping mass fraction of described hole-injecting material is 25% ~ 35%; Described hole-injecting material is MoO 3, WO 3, V 2o 5and ReO 3in one, described hole mobile material is N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, 4,4 ', 4 "-three (carbazole-9-base) triphenylamine, 4,4 '-two (9-carbazole) biphenyl, N; N '-two (3-aminomethyl phenyl)-N; the one in N '-diphenyl-4,4 '-benzidine, 1,1-bis-[4-[N; N '-two (p-tolyl) is amino] phenyl] cyclohexane, the thickness of described hole injection layer is 10nm ~ 15nm.
6. transparent organic electroluminescent device according to claim 1, it is characterized in that, the material of described electron injecting layer comprises electron transport material and is entrained in the alkali metal sulfates in described electron transport material, and lithium salts or cesium salt, the doping mass fraction of described alkali metal sulfates is 6% ~ 25%, and the doping mass fraction of described lithium salts or cesium salt is 25% ~ 35%; Described alkali metal sulfates is Li 2sO 4, Na 2sO 4, K 2sO 4, Rb 2sO 4and Cs 2sO 4in any one, described lithium salts is LiF, LiN 3and Li 3any one in N, described cesium salt is CsF, CsN 3and Cs 3any one in N, described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phens, 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2, one in 4-triazole and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene; The thickness of described electron injecting layer is 15nm ~ 45nm.
7. a preparation method for transparent organic electroluminescent device, is characterized in that, comprises the steps:
(1) substrate of glass is provided;
(2) prepare transparent anode on the glass substrate, described transparent anode comprises hydroxyl germane organic matter layer and metal level; First the mode made by spin coating prepares hydroxyl germane organic matter layer on the glass substrate, the material of described hydroxyl germane organic matter layer is (3-hydroxypropyl) trimethoxy germane, (3-hydroxyethyl) trimethoxy germane, (3-hydroxymethyl) trimethoxy germane and O, O, at least one in O-trimethyl-hydroxyl germane, rotating speed is 2000rpm ~ 5000rpm; Then on described hydroxyl germane organic matter layer, adopt the mode of vacuum evaporation to make metal level, the material of described metal level is at least one in magnesium silver alloy, lithium-aluminium alloy, barium and calcium, and evaporation rate is vacuum degree is 1 × 10 -5pa ~ 1 × 10 -3pa;
(3) on described metal level, adopt the mode of vacuum evaporation to prepare hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer and electron injecting layer successively, the vacuum degree of employing is 1 × 10 -5p a~ 1 × 10 -3pa; First prepare hole injection layer, evaporation rate is and then prepare hole transmission layer, evaporation rate is then be green light emitting layer, evaporation rate is prepare electron transfer layer again, evaporation rate is be finally electron injecting layer, evaporation rate is
(4) finally on described electron injecting layer, magnetron sputtering prepares transparent cathode, obtains transparent organic electroluminescent device; Described transparent cathode material is indium tin oxide, aluminium zinc oxide or indium-zinc oxide, and the accelerating voltage of magnetron sputtering controls at 300V ~ 800V, and magnetic flux density is 50G ~ 200G, and power density is 10W/cm 2~ 40W/cm 2, background vacuum is 1 × 10 -5pa ~ 1 × 10 -3pa.
8. the preparation method of transparent organic electroluminescent device according to claim 7, is characterized in that, the thickness of described hydroxyl germane organic matter layer is 2nm ~ 4nm.
9. the preparation method of transparent organic electroluminescent device according to claim 7, is characterized in that, the thickness of described metal level is 10nm ~ 20nm.
10. the preparation method of transparent organic electroluminescent device according to claim 7, is characterized in that, the thickness of described transparent cathode is 100nm ~ 150nm.
CN201310449353.5A 2013-09-27 2013-09-27 Transparent organic electroluminescent device and preparation method thereof Pending CN104518130A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105641714A (en) * 2015-12-28 2016-06-08 四川大学 Folic acid modified VEGFR2/Tie2 double gene composition
CN110330891A (en) * 2019-07-05 2019-10-15 武汉华星光电半导体显示技术有限公司 Flexible cover plate and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105641714A (en) * 2015-12-28 2016-06-08 四川大学 Folic acid modified VEGFR2/Tie2 double gene composition
CN110330891A (en) * 2019-07-05 2019-10-15 武汉华星光电半导体显示技术有限公司 Flexible cover plate and preparation method thereof
CN110330891B (en) * 2019-07-05 2021-08-03 武汉华星光电半导体显示技术有限公司 Flexible cover plate and manufacturing method thereof

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