CN100470877C - Organic electro phosphorescent device and its preparation method - Google Patents
Organic electro phosphorescent device and its preparation method Download PDFInfo
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Abstract
The present invention relates to an organic electro phosphorescent device and its preparation method. Said device comprises a transparent base sheet, an anode layer, organic functional layer and a cathode layer, wherein the organic functional layer comprises organic luminous layer and one ore more layers selected from a positive hole injection layer, a positive hole transport layer, an electronic transport layer and an electron injection layer, said organic luminous layer includes a body material and a phosphorescent coloring agent, the doping concentration of said phosphorescent coloring agent gradually rises or drops with the thickness increase of the organic luminous layer to form a gradient doping structure. For said device, by doping the phosphorescent coloring agent into the body material in the organic luminous layer with a gradient doping manner, the luminous area of the device is expanded and the use ratio of the phosphorescent coloring agent is improved; it is also helpful to the exciton formation from electronic and positive hole, then light-emitting efficiency and lighteness of the device are improved, and the stability is improved; at the same time, the shortcomings of low light-emitting efficiency and poor stability of the device under large electric current are overcome.
Description
Technical field
The present invention relates to a kind of organic electro phosphorescent device, also relate to this preparation of devices method, belong to technical field of organic electroluminescence.
Background technology
Now, along with the arriving of Development of Multimedia Technology and information-intensive society, more and more higher to the flat-panel monitor performance demands.In recent years emerging three kinds of Display Techniques: plasma display, Field Emission Display and display of organic electroluminescence have all remedied the deficiency of cathode ray tube and LCD to a certain extent.Wherein, display of organic electroluminescence has from main light emission, low-voltage DC driven, complete curings, wide visual angle, color and a series of advantage such as enriches, compare with LCD, display of organic electroluminescence does not need backlight, and the visual angle is big, and power is low, its response speed can reach 1000 times of LCD, its manufacturing cost but is lower than the LCD of equal resolution, and therefore, display of organic electroluminescence has broad application prospects.
1987, people such as the C.W.Tang (C.W.Tang of U.S. Kodak company, S.A.Vanslyke, Appl.Phys.Lett., 1987,51,913) select to have the triphenylamine analog derivative of better filming performance and Alq3 respectively as hole transmission layer and the luminescent layer electron transfer layer of holding concurrently, prepare high-quantum efficiency (1%), high-luminous-efficiency (〉 1.51m/W), high brightness (〉 1000cd/m2) and low driving voltage (＜10V) organic electroluminescence device (Organic Electroluminescent Devices is hereinafter to be referred as OLEDs).This breakthrough is that new power has been injected in the development of organic electroluminescence device, and the organic electroluminescent technology has demonstrated its potential practical value.1989, people such as C.W.Tang (C.W.Tang, S.A.Vanslyke, J.Appl.Phys, 1989,65,913) doped with fluorescent dyes improves the efficient of OLEDs in luminescent layer, because the doping content of fluorescent dye is lower, it can directly capture charge carrier, the cancellation that the fluorescent dye self-absorption causes in the time of preventing high-dopant concentration simultaneously.The structure of this doped with fluorescent dyes device is generally double-heterostructure, they have independently hole transmission layer and electron transfer layer, electronics-hole can be carried out effectively compound in luminescent layer, make the efficient of device reach the theoretical limit (internal quantum efficiency 25%, external quantum efficiency 5%) of organic electroluminescence fluorescent device.
Nineteen ninety, people (Burroughes JH such as the breadboard R.H.Friend of the Britain Cavendish of Cambridge university, BradleyDDC, BrownAR, R.H.Friend.Nature (London), 1990,347,539) be that luminescent material has been made polymer OLEDs with poly-phenylene vinylene (ppv) (hereinafter to be referred as PPV), opened up another frontier of luminescent device---thin polymer film electroluminescent device.Polymer luminescent material has characteristics such as the easily adjusting of Heat stability is good, molecular structure, good film-forming property, filming technology be simple.The researcher makes remarkable progress at aspects such as improving the dissolubility of polymer luminescent material, raising glass transition temperature, strengthen photochemical stability, mate the charge carrier injection and transmit balance, raising quantum efficiency, regulate glow color, though start late, the performance of polymer LED is also near the practicability level.
Another breakthrough of OLEDs research is a Doping Phosphorus photoinitiator dye in the device luminescent layer, and the introducing of phosphorescent coloring makes device can effectively utilize singlet and triplet excitons, makes the internal quantum efficiency of device near the theoretical upper limit 100%.U.S. Pat 6,303,228 (the days for announcing: October 16 calendar year 2001, patentee: Princeton University, University of Southern California) proposes first in to adopt phosphorescent coloring to prepare the thought of high efficiency OLEDs as dopant, (M.A.Baldo in this part patent and the Forrest of the Princeton University group bibliographical information subsequently, D.F.O ' Brien, Y.You et al.Nature, 1998,395,151) all disclose with phosphorescent coloring PtOEP and be entrained in device research among the luminescent layer material of main part Alq3 as the object luminescent material.Because the exciton restriction that is subjected to spinning and prohibits, their utilances in fluorescent small molecule OLEDs lower (theoretical maximum is 25%), and limited the external quantum efficiency (＜5%) of device.Doping Phosphorus photoinitiator dye in the OLEDs luminescent layer, then the utilance of exciton can reach 100% in theory, will improve the efficient of device greatly.
In the organic electroluminescent field, since C.W.Tang etc. has delivered in 1989 in main body or host material in (Host) since dopant dye (Guest or dopant) the preparation luminescent layer first, mixing becomes one of main method of preparation high performance device.So-called doping is meant a spot of luminescent material is incorporated in the luminous host.The advantage of mixing is that luminescent material is separated with transferring material, needn't consider the carrier transmission performance of luminescent material.Because the luminescent material that simultaneously excellent luminescent properties and carrier transmission performance is arranged seldom, doping can be widened the range of choice of luminescent material greatly, also can improve the luminescent properties of device simultaneously.
In the organic electroluminescence device that mixes, most important physical process is the energy transfer process between substrate luminescent material and the doped luminescent material.It has important or even decisive influence to the performance of device.In addition, the energy transfer process of understanding in the doping system can also be the optimised devices structure, and further improving device performance provides guidance.In dye adulterated organic EL device, relate generally to following several energy transfer process, that is:
Energy delivery, Dexter energy delivery and current-carrying capture.
The energy delivery mechanism that fluorescence mixes and phosphorescence mixes compares:
The Dexter energy delivery is by electron exchange mechanism domination, and electronic switching takes place between the excitation state by giving body and the ground state of acceptor.Can be expressed as follows:
D
*+A→(D…A)
*→D+A
* (1)
Wherein, D represents that to body, A represents acceptor,
*Expression excitation state.
Because exist one may be the bimolecular intermediate of exciplex or collision complex compound, bimolecular intermediate generation relaxation be got back to ground state to body then, and acceptor is in excitation state.Energy delivery under this mechanism is a kind of short distance phenomenon, and when distance surpassed 2nm between to body and acceptor, this effect just can have been ignored.The Dexter energy delivery can be expressed as follows:
3D
*+1A→1D+3A
* (2)
1D
*+1A→1D+1A
* (3)
Wherein, 3 expression triplet states, 1 expression singlet.
Triplet state-singlet energy delivery (formula 2) allows in the Dexter energy delivery, but
Prohibit strongly in the energy delivery,
Energy delivery only can be carried out the singlet energy delivery.
For the device of doped with fluorescent dyes, though
Can both realize 1D with two kinds of pass through mechanism of Dexter
*+ 1A → 1D+1A
*, but because the dye strength that mixes usually less than 1%, so mainly by long-range
Mechanism is transmitted energy.Simultaneously, because the device of doped with fluorescent dyes only can carry out the singlet energy delivery, its exciton utilance only is 25%.
For the El element of Doping Phosphorus photoinitiator dye, in order to realize effective Dexter energy delivery, the dye strength of doping is usually greater than 5%.Singlet that generates in the matrix and triplet state swashed the triplet excitons that can both effectively pass to dyestuff and luminous, thereby made full use of in the matrix 100% exciton, improved device efficiency greatly.
Carrier capture also is the possible approach that dye molecule is excited.The band gap of main body or host material is wideer than the band gap of the dyestuff wherein that mixes usually in the luminescent layer, and the band gap position of dyestuff is positioned at the band gap of main body or host material, makes dye molecule form ＂ trap ＂.Doping such as rubrene.
The grade doping structure has been widely used in traditional III-V family semiconductor device.People such as R.H.Friend have also used the notion (R.H.Friend of gradient-structure in polymer OLEDs, et al.Nature, 2000,404,481), in this device, a kind of hole transmission layer with concentration gradient is deposited on tin indium oxide (hereinafter to be referred as the ITO) anode, make the charge carrier injection of device reach balance, and then improved the luminous efficiency of device.
Gradient-structure also has application in micromolecule fluorescence OLEDs, people such as Anna B.Chwang have reported a kind of OLEDs (A.B.Chwang, R.C.Kwong, and J.J.Brown, Appl.Phys.Lett.2002,80,725) with gradient hybrid illuminating layer.In this device, it is mixed in together that hole mobile material NPB and electric transmission/luminescent material Alq3 presses variable concentrations in zones of different, the concentration of the concentration of NPB from the anode buffer layer to the negative electrode reduces gradually, and the concentration of Alq3 raises from the anode buffer layer to the negative electrode gradually, forms the structure of concentration gradient.In the luminescent layer of this device, the mass concentration ratio of NPB and Alq3 is 1:1, the fluorescent dye C545T of the 1wt% that wherein also evenly mixed, and the structure of device is: ITO/CuPc (
)/NPB:Alq3 (
, 5wt%)/NPB:Alq3 (
, 20wt%)/NPB:Alq3 (
, 35wt%)/NPB:Alq3:C545T (
, [1:1]: 1wt%)/NPB:Alq3 (
, 90wt%)/LiF (
)/Al (
).Although the device efficiency of this structure is lower than the luminous efficiency of traditional heterojunction structure device of doping same concentrations C545T, the stability of device has obtained very big improvement.People such as Dongge Ma have also reported a kind of bipolarity luminescent layer device (Dongge Ma with gradient-structure, C.S.Lee, S.T.Lee, and L.S.Hung, Appl.Phys.Lett.2002,80,3641), the structure of this device is: the bipolarity luminescent layer/Alq3/Mg:Ag of ITO/NPB/ gradient-structure, and wherein the NPB layer is as hole transmission layer, the Alq3 layer is as electron transfer layer, and the bipolarity luminescent layer is to be prepared by different mass concentration ratios in zones of different with Alq3 by NPB.In the bipolarity luminescent layer of this device, NPB from the hole transmission layer to the electron transfer layer between concentration reduce gradually, and Alq3 from the hole transmission layer to the electron transfer layer between concentration raise gradually, this structure can be controlled the transmission of charge carrier and compound better.The device of this structure is higher 1.5 times than the efficient of the device of traditional heterojunction structure, remains unchanged and play bright voltage.
At present, the phosphorescent coloring in the organic electro phosphorescent device luminescent layer evenly is entrained in the material of main part.People's such as E.Tutis result of study shows (E.Tutis, D Berner, and L.Zuppiroli, Appl.Phys.Lett.2003,93,4594), current-carrying (electronics and hole) distribution in OLEDs be uneven.In general device, how sub the hole is, and electronics is few son.In the luminescent layer of phosphorescence device, along electron transfer layer to the hole transmission layer direction, the CONCENTRATION DISTRIBUTION of electronics is non-linear decline trend.Thereby the phosphorescence device that evenly mixes, the dyestuff that only is positioned at light-emitting zone could be luminous, and its luminous efficiency and brightness all have been subjected to certain restriction.
Summary of the invention
The purpose of this invention is to provide that a kind of luminous efficiency height, brightness are big, the organic electro phosphorescent device of good stability.
Another object of the present invention provides a kind of preparation method of organic electro phosphorescent device.
For achieving the above object, of the present invention technical scheme provides a kind of organic electro phosphorescent device, this device comprises transparent substrate, anode layer, organic function layer, cathode layer, wherein organic function layer comprises organic luminous layer, optionally has hole injection layer, hole transmission layer, electron transfer layer, in the electron injecting layer one or more layers, organic luminous layer comprises material of main part and phosphorescent coloring, and the direction of the doping content of described phosphorescent coloring along anode layer to cathode layer rises gradually along with the increase of organic light emission layer thickness or descend gradually and form the grade doping structure.
Average doping content at the phosphorescent coloring described in the technical scheme of the present invention is 0.1～50wt%.
In OLEDs, the generally non-linear reduction from the electron transfer layer to the hole transmission layer of the CONCENTRATION DISTRIBUTION of electronics.In the technique scheme in the organic luminous layer phosphorescent coloring Gradient distribution of doping content in material of main part be in order to make the distribution trend of phosphorescent coloring in material of main part meet the distribution trend of electronics in material of main part, such CONCENTRATION DISTRIBUTION has enlarged the light-emitting zone of device, the utilance of phosphorescent coloring is improved, also helps electronics and the hole is combined into exciton.
The direction of the doping content of phosphorescent coloring along anode layer to cathode layer rises gradually along with the increase of organic light emission layer thickness or downward trend is by the character decision of phosphorescent coloring self in the technique scheme.Phosphorescent coloring self is wherein a main determining factor to the transmittability in electronics or hole.For the strong phosphorescent coloring of electron transport ability, its doping content distributes and rises gradually with the increase of light emitting layer thickness to the cathode layer direction along anode layer, otherwise the strong phosphorescent coloring of cavity transmission ability then.
The organic electro phosphorescent device that the present invention proposes, have the following advantages: phosphorescent coloring is entrained in the material of main part in the grade doping mode in organic luminous layer, enlarged the light-emitting zone of device, the utilance of phosphorescent coloring is improved, also help electronics and the hole is combined into exciton, thereby improved the luminous efficiency and the brightness of device, improved its stability, also overcome simultaneously under big electric current, the luminous efficiency of device is hanged down the shortcoming with poor stability.
Another technical scheme of the present invention provides a kind of preparation method of organic electro phosphorescent device, and this method comprises the organic electro phosphorescent device of following four processing steps manufacturing different structure:
The processing step of first kind of structure:
1. successively transparent conduction base sheet is carried out ultrasonic cleaning, oven dry, preliminary treatment, wherein the conducting film above the conductive substrate is as the anode layer of device;
2. place in the vacuum chamber with above-mentioned cleaning, drying and through pretreated transparent conduction base sheet, vacuumize, then evaporation hole transmission layer on above-mentioned conducting film;
3. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned hole transmission layer, continue the organic luminous layer that evaporation is doped with phosphorescent coloring, adopt the method for double source evaporation to carry out grade doping, respectively material of main part and phosphorescent coloring are placed different evaporation sources, by controlling the evaporation speed of two evaporation sources, the doping content of phosphorescent coloring in material of main part risen or decline gradually along with the increase of organic light emission layer thickness;
4. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned organic luminous layer, continue the evaporation electron transfer layer;
5. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned electron transfer layer, continue the cathode layer of evaporated metal layer as device.
The processing step of second kind of structure:
1. successively transparent conduction base sheet is carried out ultrasonic cleaning, oven dry, preliminary treatment, wherein the conducting film above the conductive substrate is as the anode layer of device;
2. place in the vacuum chamber with above-mentioned cleaning, drying and through pretreated transparent conduction base sheet, vacuumize, evaporation is doped with the organic luminous layer of phosphorescent coloring on above-mentioned anode layer, adopt the method for double source evaporation to carry out grade doping, respectively material of main part and phosphorescent coloring are placed different evaporation sources, by controlling the evaporation speed of two evaporation sources, the doping content of phosphorescent coloring in material of main part risen or decline gradually along with the increase of organic light emission layer thickness;
3. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned organic luminous layer, continue the evaporation electron transfer layer;
4. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned electron transfer layer, continue the cathode layer of evaporated metal layer as device.The processing step of the third structure:
1. successively transparent conduction base sheet is carried out ultrasonic cleaning, oven dry, preliminary treatment, wherein the conducting film above the conductive substrate is as the anode layer of device;
2. place in the vacuum chamber with above-mentioned cleaning, drying and through pretreated transparent conduction base sheet, vacuumize, then evaporation hole transmission layer on above-mentioned conducting film;
3. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned hole transmission layer, continue the organic luminous layer that evaporation is doped with phosphorescent coloring, adopt the method for double source evaporation to carry out grade doping, respectively material of main part and phosphorescent coloring are placed different evaporation sources, by controlling the evaporation speed of two evaporation sources, the doping content of phosphorescent coloring in material of main part risen or decline gradually along with the increase of organic light emission layer thickness;
4. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned organic luminous layer, continue the cathode layer of evaporated metal layer as device.The processing step of the 4th kind of structure:
1. successively transparent conduction base sheet is carried out ultrasonic cleaning, oven dry, preliminary treatment, wherein the conducting film above the conductive substrate is as the anode layer of device;
2. place in the vacuum chamber with above-mentioned cleaning, drying and through pretreated transparent conduction base sheet, vacuumize, evaporation is doped with the organic luminous layer of phosphorescent coloring on anode layer, adopt the method for double source evaporation to carry out grade doping, respectively material of main part and phosphorescent coloring are placed different evaporation sources, by controlling the evaporation speed of two evaporation sources, the doping content of phosphorescent coloring in material of main part risen or decline gradually along with the increase of organic light emission layer thickness;
4. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned organic luminous layer, continue the cathode layer of evaporated metal layer as device.
Description of drawings
Be illustrated by embodiment, embodiment below in conjunction with accompanying drawing, it is clearer that the present invention can become.
Fig. 1 is the structural representation of the organic electro phosphorescent device that proposes of the present invention, and wherein 1 is transparent substrate, the 2nd, and anode layer, the 3rd, hole transmission layer, the 4th, organic luminous layer, the 5th, electron transfer layer, the 6th, cathode layer, the 7th, power supply.
Fig. 2 is the concentration profile of phosphorescent coloring among the OLED1 of the embodiment of the invention 1 preparation.
Fig. 3 is that the OLED of the OLED1 of the embodiment of the invention 1 preparation and Comparative Examples 1 preparation is to brightness-voltage curve of 1.
Fig. 4 is that the OLED of the OLED1 of the embodiment of the invention 1 preparation and Comparative Examples 1 preparation is to luminous efficiency-current density curve of 1.
Fig. 5 be the OLED of the OLED1 of the embodiment of the invention 1 preparation and Comparative Examples 1 preparation to 1 normalization life curve (being brightness-fluorescent lifetime curve), the original intensity of OLED1 is 1300cd/m2, OLED is 900cd/m2 to 1 original intensity.
Fig. 6 be the OLED of the OLED1 of the embodiment of the invention 1 preparation and Comparative Examples 1 preparation to 1 EL spectrogram, OLED1, OLED are wherein arranged to 1 luminous chromaticity coordinates in the CIE1931 chromatic diagram.
Fig. 7 is the concentration profile of phosphorescent coloring among the OLED4 of the embodiment of the invention 4 preparation.
Fig. 8 is the concentration profile of phosphorescent coloring among the OLED5 of the embodiment of the invention 5 preparation.
Elaborate content of the present invention below in conjunction with the drawings and specific embodiments, should be appreciated that the present invention is not limited to following preferred implementation, preferred implementation is as just illustrative embodiment of the present invention.
Embodiment
For the purpose of reference, list the abbreviation of some organic materials that relate in this specification and full name as follows:
Table 1
A kind of structure of the organic electro phosphorescent device that the present invention proposes as shown in Figure 1, wherein: 1 be transparent substrate, can be glass or flexible substrate, a kind of material in flexible substrate employing polyesters, the polyimides compounds; 2 is anode layer, can adopt inorganic material or organic conductive polymer, inorganic material is generally the higher metals of work function such as metal oxides such as ITO, zinc oxide, zinc tin oxide or gold, copper, silver, the optimized ITO that is chosen as, organic conductive polymer are preferably a kind of material among PEDOT:PSS, the PANI; 3 is hole transmission layer, adopts the stronger p type organic semiconducting materials of cavity transmission ability, is generally the triphenylamine compounds, a kind of as in the materials such as NPB, TPD, MTDATA, and the present invention is preferably NPB; 4 is organic luminous layer, adopt small molecule material as material of main part, this small molecule material has higher triplet, can give phosphorescent coloring with energy delivery effectively, make phosphorescent coloring luminous, the micromolecule material of main part generally uses biphenyl-carbazoles (as CBP) or benzene-carbazoles (as DCB, CPF) a kind of material in the compound, the direction of doping content along hole transmission layer to electron transfer layer that is entrained in the phosphorescent coloring in the material of main part rises gradually along with the increase of organic light emission layer thickness or descends gradually and form the grade doping structure, be generally metal organic complex, as FIrpic (blueness), Ir (piq)
2(acac) (redness), PtOEP (redness), Ir (ppy)
3(green), Ir (ppy)
2(acac) a kind of in the materials such as (greens), its average doping content is 0.1～50wt%, preferred average doping content is 1～30wt%; 5 is electron transfer layer, is generally metal organic complex (as Alq
3, BAlq, Gaq
3, Al (Saph-q) or Ga (Saph-q)), aromatic condensed ring class (as pentacene, perylene), o-phenanthroline class be (as a kind of material in Bphen, BCP) Huo oxadiazole class (as the PBD) compound; 6 is cathode layer (metal level), generally adopts the alloy of the lower metal of work functions such as lithium, magnesium, calcium, strontium, aluminium, indium or they and copper, gold, silver, and the present invention is preferably Mg:Ag alloy-layer, Ag layer or LiF layer successively, Al layer successively.
The organic electro phosphorescent device that the present invention proposes also can comprise anode buffer layer (not showing among Fig. 1), anode buffer layer is between anode layer and hole transmission layer, the general a kind of material that adopts in phthalocyanines, polyacrylate, polyimide, fluoropolymer, inorganic fluoride salt, inorganic oxide or the diamond is as CuPc etc.
The preferred a kind of phosphorescent OLED s of said structure has following structural formula (1):
Glass/ITO/NPB/ organic luminous layer 1/Bphen/Mg:Ag/Ag (1)
The material of main part of organic luminous layer 1 is DCB in the said structure formula (1), is doped with phosphorescent coloring FIrpic in the grade doping mode in this layer.
According to said structure formula (1), be described below in conjunction with the detailed execution mode of preparation process of device:
The washing agent of 1. utilization heat is ultrasonic to be cleaned the transparent conduction base sheet ito glass with the ultrasonic method of deionized water, place it in oven dry under the infrared lamp after the cleaning, ito glass to oven dry carries out the preliminary treatment that UV ozone is cleaned and the low energy oxygen ion beam bombards then, wherein the ITO film above the conductive substrate is as the anode layer of device, the square resistance of ITO film is 5 Ω～100 Ω, and thickness is 80～280nm;
2. place in the vacuum chamber with above-mentioned cleaning, drying and through pretreated ito glass, be evacuated to 1 * 10
-5～9 * 10
-3Pa, evaporation one deck NPB is as the hole transmission layer of device on above-mentioned ITO film then, and the evaporation speed of NPB film is 0.01～0.5nm/s, and thickness is 20～80nm;
3. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned NPB hole transmission layer, continue the organic luminous layer that evaporation is doped with phosphorescent coloring FIrpic in the grade doping mode, adopt the method for double source evaporation to carry out grade doping, respectively material of main part DCB and FIrpic are placed different evaporation sources, with two film thickness monitoring instrument probes the evaporation speed of two evaporation sources is monitored respectively simultaneously at evaporation, by controlling the evaporation speed of two evaporation sources, the doping content of FIrpic in DCB risen gradually along with the increase of organic luminous layer evaporation thickness, DCB, the evaporation speed ratio of FIrpic is 1000:1～1:1000, the average doping content of FIrpic in DCB is 1～30wt%, the total speed of evaporation is 0.02～0.6nm/s, and total film thickness is 20～100nm;
4. keep above-mentioned vacuum chamber internal pressure constant, continue the electron transfer layer of evaporation one deck Bphen as device on above-mentioned organic luminous layer, the evaporation speed of Bphen film is 0.01～0.5nm/s, and thickness is 20～80nm;
5. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned Bphen electron transfer layer successively evaporation Mg:Ag alloy-layer, Ag layer as the cathode layer of device, wherein alloy-layer adopts the method for double source evaporation to mix, Mg, Ag evaporation speed ratio are 10:1 in the alloy-layer, the total speed of evaporation is 0.6～2nm/s, the evaporation gross thickness is 50～200nm, and the evaporation speed of Ag layer is 0.3～0.8nm/s, and thickness is 40～200nm.
The preferred another kind of phosphorescent OLED s of said structure has following structural formula (2):
Glass/ITO/NPB/ organic luminous layer 1/BAlq/LiF/Al (2)
The material of main part of organic luminous layer 1 is DCB in the said structure formula (2), is doped with phosphorescent coloring FIrpic in the grade doping mode in this layer.
According to said structure formula (2), be described below in conjunction with the detailed execution mode of preparation process of device:
1.～3. with in above-mentioned structural formula (1) preparation process 1.～3.;
4. keep above-mentioned vacuum chamber internal pressure constant, continue the electron transfer layer of evaporation one deck BAlq as device on above-mentioned organic luminous layer, the evaporation speed of BAlq film is 0.01～0.5nm/s, and thickness is 20～80nm;
5. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned BAlq electron transfer layer successively evaporation LiF layer, Al layer as the cathode layer of device, wherein the thickness of LiF layer is 0.2～2nm, evaporation speed is 0.01～0.1nm/s, the thickness of Al layer is 40～200nm, and evaporation speed is 0.01～0.5nm/s.
The device with transparent substrate, anode, organic luminous layer, electron transfer layer structure that the present invention proposes is preferably following structural formula (3):
Glass/ITO/teflon/ organic luminous layer 1/BAlq/LiF/Al (3)
The material of main part of organic luminous layer 1 is DCB in the said structure formula (3), is doped with phosphorescent coloring FIrpic in the grade doping mode in this layer.
According to said structure formula (3), be described below in conjunction with the detailed execution mode of preparation process of device:
1. with in above-mentioned structural formula (1) preparation process 1.
2. place in the vacuum chamber with above-mentioned cleaning, drying and through pretreated ito glass, be evacuated to 1 * 10
-5～9 * 10
-3Pa, evaporation one deck teflon is as the anode modification layer of device on above-mentioned ITO film then, and the evaporation speed of teflon film is 0.001～0.1nm/s, and thickness is 2～20nm;
3.～5. with in above-mentioned structural formula (2) preparation process 3.～5.
The device with transparent substrate, anode, organic luminous layer, cathode construction that the present invention proposes is preferably following structural formula (4):
Glass/ITO/teflon/ organic luminous layer 1/Mg:Ag/Ag (4)
According to said structure formula (4), be described below in conjunction with the detailed execution mode of preparation process of device:
1.～2. with in above-mentioned structural formula (3) preparation process 1.～2.
3. with in above-mentioned structural formula (3) preparation process 3.
4. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned luminescent layer successively evaporation Mg:Ag alloy-layer, Ag layer as the cathode layer of device, wherein alloy-layer adopts the method for double source evaporation to mix, Mg, Ag evaporation speed ratio are 10:1 in the alloy-layer, the total speed of evaporation is 0.6～2nm/s, the evaporation gross thickness is 50～200nm, and the evaporation speed of Ag layer is 0.3～0.8nm/s, and thickness is 40～200nm.
The device with transparent substrate, anode, hole transmission layer, organic luminous layer, cathode construction that the present invention proposes is preferably following structural formula:
Glass/ITO/NPB/ organic luminous layer 1/Mg:Ag/Ag (5)
According to said structure formula (5), be described below in conjunction with the detailed execution mode of preparation process of device:
1.～3. with in above-mentioned structural formula (1) preparation process 1.～3.
4. keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned luminescent layer successively evaporation Mg:Ag alloy-layer, Ag layer as the cathode layer of device, wherein alloy-layer adopts the method for double source evaporation to mix, Mg, Ag evaporation speed ratio are 10:1 in the alloy-layer, the total speed of evaporation is 0.6～2nm/s, the evaporation gross thickness is 50～200nm, and the evaporation speed of Ag layer is 0.3～0.8nm/s, and thickness is 40～200nm.
Embodiment 1 (device number OLED1)
With preparing with above-mentioned that the identical method of device prepares OLED1 shown in the structural formula (1).
Comparative Examples 1 (device number OLED is to 1)
With preparing OLED to 1 with embodiment 1 same method, the evaporation speed ratio of double source evaporation remains unchanged when wherein continuing the evaporation organic luminous layer on the NPB of device hole transmission layer, i.e. even doped F Irpic among the DCB.
Embodiment 2 (device number OLED2)
With preparing with above-mentioned that the identical method of device prepares OLED2 shown in the structural formula (1), wherein the material of main part of device organic luminous layer adopts CBP, and phosphorescent coloring adopts Ir (ppy)
3, make Ir (ppy) by the evaporation speed ratio of control double source evaporation
3Doping content in CBP descends gradually along with the increase of organic luminous layer evaporation thickness.
Comparative Examples 2 (device number OLED is to 2)
With preparing OLED to 2 with embodiment 2 same methods, the evaporation speed ratio of double source evaporation remains unchanged when wherein continuing the evaporation organic luminous layer on the NPB of device hole transmission layer, i.e. even doping Ir (ppy) among the CBP
3
Embodiment 3 (device number OLED3)
With preparing with above-mentioned that the identical method of device prepares OLED3 shown in the structural formula (1), wherein the material of main part of device organic luminous layer adopts CBP, and phosphorescent coloring adopts Ir (piq)
2(acac), the evaporation speed ratio by control double source evaporation makes Ir (piq)
2(acac) doping content in CBP descends gradually along with the increase of organic luminous layer evaporation thickness.
Comparative Examples 3 (device number OLED is to 3)
With preparing OLED to 3 with embodiment 3 same methods, the evaporation speed ratio of double source evaporation remains unchanged when wherein continuing the evaporation organic luminous layer on the NPB of device hole transmission layer, i.e. even doping Ir (piq) among the CBP
2(acac).
The prepared device architecture of the foregoing description 1-3 and Comparative Examples 1-3 is as shown in table 2, device parameters is as shown in table 3, and the OLED of the OLED1 of embodiment 1 preparation and Comparative Examples 1 preparation sees Fig. 3-6 respectively to 1 brightness-voltage curve, luminous efficiency-current density curve, normalization life curve, EL spectrogram and chromaticity coordinates.
Table 3
As can be seen from Table 3, the brightness of the device OLED1-3 of organic luminous layer grade doping phosphorescent coloring is better than the device OLED of even Doping Phosphorus photoinitiator dye respectively to 1-3 (identical the comparing of device glow color) with luminous efficiency, show because the Gradient distribution of phosphorescent coloring doping content in material of main part, met the distribution trend of electronics in the device, the performance of device has been greatly improved.
As can be seen from Figure 5, the life-span of OLED1 is more a lot of to 1 length than OLED, Fig. 6 shows simultaneously, both EL spectrum is also had any different, this is owing to make the charge carrier recombination region (light-emitting zone) of device widen with the grade doping mode phosphorescent coloring that mixed in the organic luminous layer material of main part, luminescence center is to the organic luminous layer intermediate transfer, and the light that device sends is by the cathode layer reflection and go out, owing to the lengthening of reflective distance makes the cause that the long light intensity of ripple is strengthened.
Embodiment 4 (device number OLED4)
With preparing with above-mentioned that the identical method of device prepares OLED4 shown in the structural formula (1), wherein the material of main part of device organic luminous layer adopts CPF, phosphorescent coloring adopts FIrpic, by the evaporation speed ratio of controlling the double source evaporation doping content of FIrpic in CPF is risen gradually along with the increase of organic luminous layer evaporation thickness.
Embodiment 5 (device number OLED5)
With preparing with above-mentioned that the identical method of device prepares OLED5 shown in the structural formula (1), wherein the material of main part of device organic luminous layer adopts CBP, phosphorescent coloring adopts FIrpic, by the evaporation speed ratio of controlling the double source evaporation doping content of FIrpic in CBP is risen gradually along with the increase of organic luminous layer evaporation thickness.
Embodiment 6 (device number OLED6)
With preparing with above-mentioned that the identical method of device prepares OLED6 shown in the structural formula (2), wherein the material of main part of device organic luminous layer adopts CPF, and phosphorescent coloring adopts Ir (ppy)
2(acac), the evaporation speed ratio by control double source evaporation makes Ir (ppy)
2(acac) doping content in CPF descends gradually along with the increase of organic luminous layer evaporation thickness.
Embodiment 7 (device number OLED7)
With preparing with above-mentioned that the identical method of device prepares OLED7 shown in the structural formula (2), wherein the material of main part of device organic luminous layer adopts CBP, phosphorescent coloring adopts PtOEP, by the evaporation speed ratio of controlling the double source evaporation doping content of PtOEP in CBP is descended gradually along with the increase of organic luminous layer evaporation thickness.
Embodiment 8 (device number OLED8)
With preparing with above-mentioned that the identical method of device prepares OLED8 shown in the structural formula (2), wherein the material of main part of device organic luminous layer adopts CPF, and phosphorescent coloring adopts Ir (piq)
2(acac), the evaporation speed ratio by control double source evaporation makes Ir (piq)
2(acac) doping content in CPF descends gradually along with the increase of organic luminous layer evaporation thickness.
The prepared device architecture of the foregoing description 4-8 is as shown in table 4, and device parameters is as shown in table 5.
Table 5
Embodiment 9 (device number OLED 9)
With preparing with above-mentioned that the identical method of device prepares OLED9 shown in the structural formula (3), wherein the material of main part of device organic luminous layer adopts CBP, phosphorescent coloring adopts FIrpic, by the evaporation speed ratio of controlling the double source evaporation doping content of FIrpic in CBP is risen gradually along with the increase of organic luminous layer evaporation thickness.
Embodiment 10 (device number OLED 10)
With preparing with above-mentioned that the identical method of device prepares OLED10 shown in the structural formula (4), wherein the material of main part of device organic luminous layer adopts DCB, phosphorescent coloring adopts FIrpic, by the evaporation speed ratio of controlling the double source evaporation doping content of FIrpic in DCB is risen gradually along with the increase of organic luminous layer evaporation thickness.
Embodiment 11 (device number OLED 11)
With preparing with above-mentioned that the identical method of device prepares OLED11 shown in the structural formula (5), wherein the material of main part of device organic luminous layer adopts CPF, phosphorescent coloring adopts FIrpic, by the evaporation speed ratio of controlling the double source evaporation doping content of FIrpic in CPF is risen gradually along with the increase of organic luminous layer evaporation thickness.
Table 6
| The embodiment numbering | Device number | The OLEDs structure |
| Embodiment 9 | OLED9 | The thickness of Glass/ITO/teflon/CBP:FIrpic/BAlq/LiF/Al organic luminous layer is 35nm, and the average doping content of FIrpic is 25wt%.The thickness of ITO layer is 200nm, and the thickness of teflon layer is 6nm, and the thickness of BAlq layer is 30nm, and the thickness of LiF alloy-layer is 1nm, and the thickness of Al layer is 100nm |
| |
|
The thickness of Glass/ITO/Teflon/DCB:FIrpic/Mg:Ag/Ag organic luminous layer is 50nm, and the average doping content of FIrpic is 30wt%.The thickness of ITO layer is 200nm, and the thickness of teflon layer is 4nm, and the thickness of Mg:Ag alloy-layer is 100nm, and the thickness of Ag layer is 50nm |
| Embodiment 11 | |
The thickness of Glass/ITO/NPB/CPF:FIrpic/Mg:Ag/Ag organic luminous layer is 40nm, and the average doping content of FIrpic is 20wt%.The thickness of ITO layer is 200nm, and the thickness of NPB layer is 40nm, and the thickness of Mg:Ag alloy-layer is 100nm, and the thickness of Ag layer is 50nm |
Table 7
Although describe the present invention in conjunction with the preferred embodiments, but the present invention is not limited to the foregoing description and accompanying drawing, should be appreciated that under the guiding of the present invention's design, those skilled in the art can carry out various modifications and improvement, and claims have been summarized scope of the present invention.
Claims (26)
1. organic electro phosphorescent device, this device comprises transparent substrate, anode layer, hole transmission layer, organic luminous layer, electron transfer layer and cathode layer successively, described organic luminous layer comprises material of main part and phosphorescent coloring, it is characterized in that: the direction of the doping content of described phosphorescent coloring along hole transmission layer to electron transfer layer rises gradually along with the increase of organic light emission layer thickness or descends gradually and form the grade doping structure.
2. organic electro phosphorescent device according to claim 1 is characterized in that, the average doping content of described phosphorescent coloring is 0.1～50wt%.
3. organic electro phosphorescent device according to claim 2 is characterized in that, the average doping content of described phosphorescent coloring is 1～30wt%.
4. organic electro phosphorescent device according to claim 1 is characterized in that, described material of main part is a kind of material in biphenyl-carbazoles or the benzene-carbazole compound.
5. organic electro phosphorescent device according to claim 4, it is characterized in that, described biphenyl-carbazole compound comprises 4,4 '-N, N '-two carbazoles-biphenyl, described benzene-carbazole compound comprises N, N '-two carbazyl-1,4-dimethylene benzene or 9,9-two (4-two carbazoles-phenyl) fluorenes.
6. organic electro phosphorescent device according to claim 1 is characterized in that, described phosphorescent coloring is a kind of metal organic complex.
7. organic electro phosphorescent device according to claim 6 is characterized in that, described metal organic complex comprises two [2-(4, the 6-difluorophenyl) pyridine radicals-N, C
2 '] picolinic acid iridium (III), two (1-phenyl-isoquinolyl) (acetylacetone,2,4-pentanedione) iridium (III), octaethylporphyrin platinum, three (2-phenylpyridine) iridium (III) or two (2-phenylpyridine) (acetylacetone,2,4-pentanedione) iridium (III).
8. organic electro phosphorescent device according to claim 1 is characterized in that, described hole transmission layer adopts a kind of material in the triphenylamine compounds.
9. organic electro phosphorescent device according to claim 8 is characterized in that, described triphenylamine compounds comprises N, N '-two-(1-naphthyl)-N, N '-diphenyl-1,1 '-xenyl-4,4 '-diamines, N, N '-diphenyl-N, N '-two (aminomethyl phenyl)-1,1 '-xenyl-4,4 '-diamines or 4,4 ', 4 " (3 aminomethyl phenyl aniline) triphenylamine-three.
10. organic electro phosphorescent device according to claim 1 is characterized in that, described electron transfer layer adopts a kind of material in metal organic complex, aromatic condensed ring class, the o-phenanthroline Lei Huo oxadiazole compounds.
11. organic electro phosphorescent device according to claim 10, it is characterized in that, described metal organic complex comprises three (oxine) aluminium, two (2-methyl-8-quinolyl)-4-phenylphenol aluminium (III), three (oxine) gallium, (the adjacent amine phenol of salicylidene)-(8-oxyquinoline) closes aluminium (III) or (the adjacent amine phenol of salicylidene)-(8-oxyquinoline) closes gallium (III), described aromatic condensed ring compounds comprises pentacene Huo perylene, described o-phenanthroline compounds comprises 4,7-diphenyl-1,10-o-phenanthroline or 2,9-dimethyl-4,7-diphenyl-1, the 10-o-phenanthroline, Suo Shu De oxadiazole compounds comprises 2-(4-t-butyl-phenyl)-5-(4-xenyl)-1,3, the 4-oxadiazole.
12. organic electro phosphorescent device, this device comprises transparent substrate, anode layer, organic function layer, cathode layer, wherein organic function layer comprises organic luminous layer, described organic luminous layer comprises material of main part and phosphorescent coloring, it is characterized in that: the direction of the doping content of described phosphorescent coloring along anode layer to cathode layer rises gradually along with the increase of organic light emission layer thickness or descends gradually and form the grade doping structure.
13. organic electro phosphorescent device according to claim 12 is characterized in that, described organic function layer comprises hole transmission layer.
14. organic electro phosphorescent device according to claim 12 is characterized in that, described organic function layer comprises electron transfer layer.
15., it is characterized in that described organic function layer comprises hole injection layer according to claim 13 or 14 described organic electro phosphorescent devices.
16., it is characterized in that described organic function layer comprises electron injecting layer according to claim 13 or 14 described organic electro phosphorescent devices.
17. organic electro phosphorescent device according to claim 12 is characterized in that, the average doping content of described phosphorescent coloring is 0.1～50wt%.
18. organic electro phosphorescent device according to claim 12 is characterized in that, the average doping content of described phosphorescent coloring is 1～30wt%.
19. organic electro phosphorescent device according to claim 12 is characterized in that, described material of main part is a kind of material in biphenyl-carbazoles or the benzene-carbazole compound.
20. organic electro phosphorescent device according to claim 19, it is characterized in that, described biphenyl-carbazole compound comprises 4,4 '-N, N '-two carbazoles-biphenyl, described benzene-carbazole compound comprises N, N '-two carbazyl-1,4-dimethylene benzene or 9,9-two (4-two carbazoles-phenyl) fluorenes.
21. organic electro phosphorescent device according to claim 12 is characterized in that, described phosphorescent coloring is a kind of metal organic complex.
22. organic electro phosphorescent device according to claim 21 is characterized in that, described metal organic complex comprises two [2-(4, the 6-difluorophenyl) pyridine radicals-N, C
2 '] picolinic acid iridium (III), two (1-phenyl-isoquinolyl) (acetylacetone,2,4-pentanedione) iridium (III), octaethylporphyrin platinum, three (2-phenylpyridine) iridium (III) or two (2-phenylpyridine) (acetylacetone,2,4-pentanedione) iridium (III).
23. organic electro phosphorescent device according to claim 13 is characterized in that, described hole transmission layer adopts a kind of material in the triphenylamine compounds.
24. organic electro phosphorescent device according to claim 23 is characterized in that, described triphenylamine compounds comprises N, N '-two-(1-naphthyl)-N, N '-diphenyl-1,1 '-xenyl-4,4 '-diamines, N, N '-diphenyl-N, N '-two (aminomethyl phenyl)-1,1 '-xenyl-4,4 '-diamines or 4,4 ', 4 " (3-aminomethyl phenyl aniline) triphenylamine-three.
25. organic electro phosphorescent device according to claim 14 is characterized in that, described electron transfer layer adopts a kind of material in metal organic complex, aromatic condensed ring class, the o-phenanthroline Lei Huo oxadiazole compounds.
26. organic electro phosphorescent device according to claim 25, it is characterized in that, described metal organic complex comprises three (oxine) aluminium, two (2-methyl-8-quinolyl)-4-phenylphenol aluminium (III), three (oxine) gallium, (the adjacent amine phenol of salicylidene)-(8-oxyquinoline) closes aluminium (III) or (the adjacent amine phenol of salicylidene)-(8-oxyquinoline) closes gallium (III), described aromatic condensed ring compounds comprises pentacene Huo perylene, described o-phenanthroline compounds comprises 4,7-diphenyl-1,10-o-phenanthroline or 2,9-dimethyl-4,7-diphenyl-1, the 10-o-phenanthroline, Suo Shu De oxadiazole compounds comprises 2-(4-t-butyl-phenyl)-5-(4-xenyl)-1,3, the 4-oxadiazole.
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| US8501328B2 (en) * | 2005-11-07 | 2013-08-06 | Lg Display Co., Ltd. | Red phosphorescent compounds and organic electroluminescent devices using the same |
| US9023489B2 (en) | 2005-11-07 | 2015-05-05 | Lg Display Co., Ltd. | Red phosphorescent compounds and organic electroluminescent devices using the same |
| JP5380275B2 (en) * | 2007-02-19 | 2014-01-08 | 大日本印刷株式会社 | Organic electroluminescence device |
| DE102008039361A1 (en) * | 2008-05-30 | 2009-12-03 | Osram Opto Semiconductors Gmbh | Electronic device |
| KR102198635B1 (en) | 2012-04-20 | 2021-01-05 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Organic compound, light-emitting element, light-emitting device, electronic device, and lighting device |
| CN104183716A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Organic light-emitting device and preparation method thereof |
| CN104183721A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Organic light emitting diode and preparation method thereof |
| CN104183725A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Preparation method of organic light emitting diode |
| CN104183794A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Preparation method of organic light emitting diode |
| US9666822B2 (en) * | 2013-12-17 | 2017-05-30 | The Regents Of The University Of Michigan | Extended OLED operational lifetime through phosphorescent dopant profile management |
| CN104078623B (en) * | 2014-06-17 | 2016-08-17 | 京东方科技集团股份有限公司 | A kind of organic electroluminescence device, organic electroluminescence display device and method of manufacturing same |
| CN104393185B (en) * | 2014-11-25 | 2017-05-24 | 京东方科技集团股份有限公司 | Laminated organic electroluminescence device and manufacturing method thereof |
| CN106098958B (en) * | 2016-08-26 | 2018-04-03 | 昆山工研院新型平板显示技术中心有限公司 | White light organic electroluminescent device and preparation method thereof |
| CN107611276B (en) * | 2017-09-22 | 2019-03-12 | 京东方科技集团股份有限公司 | Organic Light Emitting Diode and display panel |
| CN108365113B (en) * | 2018-01-29 | 2019-08-20 | 苏州大学 | Super-efficient organic electroluminescent diode device |
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| CN113328044B (en) * | 2021-05-25 | 2023-04-18 | 武汉华星光电技术有限公司 | Display panel, preparation method thereof and display device |
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