CN104269500B - Red organic electroluminescent device and preparation method thereof - Google Patents
Red organic electroluminescent device and preparation method thereof Download PDFInfo
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- CN104269500B CN104269500B CN201410605228.3A CN201410605228A CN104269500B CN 104269500 B CN104269500 B CN 104269500B CN 201410605228 A CN201410605228 A CN 201410605228A CN 104269500 B CN104269500 B CN 104269500B
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
- H10K50/121—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants for assisting energy transfer, e.g. sensitization
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- 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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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
Abstract
The invention provides a red organic electroluminescent device which comprises a substrate, an anode layer, an anode modification layer, a hole transport-electronic barrier layer, a hole leading luminescent layer, an electronic leading luminescent layer, a hole barrier-electronic transport layer, a cathode modification layer and a cathode layer which are sequentially arranged. The electronic leading luminescent layer comprises 0.05 weight percent to 2.0 weight percent of organic sensitized material, 1.0 weight percent to 8.0 weight percent of red organic luminescent material and the balance of electronic organic main body material, wherein the organic sensitized material is a transition metal complex with matched energy level. According to the invention, the organic sensitized material is doped in the electronic leading luminescent layer, the organic sensitized material takes effects of a charge carrier deep restraint center and an energy transfer step and is beneficial for balancing distribution of charge carriers, widening a luminous interval of the device and accelerating energy transfer from the main body material to the luminescent material so as to improve efficiency of the device and reduce a working voltage of the device.
Description
Technical field
The present invention relates to electroluminescent technology field, more particularly to a kind of red organic electroluminescence device and its preparation side
Method.
Background technology
Organic electroluminescence device is a kind of selfluminous element, when electric charge is injected into hole injecting electrode (anode) and electricity
During organic membrane between sub- injecting electrode (negative electrode), electronics and hole combine and subsequently bury in oblivion, thus generation light.Organic electroluminescence is sent out
Optical device has the characteristics such as low-voltage, high brightness, wide viewing angle, therefore organic electroluminescence device has obtained in recent years swift and violent
Development.Wherein, red organic electroluminescence device due to it is monochromatic show, the application prospect of the aspect such as white light modulation, into
For current study hotspot.
All the time, trivalent complex of iridium because have the advantages that luminous efficiency high adjustable with glow color and by academia
It is considered as preferable electroluminescent organic material with industrial circle, many research teams both domestic and external are from materials synthesis and device optimization side
Face is set about, and makes great efforts the combination property for improving red organic electroluminescence device to meeting the needs of industrialization.For example, calendar year 2001
S.R.Forrest of Princeton university et al. is using the complex of iridium btp with canonical red transmitting2Ir (acac) makees
For luminescent material, organic electroluminescence device is obtained by the method adulterated.Although the device shows that ideal HONGGUANG is sent out
Penetrate, but the efficiency of the device and brightness is relatively low, running voltage is higher.
In order to solve these problems, 2009, Ma Dongge of Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences et al. was selected
Efficient complex of iridium (fbi)2Ir (acac) is mixed and be obtained in material of main part multiple structure as red dye
Red organic electroluminescence device.Although the device is with higher maximum luminous efficiency and high-high brightness, its luminous effect
Rate promptly decays with the raising of electric current density；In addition, the device architecture of complexity not only causes the cost of manufacture of device higher
And be unfavorable for reducing the running voltage of device.2013, the red platinum complex of Hong Kong University Zhi Zhiming et al. synthesis was used as sending out
Luminescent material, designs and optimizes double emitting layers device architecture, obtains the organic electroluminescence device with pure red emission.Should
The efficiency decay of device is significantly alleviated, but device yet suffers from the higher problem of running voltage.
The content of the invention
It is an object of the invention to provide a kind of red organic electroluminescence device and preparation method thereof, what the present invention was provided
Red organic electroluminescence device running voltage is relatively low.
The invention provides a kind of red organic electroluminescence device, repaiies including the substrate, anode layer, anode for setting gradually
Decorations layer, hole transport-electronic barrier layer, the leading luminescent layer in hole, electronics leading luminescent layer, hole barrier-electron transfer layer, the moon
Pole decorative layer and cathode layer；
The leading luminescent layer of the electronics is prepared by the material including following components：
The organic sensitized material of 0.05wt%～2.0wt%, the organic sensitized material is the transition of energy levels matching
Metal complex；
The red luminous organic material of 1.0wt%～8.0wt%；
The electron type organic host material of surplus.
Preferably, the organic sensitized material include double (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics close iridium and/or
Double (the fluoro- 2,3- bipyridyls of 4- tertiary butyls -2,6- two) acetyl acetone iridium.
Preferably, the electron type organic host material include 2,6- bis- [3- (9H-9- carbazyls) phenyl] pyridine, Isosorbide-5-Nitrae-
Double (tri-phenyl-silane base) benzene, 2,2 '-bis- (4- (9- carbazyls) phenyl) biphenyl, three [2,4,6- trimethyl -3- (3- pyridine radicals)
Phenyl] borine, 1,3,5- tri- [(3- pyridines) -3- phenyl] benzene, 1,3- double [3,5- bis- (3- pyridine radicals) phenyl] benzene, 1,3,5- tri-
Double (triphenyl the silicon substrate) -9H- carbazoles of (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene, 9- (4- t-butyl-phenyls) -3,6- and 9-
One or more in (8- diphenylphosphoryls)-hexichol azoles [b, d] furan -9H- carbazoles.
Preferably, the red luminous organic material is two (2- phenylchinolines)-(2,2,6,6- tetramethyl -3,5- heptan two
Keto acid) close iridium, two (2- benzene azoles [b] 2- thienylpyridines) acetyl acetone iridium, three (1- phenyl isoquinolin quinolines) conjunction iridium, two (1- benzene
Base isoquinolin) (acetylacetone,2,4-pentanedione) close iridium, two [1- (9,9- dimethyl -9H- fluorenes -2- bases)-isoquinolin] (acetylacetone,2,4-pentanediones) close iridium, two
[2- (9,9- dimethyl -9H- fluorenes -2- bases) quinoline] (acetylacetone,2,4-pentanedione) closes iridium, two (2- phenylchinolines) (2- (3- aminomethyl phenyls) pyrrole
Pyridine) close iridium, three [2- phenyl -4- methylquinolines] conjunction iridium, double (phenyl isoquinolin quinolines) (2,2,6,6- tetramethyl hexane -3,5- diketone)
Close iridium, two (2- methyldiphenyl azoles [f, h] quinoxalines) (acetylacetone,2,4-pentanediones) and close iridium and two [2- (2- aminomethyl phenyls) -7- methyl-quinolines
Quinoline] (acetylacetone,2,4-pentanedione) close iridium in one or more.
Preferably, the leading luminescent layer of the electronics includes the organic sensitized material of 0.1wt%～1.0wt%.
Preferably, the leading luminescent layer of the electronics includes the red luminous organic material of 2.0wt%～6.5wt%.
Preferably, the thickness of the leading luminescent layer of the electronics is 5nm～20nm.
Preferably, the leading luminescent layer in the hole is prepared by the material including following components：
The red luminous organic material of 1.0wt%～8.0wt%；
The cavity type organic host material of surplus.
Preferably, the red luminous organic material in the leading luminescent layer in the hole include two (2- phenylchinolines)-(2,2,
The acid of 6,6- tetramethyl -3,5- heptadione) close iridium, two (2- benzene azoles [b] 2- thienylpyridines) acetyl acetone iridium, three (1- phenyl
Isoquinolin) close iridium, two (1- phenyl isoquinolin quinolines) (acetylacetone,2,4-pentanediones) conjunction iridium, two [1- (9,9- dimethyl -9H- fluorenes -2- bases)-isoquinolines
Quinoline] (acetylacetone,2,4-pentanedione) close iridium, two [2- (9,9- dimethyl -9H- fluorenes -2- bases) quinoline] (acetylacetone,2,4-pentanediones) close iridium, two (2- phenyl quinazolines
Quinoline) (2- (3- aminomethyl phenyls) pyridine) close iridium, three [2- phenyl -4- methylquinolines] close iridium, double (phenyl isoquinolin quinoline) (2,2,6,6-
Tetramethyl hexane -3,5- diketone) close iridium, two (2- methyldiphenyl azoles [f, h] quinoxalines) (acetylacetone,2,4-pentanediones) conjunction iridium and two [2- (2-
Aminomethyl phenyl) -7- Methyl-quinolines] (acetylacetone,2,4-pentanedione) close iridium in one or more.
Preferably, the cavity type organic host material includes 4,4 '-N, the N carbazole diphenyl of '-two, the carbazole -9- of 1,3- bis-
Base benzene, 9,9'- (5- (tri-phenyl-silane base) -1,3- phenyl) two -9H- carbazoles, 1,3,5- tri- (9- carbazyls) benzene, 4,4', 4 "
One or more in three (base of carbazole 9) triphenylamines and double (tri-phenyl-silane base) biphenyl of 1,4-.
Preferably, the thickness of the anode modification layer is 1nm～10nm；
The thickness of the hole transport-electronic barrier layer is 30nm～60nm；
The thickness of the leading luminescent layer in the hole is 5nm～20nm；
The thickness of the hole barrier-electron transfer layer is 30nm～60nm；
The thickness of the cathodic modification layer is 0.8nm～1.2nm；
The thickness of the cathode layer is 90nm～300nm.
The invention provides the preparation method of red organic electroluminescence device described in above-mentioned technical proposal, including following step
Suddenly：
Anode layer is set on substrate；
It is leading luminous that anode modification layer, hole transport-electronic barrier layer, hole are deposited with successively in the anode layer surface
Layer, electronics leading luminescent layer, hole barrier-electron transfer layer, cathodic modification layer and cathode layer, obtain red organic illuminator
Part.
Preferably, also include before anode layer surface evaporation anode modification layer：The substrate for being provided with anode layer is entered
The process of row low pressure plasma；
The time that the low pressure plasma is processed is 1min～10min.
Preferably, anode modification layer, hole transport-electronic barrier layer, hole master are deposited with successively in the anode layer surface
The vacuum for leading the leading luminescent layer of luminescent layer, electronics and hole barrier-electron transfer layer is 1 × 10-5Pa～2 × 10-5Pa；
The vacuum of the evaporation cathode decorative layer and cathode layer is 4 × 10-5Pa～6 × 10-5Pa。
The invention provides a kind of red organic electroluminescence device, repaiies including the substrate, anode layer, anode for setting gradually
Decorations layer, hole transport-electronic barrier layer, the leading luminescent layer in hole, electronics leading luminescent layer, hole barrier-electron transfer layer, the moon
Pole decorative layer and cathode layer；The leading luminescent layer of the electronics includes following components：0.05wt%～2.0wt%'s has Smart material
Material, the organic sensitized material is the transient metal complex of energy levels matching；1.0wt%～8.0wt%'s is red organic
Luminescent material；The electron type organic host material of surplus.Leading of electronics in the red organic luminescent device that the present invention is provided
Mixed with organic sensitized material in photosphere, the organic sensitized material can play a part of carrier constraint center deeply, be conducive to
The distribution of equilbrium carrier, the luminous interval for widening device, so as to reduce the running voltage of luminescent device.And the present invention is carried
For emitting red light device also there is higher luminous efficiency, efficiency decay is slow, with higher working life.Experimental result
Show, the bright voltage of the red organic electroluminescence device that the embodiment of the present invention 1～3 is obtained be respectively 2.8V, 2.9V and
2.9V；Maximum current efficiency is respectively 62.22cd/A, 63.56cd/A and 59.87cd/A；Maximum power efficiency is respectively
69.22lm/W, 68.82lm/W and 64.83lm/W.
And, in the present invention, the organic sensitized material can also play a part of energy transmission ladder, so as to accelerate
Energy transmission from material of main part to luminescent material, alleviates material of main part caused by luminescent material carrier capture scarce capacity and sends out
Optical issue, so that the red organic electroluminescence device that the present invention is provided has higher excitation.And the present invention is carried
For electroluminescent device spectrum stability it is high, its luminescent properties is relatively low to the dependency of luminescent material doping content.Experiment
As a result show, under the driving of forward voltage, the red organic electroluminescence device that the embodiment of the present invention is obtained can send
The HONGGUANG of 592nm；And with the change of running voltage, chromaticity coordinates is almost unchanged.
Description of the drawings
Fig. 1 is the structural representation of red organic electroluminescence device provided in an embodiment of the present invention；
Fig. 2 is the voltage-current density-light characteristic of the red organic electroluminescence device that the embodiment of the present invention 1 is obtained
Curve；
Fig. 3 is the electric current density-power efficiency-electric current of the red organic electroluminescence device that the embodiment of the present invention 1 is obtained
Efficiency characteristic device；
It is 20000cd/m in brightness that Fig. 4 is the red organic electroluminescence device that the embodiment of the present invention 1 is obtained2When light
Spectrogram.
Specific embodiment
The invention provides a kind of red organic electroluminescence device, repaiies including the substrate, anode layer, anode for setting gradually
Decorations layer, hole transport-electronic barrier layer, the leading luminescent layer in hole, electronics leading luminescent layer, hole barrier-electron transfer layer, the moon
Pole decorative layer and cathode layer；
The leading luminescent layer of the electronics includes following components：
The organic sensitized material of 0.05wt%～2.0wt%, the organic sensitized material is the transition of energy levels matching
Metal complex；
The red luminous organic material of 1.0wt%～8.0wt%；
The electron type organic host material of surplus.
It is described mixed with organic sensitized material in the leading luminescent layer of electronics in the red organic luminescent device that the present invention is provided
Organic sensitized material can play a part of carrier constraint center deeply, be conducive to the distribution of equilbrium carrier, widen device
Luminous interval, so as to reduce the running voltage of luminescent device.And the emitting red light device that the present invention is provided is also with higher
Luminous efficiency, efficiency decay is slow, with higher working life.
And, in the present invention, the organic sensitized material can also play a part of energy transmission ladder, so as to accelerate
Energy transmission from material of main part to luminescent material, alleviates material of main part caused by luminescent material carrier capture scarce capacity and sends out
Optical issue so that the red organic electroluminescence device that the present invention is provided has higher excitation.And present invention offer
The spectrum stability of electroluminescent device is high, and its luminescent properties is relatively low to the dependency of luminescent material doping content.
Referring to Fig. 1, Fig. 1 is the structural representation of red organic electroluminescence device provided in an embodiment of the present invention, wherein 1
It is anode layer, 3 is anode modification layer, 4 is hole transport-electronic barrier layer, 5 is the leading luminescent layer in hole, 6 is electricity for substrate, 2
The leading luminescent layer of son, 7 be hole barrier-electron transfer layer, 8 be cathodic modification layer, 9 be cathode layer.
The red organic electroluminescence device that the present invention is provided includes substrate.Material and source of the present invention to the substrate
Without special restriction, using those skilled in the art the substrate as electroluminescent device is known.In the reality of the present invention
In applying example, the substrate is preferably glass substrate, quartz substrate, multicrystalline silicon substrate, monocrystalline substrate or graphene film.
The red organic electroluminescence device that the present invention is provided includes anode layer, and the anode layer is arranged on the substrate
On.Material to the anode layer of the invention and source are used for without special restriction using well known to those skilled in the art
Anode layer in electroluminescent device.In the present invention, the material for preparing the anode layer is preferably indium tin oxide
(ITO)；The face resistance of the indium tin oxide is preferably 5 Ω～25 Ω, most preferably more preferably 5 Ω～10 Ω, 6 Ω～8 Ω.
The present invention does not have special restriction to the shape of the anode layer, using the sun in luminescent device well known to those skilled in the art
Pole layer；In the present invention, the anode layer is preferably the electrode of strip.
The red organic electroluminescence device that the present invention is provided includes anode modification layer, and the anode modification layer is arranged on institute
State on anode layer.The present invention to the material of the anode modification layer and source without special restriction, using people in the art
For the anode modification layer in electroluminescent device known to member.In the present invention, the material of the anode modification layer is prepared
Material is preferably molybdenum oxide (MoO3).In the present invention, the thickness of the anode modification layer is preferably 1nm～10nm, more preferably
2nm～8nm.
The present invention provide red organic electroluminescence device include hole transport-electronic barrier layer, the hole transport-
Electronic barrier layer is arranged in the anode modification layer.In the present invention, the thickness of the hole transport-electronic barrier layer is preferred
For 30nm～60nm, most preferably more preferably 35nm～55nm, 40nm～50nm.
In the present invention, prepare the hole transport-electronic barrier layer material preferably include 4,4'- cyclohexyl two [N,
N- bis- (4 aminomethyl phenyl) aniline] (TAPC), two pyrazine [2,3-f:2 ', 3 '-h] itrile groups of quinoxaline -2,3,6,7,10,11- six
(HAT-CN), N4, N4'- bis- (naphthalene -1- bases)-N4, N4'- double (4- ethenylphenyls) biphenyl -4,4'- diamidogen (VNPB), N, N'-
Double (3- aminomethyl phenyls)-N, N'- double (phenyl) -2,7- diamidogen -9,9- spiro-bisfluorenes (Spiro-TPD), N, N, N', N'- tetra--(3-
Aminomethyl phenyl) -3-3 '-dimethyl benzidine (HMTPD), 2,2'- bis- (3- (N, N- bis--p-totuidine base) phenyl) connection
Benzene (3DTAPBP), N, N'- bis- (naphthalene -2- bases)-N, N'- bis- (phenyl) benzidine (β-NPB), N, N'- bis- (base of naphthalene -1) -
N, N'- diphenyl -2,7- diaminourea -9,9- spiro-bisfluorenes (Spiro-NPB), N, N'- bis- (3- aminomethyl phenyls)-N, N'- diphenyl -
2,7- diaminourea -9,9- dimethyl fluorenes (DMFL-TPD), N, N'- bis- (naphthalene -1- bases)-N, N'- diphenyl -2,7- diaminourea -9,
9- dimethyl fluorenes (DMFL-NPB), N, N'- bis- (3- aminomethyl phenyls)-N, N'- diphenyl -2,7- diaminourea -9,9- diphenylfluorenes
(DPFL-TPD), N, N'- bis- (naphthalene -1- bases)-N, N'- -2,2 '-tolidines of diphenyl (α-NPD), 2,2', 7,
7'- tetra- (N, N- diphenyl amino) -2,7- diaminourea -9,9- spiro-bisfluorenes (Spiro-TAD), [4- (N, the N- dinaphthyl -2- of 9,9- bis-
Base-amino) phenyl] -9H- fluorenes (NPAPF), 9,9- [4- (base-N- aniline of N- naphthalenes -1)-phenyl] -9H- fluorenes (NPBAPF), 2,2 ' -
Two [N, N- bis- (4- phenyl) amino] -9,9- spiro-bisfluorenes (2,2'-Spiro-DBP), 2,2 '-bis- (N, N- phenylamino) -9,9- spiral shells
Double fluorenes (Spiro-BPA), N, N '-diphenyl-N, N '-(1- naphthyls) -1,1 '-biphenyl -4,4 '-diamidogen (NPB) and 4,4 '-two
One or more in [N- (p- tolyl)-N- phenyl-aminos] diphenyl (TPD).
The red organic electroluminescence device that the present invention is provided includes the leading luminescent layer in hole, and luminescent layer is dominated in the hole
It is arranged on the hole transport-electronic barrier layer.In the present invention, the thickness of the leading luminescent layer in the hole is preferably 5nm
～20nm, more preferably 5nm～10nm, most preferably 6nm～8nm.In the present invention, the leading luminescent layer in the hole preferably by
Prepare including the material of following components：
The red luminous organic material of 1.0wt%～8.0wt%；
The cavity type organic host material of surplus.
In the present invention, the leading luminescent layer in the hole preferably includes the red organic light emission material of 1.0wt%～8.0wt%
Material, most preferably more preferably 1.5wt%～6.5wt%, 2.0wt%～5.0wt%.In the present invention, the redness is organic
Luminescent material includes that iridium (PQ is closed in two (2- phenylchinolines)-(DPM dpm,dipivalomethane acid)2Ir (dpm)), two
(2- benzene azoles [b] 2- thienylpyridines) acetyl acetone iridium (Ir (btp)2(acac)), three (1- phenyl isoquinolin quinolines) close iridium (Ir
(piq)3), two (1- phenyl isoquinolin quinolines) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq)2(acac)), two [1- (9,9- dimethyl -9H- fluorenes -
2- yls)-isoquinolin] (acetylacetone,2,4-pentanedione) conjunction iridium (Ir (fliq)2(acac)), two [2- (9,9- dimethyl -9H- fluorenes -2- bases) quinoline
Quinoline] (acetylacetone,2,4-pentanedione) conjunction iridium (Ir (flq)2(acac)), two (2- phenylchinolines) (2- (3- aminomethyl phenyls) pyridine) close iridium (Ir
(phq)2Tpy), three [2- phenyl -4- methylquinolines] close iridium (Ir (Mphq)3), double (phenyl isoquinolin quinoline) (2,2,6,6- tetramethyls
Hexane -3,5- diketone) (Ir (dpm) is (piq) to close iridium2), two (2- methyldiphenyl azoles [f, h] quinoxalines) (acetylacetone,2,4-pentanediones) close iridium
(Ir(MDQ)2(acac)) and two [2- (2- aminomethyl phenyls) -7- Methyl-quinolines] (acetylacetone,2,4-pentanediones) close iridium (Ir (dmpq)2
(acac) one or more in).
In the present invention, the leading luminescent layer in the hole includes the cavity type organic host material of surplus.In the present invention,
The cavity type organic host material preferably includes 4,4 '-N, the carbazole diphenyl of N '-two (CBP), the carbazole -9- base benzene of 1,3- bis-
(mCP), 9,9'- (5- (tri-phenyl-silane base) -1,3- phenyl) two -9H- carbazoles (SimCP), 1,3,5- tri- (9- carbazyls) benzene
(TCP), 4,4', 4 " one kind in three (carbazole -9- bases) triphenylamines (TcTa) and 1,4- double (tri-phenyl-silane base) biphenyl (BSB)
Or it is several.
The red organic electroluminescence device that the present invention is provided includes the leading luminescent layer of electronics, and the electronics dominates luminescent layer
It is arranged on the leading luminescent layer in the hole.In the present invention, the leading luminescent layer of the electronics is preferably by including following components
It is prepared by material：
The organic sensitized material of 0.05wt%～2.0wt%, the organic sensitized material is the transition of energy levels matching
Metal complex；
The red luminous organic material of 1.0wt%～8.0wt%；
The electron type organic host material of surplus.
In the present invention, the leading luminescent layer of the electronics includes the organic sensitized material of 0.05wt%～2.0wt%, preferably
For 0.1wt%～1.0wt%, more preferably 0.2wt%～0.5wt%.In the present invention, the organic sensitized material is energy level
The transient metal complex of energy match, preferably includes double (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics and closes iridium
And/or double (the fluoro- 2,3- bipyridyls of 4- tertiary butyls -2,6- two) acetyl acetone iridium (FK306) (FIrpic).
The present invention adopts the transient metal complex of energy levels matching as organic sensitized material, by itself and luminescent material
In the leading luminescent layer of the electronics, the organic sensitized material serves carrier depth constraint center and energy transmission to codope
The effect of ladder, can not only equilbrium carrier distribution, widen the luminescent device of device, additionally it is possible to greatly improve material of main part
To the energy transmission of luminescent material, so as to improve luminescent device luminous efficiency, improve luminescent device excitation, reduce luminous
The running voltage of device, delay luminescent device efficiency decay, improve luminescent device spectrum stability, improve luminescent device
Working life.
In the present invention, the leading luminescent layer of the electronics includes the red luminous organic material of 1.0wt%～8.0wt%,
Preferably 2.0wt%～6.5wt%, more preferably 3.0wt%～5.0wt%.In the present invention, the red organic light emission material
Material preferably includes two (2- phenylchinolines)-(DPM dpm,dipivalomethane acid) and closes iridium (PQ2Ir (dpm)), two (2-
Benzene azoles [b] 2- thienylpyridines) acetyl acetone iridium (Ir (btp)2(acac)), three (1- phenyl isoquinolin quinolines) close iridium (Ir
(piq)3), two (1- phenyl isoquinolin quinolines) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq)2(acac)), two [1- (9,9- dimethyl -9H- fluorenes -
2- yls)-isoquinolin] (acetylacetone,2,4-pentanedione) conjunction iridium (Ir (fliq)2(acac)), two [2- (9,9- dimethyl -9H- fluorenes -2- bases) quinoline
Quinoline] (acetylacetone,2,4-pentanedione) conjunction iridium (Ir (flq)2(acac)), two (2- phenylchinolines) (2- (3- aminomethyl phenyls) pyridine) close iridium (Ir
(phq)2Tpy), three [2- phenyl -4- methylquinolines] close iridium (Ir (Mphq)3), double (phenyl isoquinolin quinoline) (2,2,6,6- tetramethyls
Hexane -3,5- diketone) (Ir (dpm) is (piq) to close iridium2), two (2- methyldiphenyl azoles [f, h] quinoxalines) (acetylacetone,2,4-pentanediones) close iridium
(Ir(MDQ)2(acac)) and two [2- (2- aminomethyl phenyls) -7- Methyl-quinolines] (acetylacetone,2,4-pentanediones) close iridium (Ir (dmpq)2
(acac) one or more in).
In the present invention, the leading luminescent layer of the electronics includes the electron type organic host material of surplus.In the present invention,
The electron type organic host material preferably includes 2,6- bis- [3- (9H-9- carbazyls) phenyl] pyridine (26DCzPPy), 1,4-
Double (tri-phenyl-silane base) benzene (UGH2), 2,2 '-bis- (4- (9- carbazyls) phenyl) biphenyl (BCBP), three [2,4,6- trimethyls-
3- (3- pyridine radicals) phenyl] borine (3TPYMB), 1,3,5- tri- [(3- pyridines) -3- phenyl] benzene (TmPyPB), the double [3,5- of 1,3-
Two (3- pyridine radicals) phenyl] benzene (BmPyPhB), 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi), 9- (4-
T-butyl-phenyl) double (triphenyl the silicon substrate) -9H- carbazoles (CzSi) of -3,6- and 9- (8- diphenylphosphoryls)-hexichol azoles [b, d]
One or more in furan -9H- carbazoles (DFCzPO).
The present invention provide red organic electroluminescence device include hole barrier-electron transfer layer, the hole barrier-
Electron transfer layer is arranged on the leading luminescent layer of the electronics.In the present invention, the thickness of the hole barrier-electron transfer layer
Preferably 30nm～60nm, more preferably 35nm～55nm, most preferably 40nm～50nm.
In the present invention, the material for preparing the hole barrier-electron transfer layer preferably include three [2,4,6- trimethyls-
3- (3- pyridine radicals) phenyl] borine (3TPYMB), 1,3,5- tri- [(3- pyridines) -3- phenyl] benzene (TmPyPB), the double [3,5- of 1,3-
Two (3- pyridine radicals) phenyl] in benzene (BmPyPhB) and 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi) one
Plant or several.
The red organic electroluminescence device that the present invention is provided includes cathodic modification layer, and the cathodic modification layer is arranged on institute
State on hole barrier-electron transfer layer.In the present invention, the thickness of the cathodic modification layer is preferably 0.8nm～1.2nm, more
Preferably 0.9nm～1.1nm.The present invention to the material of the cathodic modification layer and source without special restriction, using ability
For the cathodic modification layer in electroluminescent device known to field technique personnel.In the present invention, prepare the negative electrode to repair
The material of decorations layer is preferably lithium fluoride (LiF).
The red organic electroluminescence device that the present invention is provided includes cathode layer, and the cathode layer is arranged on the negative electrode and repaiies
On decorations layer.In the present invention, the thickness of the cathode layer is preferably 90nm～300nm, more preferably 100nm～280nm, optimum
Elect 120nm～250nm as.The present invention to the material of the cathode layer and source without special restriction, using art technology
For the cathode layer in electroluminescent device known to personnel.In the present invention, the cathode layer is preferably metallic cathode
Layer；The material for preparing the metal cathode layer is preferably metallic aluminium.
In the present invention, when forward voltage is applied on the red organic light emission provided in the present invention, the luminescent device is sent out
Go out the HONGGUANG of 592nm.
Present invention also offers the preparation method of red organic luminescent device described in above-mentioned technical proposal, including following step
Suddenly：
Anode layer is set on substrate；
It is leading luminous that anode modification layer, hole transport-electronic barrier layer, hole are deposited with successively in the anode layer surface
Layer, electronics leading luminescent layer, hole barrier-electron transfer layer, cathodic modification layer and cathode layer, obtain red organic illuminator
Part.
The present invention provides substrate, and anode layer is arranged over the substrate.In the present invention, the substrate and above-mentioned technical side
Substrate described in case is consistent, will not be described here.The present invention preferably performs etching the anode material for arranging over the substrate,
Strip shaped electric poles are formed on the substrate, anode layer is obtained over the substrate.In the present invention, the material of the anode layer with it is upper
State described in technical scheme unanimously, will not be described here.The present invention does not have special restriction to the method for the etching, using ability
Lithographic technique scheme known to field technique personnel, such as can be laser ablation.
The present invention is arranged after anode layer over the substrate, is preferably successively carried out the substrate for being provided with anode layer for obtaining
Cleanout fluid cleaning, deionized water are cleaned by ultrasonic and are dried.The present invention does not have special restriction to the species of the cleanout fluid, adopts
Cleanout fluid well known to those skilled in the art.In the present invention, the time that the deionized water is cleaned by ultrasonic is preferably
10min～20min.The present invention does not have special restriction to the method for the drying, using well known to those skilled in the art dry
Dry technical scheme；As being oven for drying in an embodiment of the present invention.
The present invention is arranged over the substrate after anode layer, and the present invention is deposited with successively anode modification on the anode layer
Layer, hole transport-electronic barrier layer, the leading luminescent layer in hole, electronics leading luminescent layer, hole barrier-electron transfer layer, negative electrode
Decorative layer and cathode layer, obtain red organic luminescent device.
Before the present invention is deposited with anode modification layer on the anode layer, the substrate of anode layer is provided with described in preferred pair to be carried out
Low pressure plasma process.The present invention is preferably by the substrate of anode layer that is provided with as carrying out low-voltage plasma in vacuum chamber
Body process.In the present invention, the vacuum that the low pressure plasma is processed is preferably 8Pa～15Pa, and more preferably 10Pa～
13Pa；The time that the low pressure plasma is processed is preferably 1min～10min, more preferably 4min～7min；Carry out described
The voltage of low pressure plasma process is preferably 350V～500V, most preferably more preferably 380V～480V, 400V～450V.
Obtain being provided with after the substrate of anode layer, the present invention is deposited with successively anode modification layer, sky in the anode layer surface
Cave transmission-electronic barrier layer, the leading luminescent layer in hole, electronics leading luminescent layer, hole barrier-electron transfer layer, cathodic modification
Layer and cathode layer, obtain red organic luminescent device.The substrate for being provided with anode layer is preferably placed in organic steaming by the present invention
In plating room, the anode layer surface be deposited with successively anode modification layer, hole transport-electronic barrier layer, the leading luminescent layer in hole,
The leading luminescent layer of electronics and hole barrier-electron transfer layer；In metal evaporation room, in the hole barrier-electric transmission
Layer surface evaporation cathode decorative layer and cathode layer successively.
In the present invention, the evaporation anode modification layer, hole transport-electronic barrier layer, hole leading luminescent layer, electronics
The vacuum of leading luminescent layer and hole barrier-electron transfer layer is preferably 1 × 10-5Pa～2 × 10-5Pa, more preferably 1.3
×10-5Pa～1.7 × 10-5Pa。
In the present invention, when the anode modification layer is deposited with, the evaporation rate of the anode modification layer material is preferably
0.01nm/s～0.2nm/s, more preferably 0.02nm/s～0.05nm/s；
When the hole transport-electronic barrier layer is deposited with, the evaporation rate of the hole transport-electronic blocking layer material
Preferably 0.05nm/s～0.2nm/s, more preferably 0.05nm/s～0.1nm/s；
In the evaporation hole during leading luminescent layer, in the leading luminescent layer in the hole, the red luminous organic material
Evaporation rate be preferably 0.001nm/s～0.005nm/s, more preferably 0.002nm/s～0.003nm/s；The cavity type
The evaporation rate of organic host material is preferably 0.05nm/s～0.1nm/s, more preferably 0.07nm/s～0.08nm/s；At this
In invention, the red luminous organic material and cavity type organic host material are preferably respectively in different evaporation sources while steam
Send out, the weight of the red luminous organic material and cavity type organic host material is caused by regulating and controlling the evaporation rate of bi-material
Measure the weight ratio than meeting red luminous organic material and cavity type organic host material described in above-mentioned technical proposal；
In the leading luminescent layer of the evaporation electronics, in the leading luminescent layer of the electronics, the steaming of the organic sensitized material
Send out speed and be preferably 0.00005nm/s～0.0005nm/s, more preferably 0.0001nm/s～0.0003nm/s；The redness has
The evaporation rate of machine luminescent material is preferably 0.001nm/s～0.005nm/s, more preferably 0.002nm/s～0.003nm/s；
The evaporation rate of the electron type organic host material is preferably 0.05nm/s～0.1nm/s, and more preferably 0.07nm/s～
0.08nm/s；In the present invention, the organic sensitized material, red luminous organic material and electron type organic host material difference
Evaporate simultaneously in different evaporation sources, by the evaporation rate for regulating and controlling three kinds of materials so that the organic sensitized material, redness
Luminous organic material and electron type organic host material meet organic sensitized material described in above-mentioned technical proposal, red organic light emission
The weight ratio of material and electron type organic host material；
When the hole barrier-electron transfer layer is deposited with, the evaporation speed of the material of the hole barrier-electron transfer layer
Rate is preferably 0.05nm/s～0.1nm/s, more preferably 0.07nm/s～0.08nm/s；
After completing the evaporation of the hole barrier-electron transfer layer, the present invention is preferably in the hole barrier-electric transmission
Metal evaporation cathodic modification layer and cathode layer successively on layer, obtain red organic electroluminescence device.The present invention preferably will include
By substrate, anode layer, anode modification layer, hole transport-electronic barrier layer, the leading luminescent layer in hole, the leading luminescent layer of electronics and
The organic electroluminescence device semi-finished product of hole barrier-electron transfer layer are placed in metal evaporation room, in the hole barrier-electricity
Evaporation cathode decorative layer and cathode layer successively in sub- transport layer.In the present invention, the evaporation cathode decorative layer and cathode layer
Vacuum is preferably 4 × 10-5Pa～6 × 10-5Pa, more preferably 4.5 × 10-5Pa～5.5 × 10-5Pa。
In the present invention, when being deposited with the cathodic modification layer, the evaporation rate of the cathodic modification layer material is preferably
0.005nm/s～0.05nm/s, more preferably 0.01nm/s～0.02nm/s；
When the cathode layer is deposited with, the evaporation rate of the cathode layer materials is preferably 0.5nm/s～2.0nm/s, more
Preferably 0.1nm/s～1.5nm/s.
The invention provides a kind of red organic electroluminescence device, repaiies including the substrate, anode layer, anode for setting gradually
Decorations layer, hole transport-electronic barrier layer, the leading luminescent layer in hole, electronics leading luminescent layer, hole barrier-electron transfer layer, the moon
Pole decorative layer and cathode layer；The leading luminescent layer of the electronics includes following components：0.05wt%～2.0wt%'s has Smart material
Material, the organic sensitized material is the transient metal complex of energy levels matching；1.0wt%～8.0wt%'s is red organic
Luminescent material；The electron type organic host material of surplus.Leading of electronics in the red organic luminescent device that the present invention is provided
Mixed with organic sensitized material in photosphere, the organic sensitized material can play a part of carrier constraint center deeply, be conducive to
The distribution of equilbrium carrier, the luminous interval for widening device, so as to reduce the running voltage of luminescent device.And the present invention is provided
Emitting red light device also there is higher luminous efficiency, efficiency decay is slow, with higher working life.Experimental result table
Bright, the bright voltage of the red organic electroluminescence device that the embodiment of the present invention 1～3 is obtained is respectively 2.8V, 2.9V and 2.9V；
Maximum current efficiency is respectively 62.22cd/A, 63.56cd/A and 59.87cd/A；Maximum power efficiency be respectively 69.22lm/W,
68.82lm/W and 64.83lm/W.
And, in the present invention, the organic sensitized material can also play a part of energy transmission ladder, so as to accelerate
Energy transmission from material of main part to luminescent material, alleviates material of main part caused by luminescent material carrier capture scarce capacity and sends out
Optical issue so that the red organic electroluminescence device that the present invention is provided has higher excitation.And present invention offer
The spectrum stability of electroluminescent device is high, and its luminescent properties is relatively low to the dependency of luminescent material doping content.Experimental result
Show, under the driving of forward voltage, the red organic electroluminescence device that the embodiment of the present invention is obtained can send 592nm's
HONGGUANG；And with the change of running voltage, chromaticity coordinates is almost unchanged.
In order to further illustrate the present invention, with reference to the red organic electroluminescence device that embodiment is provided the present invention
And preparation method thereof be described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
First by the electrode into strips of the ito anode layer laser ablation on ito glass, cleanout fluid, deionized water are then used successively
It is cleaned by ultrasonic 15 minutes and is put into oven for drying；Then the substrate after drying is put into into pretreatment vacuum chamber, is in vacuum
The low-voltage plasma carried out to ito anode 3 minutes with 400 volts of voltage under the atmosphere of 10Pa is transferred into organic steaming after processing
Plating room；
It is 1 × 10 in vacuum-5Pa～2 × 10-5In the organic vapor deposition room of Pa, on the ito layer successively with 0.01nm/s's
Speed evaporation 3nm thick MoO3Anode modification layer 3；With the thick TAPC hole transports-electronics of the speed evaporation 40nm of 0.05nm/s
Barrier layer 4；PQ is deposited with the speed of 0.002nm/s2The speed evaporation TcTa of Ir (dpm) and 0.05nm/s obtains the thick skies of 10nm
Dominate luminescent layer 5 in cave；With the speed evaporation PQ that the speed of 0.0001nm/s is deposited with FK306,0.002nm/s2Ir(dpm)、
The speed evaporation CzSi of 0.05nm/s obtains the leading luminescent layer 6 of the thick electronics of 10nm；It is thick with the speed evaporation 40nm of 0.05nm/s
TmPyPB hole barriers-electron transfer layer 7；
Next, above-mentioned unfinished device is transferred to into metal evaporation room, 4 × 10-5Pa～6 × 10-5The vacuum of Pa
With the LiF cathodic modification layers 8 of the speed evaporation 1.0nm thickness of 0.02nm/s under atmosphere；
The thick metal Al cathode layers 9 of 120nm are deposited with the speed of 1.0nm/s on LiF layers finally by mask plate, are prepared
It is ITO-MoO into structure3-TAPC-PQ2Ir (dpm) is (4wt%):TcTa (96wt%)-FK306 (0.2wt%):PQ2Ir(dpm)
(4wt%)：The organic electroluminescence device of CzSi (95.8wt%)-TmPyPB-LiF-Al.
The present invention applies DC voltage on the organic electroluminescence device for obtaining, and under direct voltage drive, launches
Positioned at the HONGGUANG of 592nm or so；
The present invention carries out performance test to the luminescent device for obtaining, and as a result as shown in Figure 2 to 4, Fig. 2 is present invention enforcement
Voltage-current density-the luminosity response of the red organic electroluminescence device that example 1 is obtained, as seen from Figure 2, this reality
The brightness of red organic electroluminescence device for applying example offer raises with the rising of electric current density and driving voltage, and device rises
Bright voltage be 2.8V, voltage be 9.6V, electric current density be 554.23mA/cm2When, device obtains high-high brightness 91947cd/m2；
With the change of running voltage, the chromaticity coordinates of device is almost unchanged；
As shown in figure 3, Fig. 3 is the electric current density-power of the red organic electroluminescence device that the embodiment of the present invention 1 is obtained
Efficiency-current efficiency characteristics curve, as seen from Figure 3, the maximum of the red organic electroluminescence device that the present embodiment is obtained
Current efficiency is 62.22cd/A, and maximum power efficiency is 69.78lm/W；
As shown in figure 4, Fig. 4 is the red organic electroluminescence device that the embodiment of the present invention 1 is obtained being in brightness
20000cd/m2When spectrogram, as seen from Figure 4, when brightness be 20000cd/m2When, the chromaticity coordinates of device for (0.594,
0.379)。
Embodiment 2
First by the electrode into strips of the ito anode layer laser ablation on ito glass, cleanout fluid, deionized water are then used successively
It is cleaned by ultrasonic 15 minutes and is put into oven for drying.Then the substrate after drying is put into into pretreatment vacuum chamber, is in vacuum
The low-voltage plasma carried out to ito anode 3 minutes with 400 volts of voltage under the atmosphere of 10Pa is transferred into organic steaming after processing
Plating room；
It is 1 × 10 in vacuum-5Pa～2 × 10-5In the organic vapor deposition room of Pa, on the ito layer successively with 0.01nm/s's
Speed evaporation 3nm thick MoO3Anode modification layer 3；With the thick TAPC hole transports-electronics of the speed evaporation 40nm of 0.05nm/s
Barrier layer 4；PQ is deposited with the speed of 0.002nm/s2The speed evaporation mCP of Ir (dpm) and 0.05nm/s obtains the thick skies of 10nm
Dominate luminescent layer 5 in cave；With the speed evaporation PQ that the speed of 0.0001nm/s is deposited with FK306,0.002nm/s2Ir (dpm) and
The speed evaporation mCP of 0.05nm/s obtains the leading luminescent layer 6 of the thick electronics of 10nm；Thick with the speed evaporation 40nm of 0.05nm/s
TmPyPB hole barriers-electron transfer layer 7；
Next, above-mentioned unfinished device is transferred to into metal evaporation room, 4 × 10-5Pa～6 × 10-5The vacuum of Pa
With the LiF cathodic modification layers 8 of the speed evaporation 1.0nm thickness of 0.02nm/s under atmosphere；
The thick metal Al cathode layers 9 of 120nm are deposited with the speed of 1.0nm/s on LiF layers finally by mask plate, are prepared
It is ITO-MoO into structure3-TAPC-PQ2Ir (dpm) is (4wt%):MCP (96wt%)-FK306 (0.2wt%):PQ2Ir(dpm)
(4wt%)：The organic electroluminescence device of CzSi (95.8wt%)-TmPyPB-LiF-Al.
The present invention applies DC voltage on the organic electroluminescence device for obtaining, and under direct voltage drive, this is organic
Electroluminescent device launches the HONGGUANG positioned at 592nm or so；
The present invention carries out performance test to the luminescent device for obtaining, and as a result shows, the red Organic Electricity that the present embodiment is obtained
The brightness of electroluminescence device is raised with the rising of electric current density and driving voltage, and the bright voltage of device is 2.9V, device
High-high brightness is 96832cd/m2；The maximum current efficiency of the red organic electroluminescence device be 63.56cd/A, peak power
Efficiency is 68.82lm/W；When brightness is 20000cd/m2When, the chromaticity coordinates of device for (0.592,0.382)；With running voltage
Change, the chromaticity coordinates of device is almost unchanged.
Embodiment 3
First by the electrode into strips of the ito anode layer laser ablation on ito glass, cleanout fluid, deionized water are then used successively
It is cleaned by ultrasonic 15 minutes and is put into oven for drying.Then the substrate after drying is put into into pretreatment vacuum chamber, is in vacuum
The low-voltage plasma carried out to ito anode 3 minutes with 400 volts of voltage under the atmosphere of 10Pa is transferred into organic steaming after processing
Plating room；
It is 1 × 10 in vacuum-5Pa～2 × 10-5In the organic vapor deposition room of Pa, on the ito layer successively with 0.01nm/s's
Speed evaporation 3nm thick MoO3Anode modification layer 3；With the thick TAPC hole transports-electronics of the speed evaporation 40nm of 0.05nm/s
Barrier layer 4；PQ is deposited with the speed of 0.002nm/s2The speed evaporation TcTa of Ir (dpm) and 0.05nm/s obtains the thick skies of 10nm
Dominate luminescent layer 5 in cave；With the speed evaporation PQ that the speed of 0.0003nm/s is deposited with FIrpic, 0.004nm/s2Ir (dpm) and
The speed evaporation 26DCzPPy of 0.1nm/s obtains the leading luminescent layer 6 of the thick electronics of 10nm；40nm is deposited with the speed of 0.05nm/s
Thick TmPyPB hole barriers-electron transfer layer 7；
Next, above-mentioned unfinished device is transferred to into metal evaporation room, 4 × 10-5Pa～6 × 10-5The vacuum of Pa
With the LiF cathodic modification layers 8 of the speed evaporation 1.0nm thickness of 0.02nm/s under atmosphere；
The thick metal Al cathode layers 9 of 120nm are deposited with the speed of 1.0nm/s on LiF layers finally by mask plate, are prepared
It is ITO-MoO into structure3-TAPC-PQ2Ir (dpm) is (4wt%):TcTa (96wt%)-FIrpic (0.3wt%):PQ2Ir
(dpm) (4wt%)：The organic electroluminescence device of 26DCzPPY (95.7wt%)-TmPyPB-LiF-Al.
The present invention applies DC voltage on the organic electroluminescence device for obtaining, and under direct voltage drive, this is organic
Electroluminescent device launches the HONGGUANG positioned at 592nm or so；
The present invention carries out performance test to the luminescent device for obtaining, and as a result shows, the red Organic Electricity that the present embodiment is obtained
The brightness of electroluminescence device is raised with the rising of electric current density and driving voltage, and the bright voltage of device is 2.9V, device
High-high brightness is 89832cd/m2；The maximum current efficiency of the red organic electroluminescence device be 59.87cd/A, peak power
Efficiency is 64.83lm/W；When brightness is 20000cd/m2When, the chromaticity coordinates of device for (0.588,0.386)；With running voltage
Change, the chromaticity coordinates of device is almost unchanged.
As seen from the above embodiment, in the leading luminescent layer of electronics in the red organic luminescent device that the present invention is provided mixed with
Organic sensitized material, the organic sensitized material can play a part of carrier constraint center deeply, be conducive to equilbrium carrier
Distribution, the luminous interval of device is widened, so as to reduce the running voltage of luminescent device.And the emitting red light that the present invention is provided
Device also has higher luminous efficiency, and efficiency decay is slow, with higher working life.Test result indicate that, the present invention
The bright voltage of the red organic electroluminescence device that embodiment 1～3 is obtained is respectively 2.8V, 2.9V and 2.9V；Maximum current
Efficiency is respectively 62.22cd/A, 63.56cd/A and 59.87cd/A；Maximum power efficiency is respectively 69.22lm/W, 68.82lm/
W and 64.83lm/W.
And, in the present invention, the organic sensitized material can also play a part of energy transmission ladder, so as to accelerate
Energy transmission from material of main part to luminescent material, alleviates material of main part caused by luminescent material carrier capture scarce capacity and sends out
Optical issue so that the red organic electroluminescence device that the present invention is provided has higher excitation.And present invention offer
The spectrum stability of electroluminescent device is high, and its luminescent properties is relatively low to the dependency of luminescent material doping content.Experimental result
Show, under the driving of forward voltage, the red organic electroluminescence device that the embodiment of the present invention is obtained can send 592nm's
HONGGUANG；And with the change of running voltage, chromaticity coordinates is almost unchanged.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (12)
1. a kind of red organic electroluminescence device, including the substrate, anode layer, anode modification layer, hole transport for setting gradually-
Electronic barrier layer, the leading luminescent layer in hole, electronics leading luminescent layer, hole barrier-electron transfer layer, cathodic modification layer and negative electrode
Layer；
The leading luminescent layer of the electronics is prepared by the material including following components：
The organic sensitized material of 0.05wt%～2.0wt%, the organic sensitized material is the transition metal of energy levels matching
Coordination compound；The organic sensitized material includes that double (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics close iridium and/or double (4- is special
The fluoro- 2,3- bipyridyls of butyl -2,6- two) acetyl acetone iridium；
The red luminous organic material of 1.0wt%～8.0wt%；
The electron type organic host material of surplus；The electron type organic host material includes the [3- (9H-9- carbazyls) of 2,6- bis-
Phenyl] pyridine, 1,4- double (tri-phenyl-silane base) benzene, 2,2 '-bis- (4- (9- carbazyls) phenyl) biphenyl, three [2,4,6- front threes
Base -3- (3- pyridine radicals) phenyl] borine, 1,3,5- tri- [(3- pyridines) -3- phenyl] benzene, the double [3,5- bis- (3- pyridine radicals) of 1,3-
Phenyl] benzene, 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene, double (the triphenyl silicon of 9- (4- t-butyl-phenyls) -3,6-
Base) one or more in -9H- carbazoles and 9- (8- diphenylphosphoryls)-hexichol azoles [b, d] furan -9H- carbazoles.
2. red organic electroluminescence device according to claim 1, it is characterised in that the red luminous organic material
Iridium, two (2- benzene azoles [b] 2- thienylpyridines) are closed for two (2- phenylchinolines)-(DPM dpm,dipivalomethane acid)
Acetyl acetone iridium, three (1- phenyl isoquinolin quinolines) close iridium, two (1- phenyl isoquinolin quinolines) (acetylacetone,2,4-pentanediones) and close iridium, two [1- (9,9- bis-
Methyl-9 H-fluorene -2- bases)-isoquinolin] (acetylacetone,2,4-pentanedione) close iridium, two [2- (9,9- dimethyl -9H- fluorenes -2- bases) quinoline] (acetyl
Acetone) close iridium, two (2- phenylchinolines) (2- (3- aminomethyl phenyls) pyridine) and close iridium, three [2- phenyl -4- methylquinolines] and close iridium, double
(phenyl isoquinolin quinoline) (2,2,6,6- tetramethyl hexane -3,5- diketone) closes iridium, two (2- methyldiphenyl azoles [f, h] quinoxalines) (second
Acyl acetone) close iridium and two [2- (2- aminomethyl phenyls) -7- Methyl-quinolines] (acetylacetone,2,4-pentanediones) close iridium one or more.
3. the red organic electroluminescence device according to claim 1～2 any one, it is characterised in that the electronics
Leading luminescent layer includes the organic sensitized material of 0.1wt%～1.0wt%.
4. the red organic electroluminescence device according to claim 1～2 any one, it is characterised in that the electronics
Leading luminescent layer includes the red luminous organic material of 2.0wt%～6.5wt%.
5. the red organic electroluminescence device according to claim 1～2 any one, it is characterised in that the electronics
The thickness of leading luminescent layer is 5nm～20nm.
6. red organic electroluminescence device according to claim 1, it is characterised in that the leading luminescent layer in the hole by
Prepare including the material of following components：
The red luminous organic material of 1.0wt%～8.0wt%；
The cavity type organic host material of surplus.
7. red organic electroluminescence device according to claim 6, it is characterised in that in the leading luminescent layer in the hole
Red luminous organic material include that two (2- phenylchinolines)-(DPM dpm,dipivalomethane acid) closes iridium, two (2-
Benzene azoles [b] 2- thienylpyridines) acetyl acetone iridium, three (1- phenyl isoquinolin quinolines) close iridium, two (1- phenyl isoquinolin quinolines) (levulinics
Ketone) close iridium, two [1- (9,9- dimethyl -9H- fluorenes -2- bases)-isoquinolin] (acetylacetone,2,4-pentanediones) close iridium, two [2- (9,9- dimethyl -
9H- fluorenes -2- bases) quinoline] (acetylacetone,2,4-pentanedione) close iridium, two (2- phenylchinolines) (2- (3- aminomethyl phenyls) pyridine) close iridium, three [2- benzene
Base -4- methylquinolines] close iridium, double (phenyl isoquinolin quinolines) (2,2,6,6- tetramethyl hexane -3,5- diketone) conjunction iridium, two (2- methyl
Hexichol azoles [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) closes iridium and two [2- (2- aminomethyl phenyls) -7- Methyl-quinolines] (acetylacetone,2,4-pentanediones) are closed
One or more in iridium.
8. red organic electroluminescence device according to claim 6, it is characterised in that the cavity type organic main body material
Material includes 4,4 '-N, the carbazole diphenyl of N '-two, the carbazole -9- base benzene of 1,3- bis-, 9,9'- (5- (tri-phenyl-silane base) -1,3- benzene
Base) two -9H- carbazoles, 1,3,5- tri- (9- carbazyls) benzene, 4,4', 4 " double (the triphenyl silicon of three (base of carbazole 9) triphenylamines and 1,4-
Alkyl) one or more in biphenyl.
9. red organic electroluminescence device according to claim 1, it is characterised in that the thickness of the anode modification layer
For 1nm～10nm；
The thickness of the hole transport-electronic barrier layer is 30nm～60nm；
The thickness of the leading luminescent layer in the hole is 5nm～20nm；
The thickness of the hole barrier-electron transfer layer is 30nm～60nm；
The thickness of the cathodic modification layer is 0.8nm～1.2nm；
The thickness of the cathode layer is 90nm～300nm.
10. the preparation method of red organic electroluminescence device described in claim 1～9 any one, comprises the following steps：
Anode layer is set on substrate；
Anode modification layer, hole transport-electronic barrier layer, hole leading luminescent layer, electricity are deposited with successively in the anode layer surface
Son leading luminescent layer, hole barrier-electron transfer layer, cathodic modification layer and cathode layer, obtain red organic luminescent device.
11. preparation methoies according to claim 10, it is characterised in that be deposited with anode modification layer in the anode layer surface
It is front also to include：The substrate for being provided with anode layer is carried out into low pressure plasma process；
The time that the low pressure plasma is processed is 1min～10min.
12. preparation methoies according to claim 10, it is characterised in that be deposited with anode successively in the anode layer surface and repair
Decorations layer, hole transport-electronic barrier layer, the leading luminescent layer in hole, the leading luminescent layer of electronics and hole barrier-electron transfer layer
Vacuum is 1 × 10-5Pa～2 × 10-5Pa；
The vacuum of the evaporation cathode decorative layer and cathode layer is 4 × 10-5Pa～6 × 10-5Pa。
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