CN110473975A - A kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving - Google Patents
A kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving Download PDFInfo
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- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
- H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent layers
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Abstract
The invention discloses a kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving, belong to technical field of organic electroluminescence, the present invention is based on double microcavity technologies, it is realized by two microcavitys of lateral laid out in parallel and double-colored (such as blue light and yellow light) microcavity effect is separately optimized, not only take full advantage of microcavity effect enhancing device performance, improve excitation purity, also by way of exchange driving, ensure that device colour temperature and brightness distinguish adjustable advantage, double microcavity technologies also compensate for different colours material lifetime bring colour cast simultaneously, to obtain the adjustable color type top emitting white light organic electroluminescent device of exchange driving spectrum-stable in conjunction with scattering device, the double microcavity top emitting white light organic electroluminescent devices of the AC driving type of this simple process and adjustable color meet the demand and large-scale production in market Cost requirement.
Description
Technical field
The invention belongs to technical field of organic electroluminescence, and in particular to a kind of double microcavity top emitting white lights of exchange driving
Organic electroluminescence device.
Background technique
Organic electroluminescence device (Organic Light-emitting Devices, OLEDs) has efficiently gently because of it
Thin, flexible rollable, low-power consumption and the advantages such as environmentally protective, display and in terms of possess huge application potential.Through
It crosses many Research Teams, the world and enterprise to pay hard by what is persevered for several decades as if it were one day in terms of material and device, at present OLEDs
The relevant technologies have been achieved for development at full speed, as the external quantum efficiency of the free base luminescent device of two-wire state has reached 27%
[Nature, 563 (2018) 536-540], the panels such as Samsung, BOE enterprise extend OLEDs production line one after another, and correlation display is shone
Bright product just gradually enters among daily life.
Compared to conventional bottom emitting OLEDs, top emitting OLEDs has many advantages: (1) break the limitation of substrate,
It can prepare on any substrate；(2) due to its higher aperture opening ratio, it is more suitable for display field application；(3) monochromatic top emitting
OLEDs can utilize microcavity effect, realize high color purity and high efficiency.But top emitting white light organic electroluminescent device is always
The difficult point in the field in the world, this is mainly due to the presence of microcavity effect in device, microcavity effect will enhance resonant cavity wave
Photon state density near long, weakens the Photon state density at other wavelength, causes the spatial distribution of device in resonant cavity wavelength
Near.It is well known that white light is the combination of different wave length color of light in visible light, usually by red green blue tricolor or champac
Equal dual base colors composition, so while white light is easily achieved in top emitting OLEDs, but due to the reason of microcavity effect, top hair
The realization for penetrating white light OLED s is but difficult, and also seldom, the top emitting white light organic electroluminescence device of adjustable color is reported in correlative study
Part is then more difficult.It is general to realize top emitting white light OLED s:(1 by two methods in current existing report) it eliminates or subtracts
Microcavity effect in weak device such as increases the transmitance method [Adv. Mater.22 (2010) 5227-5239] of top electrodes.
But this method can not enhance the advantage of device performance, while the indium tin oxide (ITO) of high transmittance using microcavity effect
The preparation process of top electrodes is complicated and can damage lower organic layer, and the transmitance of semi-transparent metals electrode is limited to metal
Intrinsic property needs to compromise between conductivity and transmitance.(2) such as long by increasing chamber using the microcavity effect in device
Realize multi-mode resonance transmitting [Semicond Sci.Technol.19 (2004) 1138-1140].But if having by increasing
Machine thickness degree, it will increase the operating voltage of device, increase device power consumption；And if passing through the compound of high reflecting metal and ITO
Electrode increases ITO thickness to realize multimodes emitting, it will increase the complexity of device preparation, and efficiency is lower.
Summary of the invention
In order to solve disadvantage mentioned above existing in the prior art, the present invention provides a kind of double microcavity tops hairs of exchange driving
Penetrate white light organic electroluminescent device and preparation method thereof, using exchange electric drive technology and double microcavity technologies (the first microcavity and
Second microcavity) microcavity effect of different colours is separately optimized, finally obtain efficient top emitting white light organic electroluminescence hair
Optical device.
The present invention adopts the following technical scheme:
A kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving, including substrate 1 and two microcavitys, institute
Two microcavity transverse direction laid out in parallel are stated on substrate 1, the microcavity includes the first microcavity and the second microcavity, and the microcavity is under
To upper successively including high reflection charge inducing layer 2, functional layer, top electrode layer 8 and light removing layer 9；The functional layer includes sky
Cave implanted layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6 and electron injecting layer 7；The high reflection charge inducing layer 2
It connects two microcavitys and generates charge inducing under extra electric field, itself do not apply any external drive signal；Two microcavitys
In luminescent layer 5 be different colours, generate white light after two kinds of color additions；Top electrode layer 8 in two microcavitys is different electricity
Pole has certain spacing between two electrodes；Entire device is applied to the difference electricity of top electrode layer 8 using ac signal
It is driven on extremely, turns DC installation without alternating current.
Further, the bottom high reflection charge inducing layer 2 with a thickness of 30nm-200nm, hole injection layer 3
With a thickness of 0.1-10nm, hole transmission layer 4 with a thickness of 20-70nm, luminescent layer 5 with a thickness of 10-50nm, electron transfer layer 6
With a thickness of 20-70nm, electron injecting layer 7 with a thickness of 0.1-10 nm, top electrode layer 8 with a thickness of 5-30nm, light takes out
Layer 9 with a thickness of 20-200nm.
Further, the functional layer, which is positive, sets structure or inverted structure；When be positive set structure when, the functional layer from
Under to being above followed successively by hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6 and electron injecting layer 7；When for be inverted
When structure, the functional layer be followed successively by from top to bottom electron injecting layer 7, electron transfer layer 6, luminescent layer 5, hole transmission layer 4 and
Hole injection layer 3.
Further, the substrate 1 is insulating material, including glass, paper, photoresist, polyethylene
High molecular polymers, cloth, the plastics such as terephthalate (PET) etc..Substrate, which can be rigid, is also possible to flexible, shape
Shape and size are unlimited.
Further, high reflection charge inducing layer 2 can be any material with high reflectance and conduction, including 30nm
The high reflecting metals such as more than thickness silver, magnesium silver alloy (1:1-50:1), aluminium, gold；It is also possible to high reflection material and other
The combination of conductive material, other conductive materials include metal oxides, carbon nanotube, silver nanowiress such as indium tin oxide (ITO)
The equal conducting polymers such as nanometer conductive materials and poly- 3,4-rthylene dioxythiophene/poly styrene sulfonate (PEDOT:PSS).
Further, the material of the hole injection layer 3 is molybdenum trioxide (MoO3), tungstic acid (WoO3) or 2,3,
Six cyano -1,4,5,8,9,12- of 6,7,10,11-, six azepine benzophenanthrene (HAT-CN)；
The material of the hole transmission layer 4 be 4,4'- cyclohexyl two (N, N- bis- (4- aminomethyl phenyl) aniline) (TAPC),
(carbazole -9- base) triphenylamine (TCTA) of 4,4', 4'- tri- or N, N'- diphenyl-N, N'- (1- naphthalene) -1,1'- biphenyl -4,4'-
Diamines (NPB).
Further, the luminescent layer 5 in first microcavity is the first luminescent layer 5-1, shining in second microcavity
Layer 5 is the second luminescent layer 5-2；The color of the first luminescent layer 5-1 and the second luminescent layer 5-2 are different, select blue yellow or any
Complementation can produce two kinds of colors of white light, and using the doped structure of material of main part and guest materials, material of main part is selected from 4,4',
4'- tri- (carbazole -9- base) triphenylamine (TCTA), 4,4'-N, bis- carbazoles of N--biphenyl (CBP), 9,9'- (2,6- pyridine diyl two -
The Asia 3,1- benzene) double -9H- carbazoles (26DCzPPy), [5- (4- tert-butyl-phenyl) -1,3,4- dislikes two to 2,2'- (1,3- phenyl) two
At least one of azoles] (OXD-7) etc.；Blue light guest materials is closed selected from bis- (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics
Iridium (Firpic), bis- (the fluoro- 2- of 3,5- bis- (2- pyridyl group-KN) phenyl-KC) (four (1H- pyrazolyl-KN1) boric acid (1-)-
KN2, KN2')-iridium (Fir6) or two (2- hydroxy phenyl pyridines) close beryllium (Be (PP)2At least one of) etc.；Green light object material
Material closes iridium [Ir (ppy) selected from three (2- phenylpyridines)3], acetopyruvic acid two (2- phenylpyridine-C2, N) close iridium (III) [Ir
(ppy)2At least one of (acac)] etc.；Yellow light guest materials is selected from (4- phenyl-thiophene [3,2-c] pyrrole of acetopyruvic acid two
Pyridine-C2, N) close iridium (III) (PO-01), acetopyruvic acid two (4- (4- tbutyl-phenyl)-thiophene [3,2-c] pyridine-C2,
N it) closes at least one of iridium (III) (PO-01-TB) etc.；Feux rouges guest materials is selected from three (1- phenyl isoquinolin quinoline) iridium [Ir
(piq)3] or (acetylacetone,2,4-pentanedione) bis- (2- methyldiphenyls simultaneously [f, h] quinoxaline) close iridium [Ir (MDQ)2Etc. (acac)] at least one in
Kind；Wherein, the mass ratio between material of main part and guest materials is 50:1-1:1.
Further, the material of the electron transfer layer 6 be 1,3,5- tri- (2-N- benzene-benzene and imidazoles) benzene (TPBi),
Bis- (bis- pyridin-3-yl phenyl of the 3,5-) benzene (BmPyPhB) of 1,3,5- tri- [(3- pyridyl group) -3- phenyl] benzene (TmPyPB), 1,3-
Or 4,7- diphenyl -1,10- phenanthroline (Bphen)；
The material of the electron injecting layer 7 is LiF, Cs2CO3Or (8-hydroxyquinoline) lithium (Liq).
Further, the top electrode layer 8 includes electrode 8-A and electrode 8-B, is semi-transparent conductive material, includes
Silver, the magnesium silver alloy (1:1-50:1), aluminium, gold for having 30nm or less conductive；Spacing distance between described two electrodes is 1nm-
20cm。
Further, the light removing layer 9 is transparent material, is passed selected from above-mentioned hole injection layer material, above-mentioned hole
Defeated layer material, above-mentioned electron transport layer materials and above-mentioned electron injecting layer material.
The present invention exchange driving double microcavity top emitting white light organic electroluminescent device driving signals can be sine wave,
Square wave, triangular wave isopolarity variation AC signal in any one, frequency 0.1Hz-1MHz.
The present invention exchanges double microcavity top emitting white light organic electroluminescent devices of driving by vacuum vapour deposition technique, spin coating
At least one of technique or spraying process are made.
Compared with prior art, the present invention has the advantage that
The present invention is based on double microcavity technologies, by two microcavitys of lateral laid out in parallel realize to it is double-colored (such as blue light and
Yellow light) microcavity effect is separately optimized, and not only takes full advantage of microcavity effect enhancing device performance, improves excitation purity, and it is also logical
Cross the mode of exchange driving, it is ensured that adjustable advantage is distinguished in device colour temperature and brightness, while double microcavity technologies also compensate for not
With color material service life bring colour cast, to obtain the adjustable color type top of exchange driving spectrum-stable in conjunction with scattering device
Emit white light organic electroluminescent device, the double microcavity top emitting white lights of the AC driving type of this simple process and adjustable color have
Organic electroluminescence devices meet the demand in market and the cost requirement of large-scale production.
Detailed description of the invention
Fig. 1: the present invention exchanges the structural schematic diagram of double microcavity top emitting white light organic electroluminescent devices of driving；
Wherein: substrate 1, high reflection charge inducing layer 2, hole injection layer 3, hole transmission layer 4, the first luminescent layer 5-1,
Two luminescent layer 5-2, electron transfer layer 6, electron injecting layer 7, top electrode layer 8 and light removing layer 9；
Fig. 2: exchange of the invention drives the preparation flow figure of double microcavity top emitting white light organic electroluminescent devices；
Fig. 3: scattering device schematic diagram of the present invention；
Fig. 4: double microcavity top emitting white light organic electroluminescent devices of exchange driving are being handed over respectively in the embodiment of the present invention 1
Current density-voltage-luminosity response under galvanic electricity positive-negative polarity voltage；
Fig. 5: double microcavity top emitting white light organic electroluminescent devices of exchange driving are being handed over respectively in the embodiment of the present invention 1
Current efficiency-brightness-power efficiency characteristic curve under galvanic electricity positive-negative polarity voltage；
Fig. 6 is double microcavity top emitting white light organic electroluminescent devices of the exchange driving of embodiment 1 in 50Hz alternating current
Drive the normalization electroluminescent spectrum under lower different angle；
Fig. 7: double microcavity top emitting white light organic electroluminescent devices of exchange driving are in 50Hz in the embodiment of the present invention 1
Spectrum under different alternating voltage combinations adjusts the working drawing under figure and different-colour；Wherein: (a) alternating current negative half-cycle voltage
VnFor -6V, positive half period voltage VpNormalization electroluminescent spectrum from 0V to 6.5V under different voltages combination；(b) alternating current is being just
Half-cycle voltage VpFor 6V, negative half-cycle voltage VnNormalization electroluminescent spectrum from 0V to -6.5V under different voltages combination；
(c) integral device finally changes to the photo to work under the different-colour of yellow light from blue light by cool white light to warm white；
Fig. 8 is that the paper base exchange of embodiment 2 drives double microcavity top emitting white light organic electroluminescent devices to exchange in 50Hz
Working drawing under electric drive；Wherein: (a) individual devices issue blue yellow double-colored work photo；(b) individual devices are attached to curved
Injector surface issues blue yellow double-colored work photo；(c) double a devices, which work at the same time, issues two blue yellow double-colored work photographs
Piece；(d) double a devices are attached to curved injector surface and issue two blue yellow double-colored work photos；
Specific embodiment
The present invention is described further with reference to the accompanying drawing.
Embodiment 1
A kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving, including substrate 1 and two microcavitys, institute
Two microcavity transverse direction laid out in parallel are stated on substrate 1, the microcavity includes the first microcavity and the second microcavity, and the microcavity is under
To upper successively including high reflection charge inducing layer 2, functional layer, top electrode layer 8 and light removing layer 9；The functional layer includes sky
Cave implanted layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6 and electron injecting layer 7；The high reflection charge inducing layer 2
It connects two microcavitys and generates charge inducing under extra electric field, itself do not apply any external drive signal；Two microcavitys
In luminescent layer 5 be different colours, generate white light after two kinds of color additions；Top electrode layer 8 in two microcavitys is different electricity
Pole has certain spacing between two electrodes；Entire device is applied to the difference electricity of top electrode layer 8 using ac signal
It is driven on extremely, turns DC installation without alternating current.
Further, the bottom high reflection charge inducing layer 2 with a thickness of 30nm-200nm, hole injection layer 3
With a thickness of 0.1-10nm, hole transmission layer 4 with a thickness of 20-70nm, luminescent layer 5 with a thickness of 10-50nm, electron transfer layer 6
With a thickness of 20-70nm, electron injecting layer 7 with a thickness of 0.1-10 nm, top electrode layer 8 with a thickness of 5-30nm, light takes out
Layer 9 with a thickness of 20-200nm.
Further, the functional layer, which is positive, sets structure or inverted structure；When be positive set structure when, the functional layer from
Under to being above followed successively by hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6 and electron injecting layer 7；When for be inverted
When structure, the functional layer be followed successively by from top to bottom electron injecting layer 7, electron transfer layer 6, luminescent layer 5, hole transmission layer 4 and
Hole injection layer 3.
Further, the substrate 1 is insulating material, including glass, paper, photoresist, polyethylene
High molecular polymers, cloth, the plastics such as terephthalate (PET) etc..Substrate, which can be rigid, is also possible to flexible, shape
Shape and size are unlimited.
Further, high reflection charge inducing layer 2 can be any material with high reflectance and conduction, including 30nm
The high reflecting metals such as more than thickness silver, magnesium silver alloy (1:1-50:1), aluminium, gold；It is also possible to high reflection material and other
The combination of conductive material, other conductive materials include metal oxides, carbon nanotube, silver nanowiress such as indium tin oxide (ITO)
The equal conducting polymers such as nanometer conductive materials and poly- 3,4-rthylene dioxythiophene/poly styrene sulfonate (PEDOT:PSS).
Further, the material of the hole injection layer 3 is molybdenum trioxide (MoO3), tungstic acid (WoO3) or 2,3,
Six cyano -1,4,5,8,9,12- of 6,7,10,11-, six azepine benzophenanthrene (HAT-CN)；
The material of the hole transmission layer 4 be 4,4'- cyclohexyl two (N, N- bis- (4- aminomethyl phenyl) aniline) (TAPC),
(carbazole -9- base) triphenylamine (TCTA) of 4,4', 4'- tri- or N, N'- diphenyl-N, N'- (1- naphthalene) -1,1'- biphenyl -4,4'-
Diamines (NPB).
Further, the luminescent layer 5 in first microcavity is the first luminescent layer 5-1, shining in second microcavity
Layer 5 is the second luminescent layer 5-2；The color of the first luminescent layer 5-1 and the second luminescent layer 5-2 are different, select blue yellow or any
Complementation can produce two kinds of colors of white light, and using the doped structure of material of main part and guest materials, material of main part is selected from 4,4',
4'- tri- (carbazole -9- base) triphenylamine (TCTA), 4,4'-N, bis- carbazoles of N--biphenyl (CBP), 9,9'- (2,6- pyridine diyl two -
The Asia 3,1- benzene) double -9H- carbazoles (26DCzPPy), [5- (4- tert-butyl-phenyl) -1,3,4- dislikes two to 2,2'- (1,3- phenyl) two
At least one of azoles] (OXD-7) etc.；Blue light guest materials is closed selected from bis- (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics
Iridium (Firpic), bis- (the fluoro- 2- of 3,5- bis- (2- pyridyl group-KN) phenyl-KC) (four (1H- pyrazolyl-KN1) boric acid (1-)-
KN2, KN2')-iridium (Fir6) or two (2- hydroxy phenyl pyridines) close beryllium (Be (PP)2At least one of) etc.；Green light object material
Material closes iridium [Ir (ppy) selected from three (2- phenylpyridines)3], acetopyruvic acid two (2- phenylpyridine-C2, N) close iridium (III) [Ir
(ppy)2At least one of (acac)] etc.；Yellow light guest materials is selected from (4- phenyl-thiophene [3,2-c] pyrrole of acetopyruvic acid two
Pyridine-C2, N) close iridium (III) (PO-01), acetopyruvic acid two (4- (4- tbutyl-phenyl)-thiophene [3,2-c] pyridine-C2,
N it) closes at least one of iridium (III) (PO-01-TB) etc.；Feux rouges guest materials is selected from three (1- phenyl isoquinolin quinoline) iridium [Ir
(piq)3] or (acetylacetone,2,4-pentanedione) bis- (2- methyldiphenyls simultaneously [f, h] quinoxaline) close iridium [Ir (MDQ)2Etc. (acac)] at least one in
Kind；Wherein, the mass ratio between material of main part and guest materials is 50:1-1:1.
Further, the material of the electron transfer layer 6 be 1,3,5- tri- (2-N- benzene-benzene and imidazoles) benzene (TPBi),
Bis- (bis- pyridin-3-yl phenyl of the 3,5-) benzene (BmPyPhB) of 1,3,5- tri- [(3- pyridyl group) -3- phenyl] benzene (TmPyPB), 1,3-
Or 4,7- diphenyl -1,10- phenanthroline (Bphen)；
The material of the electron injecting layer 7 is LiF, Cs2CO3Or (8-hydroxyquinoline) lithium (Liq).
Further, the top electrode layer 8 includes electrode 8-A and electrode 8-B, is semi-transparent conductive material, includes
Silver, the magnesium silver alloy (1:1-50:1), aluminium, gold for having 30nm or less conductive；Spacing distance between described two electrodes is 1nm-
20cm。
Further, the light removing layer 9 is transparent material, is passed selected from above-mentioned hole injection layer material, above-mentioned hole
Defeated layer material, above-mentioned electron transport layer materials and above-mentioned electron injecting layer material.
In the present embodiment, the luminescent layer 5-2 in luminescent layer 5-1 and the second microcavity in the first microcavity is with blue light and yellow light
Example is based on PET flexible substrate, and double microcavity top emitting white light organic electroluminescences of exchange driving are prepared for using vacuum vapour deposition
Device, the device architecture of blue light microcavity are PET/Mg:Ag (15:1 120nm)/MoO3 (3nm)/TAPC(30nm)/
26DCzPPy:Firpic (5:1 30nm)/Bphen (35nm)/Liq (2nm)/Ag (20nm)/TAPC (70nm), yellow light microcavity
Device architecture be PET/Mg:Ag (15:1 120nm)/MoO3 (3nm)/TAPC(40nm)/CBP:PO-01(10:1 30nm)/
Bphen (40nm)/Liq (2nm)/Ag (20nm)/TAPC (70nm), device junction composition as shown in Figure 1, detailed preparation process such as
Under:
(1), clean PET substrate is placed in organic molecule gas-phase deposition system, is then evacuated to 6 × 10- 4Pa；It maintains above-mentioned vacuum condition constant, the bottom high reflection charge inducing of two microcavitys is successively deposited simultaneously on above-mentioned substrate
Layer (Mg:Ag), hole injection layer (MoO3) and hole transmission layer (TAPC), two are successively then deposited respectively using mask technique
Luminescent layer and Partial charge transport layer (blue light subelement luminescent layer 26DCzPPy:FirPic 5:1, the yellow light subelement hair of microcavity
Photosphere CBP:PO-01 10:1), electron transfer layer (Bphen), the electron injecting layer of two microcavitys are finally successively deposited simultaneously
(Liq), top electrode layer (Ag) and light removing layer (TAPC), as shown in Figure 2.Mg:Ag layers of doping ratio is 15:1.Top electricity
Spacing distance between two electrode of layer of pole is 2mm.
(2), astigmatism device is made of convex lens and scattering sheet, as shown in figure 3, astigmatism device is placed in above-mentioned preparation
On organic electroluminescence device, final double microcavity top emitting white light organic electroluminescent devices that exchange driving can be achieved.Just
(blue light subelement top electrodes 8-A is cathode, and yellow light subelement top electrodes 8-B is anode, reversed straight when to DC powered
Galvanic electricity is in contrast) device issues blue light, and device issues yellow light when reversed DC powered, for people when 50Hz exchanges electric drive
It is blue light and yellow light for eye while shines, using scattering device, just can be realized color mixing, device under 50Hz alternating current
It is whole to issue white light.
Fig. 4 is the current density-voltage-for double microcavity top radiation organic EL parts that embodiment 1 can exchange driving
Luminosity response.In forward dc electric drive, the maximum brightness of device blue light is 11153cd/m2；Reversed DC powered
When device yellow light maximum brightness be 19563cd/m2。
Fig. 5 is current efficiency-brightness-function of double microcavity top radiation organic EL parts of the exchange driving of embodiment 1
Rate efficiency characteristic.The maximum current efficiency of blue light is 34cd/A, maximum power efficiency 18lm/ under forward dc electric drive
W；The maximum current efficiency of yellow light is 82cd/A, maximum power efficiency 67lm/W under reversed DC powered.
Fig. 6 is double microcavity top emitting white light organic electroluminescent devices of the exchange driving of embodiment 1 under different angle
Normalization electroluminescent spectrum.
Fig. 7 is double microcavity top emitting white light organic electroluminescent devices of the exchange driving of embodiment 1 in different alternating voltages
Spectrum under combination adjusts the work photo under figure and different-colour.Only in the only voltage of positive half period or negative half-cycle
There are blue spectrum or yellow spectrum；In negative half-cycle voltage VnWhen constant, with positive half period voltage VpIt is continuously increased, blue light
Spectrum constantly enhances；Positive half period voltage VpWhen constant, with negative half-cycle voltage VnIncrease, yellow spectrum constantly enhances.It hands over
The double microcavity top emitting white light organic electroluminescent devices for flowing driving can finally be changed to from blue light by cool white light to warm white
Yellow light.
Embodiment 2
In the present embodiment, the luminescent layer 5-2 in luminescent layer 5-1 and the second microcavity in the first microcavity is with blue light and yellow light
Example is based on paper flexible substrate, and double microcavity top emitting white light organic electroluminescences of exchange driving are prepared for using vacuum vapour deposition
Device, the structure of blue light microcavity are Paper/Mg:Ag (15:1 120nm)/MoO3(3nm) /TAPC(30nm)/26DCzPPy:
Firpic (5:1 30nm)/Bphen (35nm)/Liq (2nm)/Ag (20nm)/TAPC (70nm), yellow light micro-cavity structure are
Paper/Mg:Ag(15:1 120nm)/MoO3(3nm) /TAPC(40nm)/CBP:PO-01(10:1 30nm)/Bphen
(40nm)/Liq (2nm)/Ag (20nm)/TAPC (70nm), device junction composition is as shown in Figure 1, detailed preparation process is as follows:
(1), Poly (4-vinylphenol) layer is crosslinked in paper gasket bottom surface spin coating and is crosslinked 2h under 160 degree, to paper gasket
Bottom surface is modified.
(2), the paper base substrate handled well is placed in organic molecule gas-phase deposition system, then it is evacuated to 6 ×
10-4Pa；It maintains above-mentioned vacuum condition constant, the bottom high reflection charge sense of two microcavitys is successively deposited simultaneously on above-mentioned substrate
Generating layer (Mg:Ag), hole injection layer (MoO3) and hole transmission layer (TAPC), two are successively then deposited respectively using mask technique
Luminescent layer and Partial charge transport layer (blue light subelement luminescent layer 26DCzPPy:FirPic 5:1, the yellow light subelement of a microcavity
Luminescent layer CBP:PO-01 10:1), electron transfer layer (Bphen), the electron injecting layer of two microcavitys are finally successively deposited simultaneously
(Liq), top electrode layer (Ag) and light removing layer (TAPC), as shown in Figure 2.Mg:Ag layers of doping ratio is 15:1.Top electricity
Spacing distance between two electrode of layer of pole is 2mm.
Fig. 8 is that the paper base exchange of embodiment 2 drives double microcavity top emitting white light organic electroluminescent devices to exchange in 50Hz
The photo to work under electric drive, has broken the limitation of substrate in organic electroluminescence device, and opaque and surface is very coarse
Cheap paper substrates can also be used as exchange after simple modification and the substrate of double microcavity top emitting organic luminescent devices driven to use.
Embodiment 1, the thickness of vacuum thermal evaporation technique growing film as described in example 2 and growth rate produce L- by the U.S.
The control of 400 film-thickness monitorings prepares resulting device performance and uses based on the 2400 Current Voltage source Keithley and big tomb electronics
The photoelectric test system of MCPD-9800 spectrometer is tested under normal temperature condition in air.
Claims (9)
1. a kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving, which is characterized in that including substrate (1) and
Two microcavitys, for described two microcavity transverse direction laid out in parallel on substrate (1), the microcavity includes that the first microcavity and second are micro-
Chamber, the microcavity successively include high reflection charge inducing layer (2), functional layer, top electrode layer (8) and light removing layer from bottom to top
(9)；The functional layer includes hole injection layer (3), hole transmission layer (4), luminescent layer (5), electron transfer layer (6) and electronics note
Enter layer (7)；The high reflection charge inducing layer (2) connects two microcavitys and generates charge inducing under extra electric field, itself
Any external drive signal is not applied；Luminescent layer (5) in two microcavitys is different colours, is generated after two kinds of color additions white
Light；Top electrode layer (8) in two microcavitys is Different electrodes, has certain spacing between two electrodes；Entire device is adopted
It is applied on the Different electrodes of top electrode layer (8) and is driven with ac signal.
2. a kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving as described in claim 1, feature
Be, the bottom high reflection charge inducing layer (2) with a thickness of 30nm-200nm, hole injection layer (3) with a thickness of
0.1-10nm, hole transmission layer (4) with a thickness of 20-70nm, luminescent layer (5) with a thickness of 10-50nm, electron transfer layer (6)
With a thickness of 20-70nm, electron injecting layer (7) with a thickness of 0.1-10nm, top electrode layer (8) with a thickness of 5-30nm, light
Removing layer (9) with a thickness of 20-200nm.
3. a kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving as described in claim 1, feature
It is, the functional layer, which is positive, sets structure or inverted structure；When be positive set structure when, the functional layer is followed successively by from top to bottom
Hole injection layer (3), hole transmission layer (4), luminescent layer (5), electron transfer layer (6) and electron injecting layer (7)；It is tied when to be inverted
When structure, the functional layer is followed successively by electron injecting layer (7), electron transfer layer (6), luminescent layer (5), hole transmission layer from top to bottom
(4) and hole injection layer (3).
4. a kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving as described in claim 1, feature
It is, the substrate (1) is insulating material, including glass, paper, photoresist, PET, cloth or plastics.
5. a kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving as described in claim 1, feature
It is, the high reflection charge inducing layer (2) is the silver of 30nm thickness or more, magnesium silver alloy, aluminium, gold, indium tin oxide
(ITO) etc. metal oxides, carbon nanotube, silver nanowires and poly- 3,4-rthylene dioxythiophene/poly styrene sulfonate (PEDOT:
PSS)。
6. a kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving as described in claim 1, feature
It is, the material of the hole injection layer (3) is molybdenum trioxide (MoO3), tungstic acid (WoO3) or 2,3,6,7,10,11-
Six cyano -1,4,5,8,9,12-, six azepine benzophenanthrene (HAT-CN)；
The material of the hole transmission layer (4) is 4,4'- cyclohexyl two (N, N- bis- (4- aminomethyl phenyl) aniline) (TAPC), 4,
(carbazole -9- base) triphenylamine (TCTA) of 4', 4'- tri- or N, N'- diphenyl-N, N'- (1- naphthalene) -1,1'- biphenyl -4,4'- two
Amine (NPB).
7. a kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving as described in claim 1, feature
It is, the luminescent layer (5) in first microcavity is the first luminescent layer (5-1), and the luminescent layer (5) in second microcavity is the
Two luminescent layers (5-2)；First luminescent layer (5-1) is different with the color of the second luminescent layer (5-2), and selection is blue yellow or any mutual
The two kinds of colors that can produce white light are mended, using the doped structure of material of main part and guest materials, material of main part is selected from 4,4', 4'-
Three (carbazole -9- base) triphenylamines (TCTA), 4,4'-N, bis- carbazoles of N--biphenyl (CBP), 9,9'- (two -3,1- of 2,6- pyridine diyl
Sub- benzene) double -9H- carbazoles (26DCzPPy), 2,2'- (1,3- phenyl) two [5- (4- tert-butyl-phenyl) -1,3,4- oxadiazoles]
At least one of (OXD-7)；Blue light guest materials is selected from bis- (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics and closes iridium
(Firpic), bis- (the fluoro- 2- of 3,5- bis- (2- pyridyl group-KN) phenyl-KC) (four (1H- pyrazolyl-KN1) boric acid (1-)-KN2,
KN2')-iridium (Fir6) or two (2- hydroxy phenyl pyridines) close beryllium (Be (PP)2At least one of)；Green light guest materials is selected from
Three (2- phenylpyridines) close iridium [Ir (ppy)3], acetopyruvic acid two (2- phenylpyridine-C2, N) close iridium (III) [Ir (ppy)2
At least one of (acac)]；Yellow light guest materials is selected from acetopyruvic acid two (4- phenyl-thiophene [3,2-c] pyridine-C2, N)
Close iridium (III) (PO-01), acetopyruvic acid two (4- (4- tbutyl-phenyl)-thiophene [3,2-c] pyridine-C2, N) closes iridium
(III) at least one of (PO-01-TB)；Feux rouges guest materials is selected from three (1- phenyl isoquinolin quinoline) iridium [Ir (piq)3] or (second
Acyl acetone) bis- (2- methyldiphenyls simultaneously [f, h] quinoxaline) close iridium [Ir (MDQ)2At least one of (acac)]；Wherein, main body
Mass ratio between material and guest materials is 50:1-1:1.
8. a kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving as described in claim 1, feature
It is, the material of the electron transfer layer (6) is 1,3,5- tri- (2-N- benzene-benzene and imidazoles) benzene (TPBi), 1,3,5- tri-
Bis- (bis- pyridin-3-yl phenyl of the 3,5-) benzene (BmPyPhB) of [(3- pyridyl group) -3- phenyl] benzene (TmPyPB), 1,3- or 4,7- bis-
Phenyl -1,10- phenanthroline (Bphen)；The material of the electron injecting layer (7) is LiF, Cs2CO3Or (8-hydroxyquinoline) lithium
(Liq)。
9. a kind of double microcavity top emitting white light organic electroluminescent devices of exchange driving as described in claim 1, feature
Be, the top electrode layer (8) includes electrode 8-A and electrode 8-B, be the conductive silver of 30nm or less, magnesium silver alloy, aluminium or
Gold；Spacing distance between described two electrodes is 1nm-20cm.
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| CN113659087A (en) * | 2021-08-13 | 2021-11-16 | 苏州大学 | Alternating current driving organic light emitting diode device |
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