CN1700824A - An OLED - Google Patents
An OLED Download PDFInfo
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- CN1700824A CN1700824A CN 200510072373 CN200510072373A CN1700824A CN 1700824 A CN1700824 A CN 1700824A CN 200510072373 CN200510072373 CN 200510072373 CN 200510072373 A CN200510072373 A CN 200510072373A CN 1700824 A CN1700824 A CN 1700824A
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- pfa
- organic electroluminescence
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- 230000008018 melting Effects 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 9
- 229920002313 fluoropolymer Polymers 0.000 claims description 19
- 239000004811 fluoropolymer Substances 0.000 claims description 18
- 238000005401 electroluminescence Methods 0.000 claims description 15
- -1 perfluoroethylene-propylene Chemical group 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000007747 plating Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 description 71
- 230000008020 evaporation Effects 0.000 description 67
- 239000010408 film Substances 0.000 description 34
- 239000010410 layer Substances 0.000 description 32
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 15
- 239000011521 glass Substances 0.000 description 15
- 239000002356 single layer Substances 0.000 description 15
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000004809 Teflon Substances 0.000 description 7
- 229920006362 Teflon® Polymers 0.000 description 7
- 229910000861 Mg alloy Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- Electroluminescent Light Sources (AREA)
Abstract
This invention relates to one organic electrical lighting device with high efficiency, low working voltage and low vapor voltage and rapid plating rate, which comprises the following steps: the device comprises positive electrode buffer layer with melt fluorin polymer with the melting point less than 327 degrees and melting stickness less than 1010Pa.S and optimal temperature less or equal to 306 degrees and optimal melting stickness less than or equal to 104Pa.S.
Description
Technical field
The present invention relates to a kind of organic electroluminescence device.
Background technology
In organic electroluminescence device, add anode buffer layer and can regulate the charge carrier injection, raise the efficiency and stability.(APL) rolled up for the 15th phase in 1996 the 69th as " Applied Physics journal ", human copper phthalocyanines such as VanSlyke are as resilient coating.Tsing-Hua University uses polytetrafluoroethylene (PTFE on January 2nd, 2002 disclosed Chinese patent CN139459A and on April 17th, 2002 among the disclosed Chinese patent CN1345172A, hereinafter to be referred as Teflon) as anode buffer layer, every performance such as device efficiency be improved significantly.But there is evaporation air pressure height in polytetrafluoroethylene, the problem that evaporation speed is slow because fusing point and melt temperature are too high in evaporate process.
Summary of the invention
The invention provides a kind of device efficiency height, operating voltage is low, evaporation air pressure is low, evaporation speed is fast organic electroluminescence device.
Technical scheme of the present invention is: a kind of organic electroluminescence device, contain anode buffer layer, and anode buffer layer is fusible fluoropolymer.
The fusing point of fusible fluoropolymer is generally less than the fusing point (327 ℃) of polytetrafluoroethylene, and melt viscosity is generally less than 10
10PaS.The preferred temperature of the fusing point of fusible fluoropolymer is less than or equal to below 306 ℃, and preferred melt viscosity is less than or equal to 10
4PaS.
The melting fluoropolymer can be polytetrafluoroethylene-perfluoroalkyl vinyl ether (hereinafter to be referred as PFA).
The melting fluoropolymer is perfluoroethylene-propylene (hereinafter to be referred as FEP).
The melting fluoropolymer is polytrifluorochloroethylene-vinylidene (hereinafter to be referred as PVDF).
What the invention has the beneficial effects as follows organic electroluminescence device that fusible fluoropolymer forms has effectively regulated the hole injection, and the operating voltage of device is low, efficient height, and low, the evaporation speed height of fusible fluoropolymer evaporation air pressure.
Description of drawings
Fig. 1 is the current density-voltage curve of embodiment 1-5 and Comparative Examples 1.
Fig. 2 is the brightness-voltage curve of embodiment 1-5 and Comparative Examples 1.
Fig. 3 is the efficient-current density curve of embodiment 1-5 and Comparative Examples 1.
Fig. 4 is the efficient correlation curve of embodiment 1 and Comparative Examples 2.
Fig. 5 is the current density-voltage curve of embodiment 6-9 and Comparative Examples 1.
Fig. 6 is the brightness-voltage curve of embodiment 6-9 and Comparative Examples 1.
Fig. 7 is the efficient-current density curve of embodiment 6-9 and Comparative Examples 1.
Fig. 8 is the current density-voltage curve of embodiment 10 and Comparative Examples 1.
Fig. 9 is the brightness-voltage curve of embodiment 10 and Comparative Examples 1.
Figure 10 is the current efficiency-current density curve of embodiment 10 and Comparative Examples 1.
Embodiment
Anode buffer layer of the present invention is to play to regulate the layer that the hole is injected between the anode utmost point and organic layer (for example luminescent layer, hole transmission layer).
The fusible fluoropolymer of term is the fluoropolymer that presents the melt-flow state in the vacuum evaporation process, and below 327 ℃, melt viscosity is 10 generally for its fusing point
10The polymer that PaS is following.Preferred fusing point is less than or equal to 306 ℃, and melt viscosity is less than or equal to 10
4PaS.With 327 ℃ the high-melting-point of Teflon, 10
10The high melt viscosity of PaS is compared, and the fusing point of PFA is 306 ℃, and the fusing point of FEP is 275 ℃, and the fusing point of PVDF is 156 ℃, and the melt viscosity of PFA and FEP records 10 at 380 ℃
3-10
4Between the PaS.The melt viscosity of PVDF records 10 at 170-180 ℃
2-10
4Between the PaS.Under the same terms, the fusing point of fusible fluoropolymer is low more, and melt viscosity is more little, material easy more fusion in the process of evaporation, mobile, and the performance of the organic electroluminescence device of this kind material preparation is just good more.
Embodiment 1
(1) is carved with the cleaning of the glass substrate of ITO in advance: utilize the ultrasonic and ultrasonic method of deionized water of the washing agent of heat that the transparent conduction base sheet ito glass is cleaned, place it in after the cleaning infrared lamp under and dry.Wherein the ITO film above the conductive substrate is as the anode layer of device, and the square resistance of ITO film is 50 Ω, and thickness is 150nm;
(2) preparation of organic luminous layer: place in the vacuum chamber with above-mentioned cleaning, drying and through pretreated ito glass, be evacuated to 8 * 10
-3Pa, evaporation PFA buffer thin film, evaporation speed is 0.2nm/s, chamber pressure is 1.4 * 10 during evaporation
-2Pa, film thickness are 10nm.Continue evaporation three (oxine) aluminium (afterwards abbreviating Alq3 as) film, evaporation speed is 0.3nm/S, and evaporation air pressure is 8 * 10
-3Pa, film thickness are 60nm.Continue evaporation magnesium alloy silver electrode in vacuum chamber, evaporation speed is about 2nm/S, Mg: Ag=10: 1, and evaporation air pressure 8 * 10
-3Pa, film thickness 100nm, and then evaporation silver, evaporation speed 0.3nm/S, evaporation air pressure 8 * 10
-3Pa, film thickness 100nm.
Embodiment 3 preparation process are with embodiment 1, and just the thickness of PFA is 4nm.
Embodiment 5 preparation process are with embodiment 1, and just the thickness of PFA is 12nm.
Comparative Examples 1
(1) is carved with the cleaning of the glass substrate of ITO in advance: utilize the ultrasonic and ultrasonic method of deionized water of the washing agent of heat that the transparent conduction base sheet ito glass is cleaned, place it in after the cleaning infrared lamp under and dry.Wherein the ITO film above the conductive substrate is as the anode layer of device, and the square resistance of ITO film is 50 Ω, and thickness is 150nm;
(2) preparation of organic luminous layer: place in the vacuum chamber with above-mentioned cleaning, drying and through pretreated ito glass, be evacuated to 8 * 10
-3Pa, evaporating Al q3 film, evaporation speed is 0.3nm/S, evaporation air pressure is 8 * 10
-3Pa, film thickness are 60nm.Continue evaporation magnesium alloy silver electrode in vacuum chamber, evaporation speed is about 2nm/S, Mg: Ag=10: 1, and evaporation air pressure 8 * 10
-3Pa, film thickness 100nm, and then evaporation silver, evaporation speed 0.3nm/S, evaporation air pressure 8 * 10
-3Pa, film thickness 100nm.
Comparative Examples 2
(1) is carved with the cleaning of the glass substrate of ITO in advance: utilize the ultrasonic and ultrasonic method of deionized water of the washing agent of heat that the transparent conduction base sheet ito glass is cleaned, place it in after the cleaning infrared lamp under and dry.Wherein the ITO film above the conductive substrate is as the anode layer of device, and the square resistance of ITO film is 50 Ω, and thickness is 150nm;
(2) preparation of organic luminous layer: place in the vacuum chamber with above-mentioned cleaning, drying and through pretreated ito glass, be evacuated to 8 * 10
-3Pa, evaporation Teflon buffer thin film, evaporation speed is 0.01nm/s, chamber pressure is 6.0 * 10 during evaporation
-3Pa, film thickness are 6nm.Continue evaporating Al q3 film, evaporation speed is 0.01nm/S, and evaporation air pressure is 8 * 10
-3Pa, film thickness are 60nm.Continue evaporation magnesium alloy silver electrode in vacuum chamber, evaporation speed is about 2nm/S, Mg: Ag=10: 1, and evaporation air pressure 8 * 10
-3Pa, film thickness 100nm, and then evaporation silver, evaporation speed 0.3nm/S, evaporation air pressure 8 * 10
-3Pa, film thickness 100nm.
As shown in Figure 1, than the Alq3 single layer device, add after the PFA resilient coating, current density reduces, and along with the increase of PFA buffer layer thickness, current density reduces.
As shown in Figure 2, than the Alq3 single layer device, behind the adding PFA resilient coating, brightness obviously improves, and along with the increase of PFA buffer layer thickness, brightness descends gradually, but still is higher than the Alq3 single layer device far away.For example, when voltage was 13.6V, the brightness of Alq3 single layer device was 224cd/m
2, the device brightness with 10nmPFA resilient coating is 1095cd/m
2
As shown in Figure 3, than the Alq3 single layer device, add the PFA resilient coating after, efficient obviously improves, along with the increase of PFA buffer layer thickness, efficient improves earlier, when 2nm was increased to 10nm, efficient was brought up to 4.40cd/A (1000A/m by 2.40cd/A as PFA thickness
2The time); When PFA thickness continues to increase, decrease in efficiency.
As shown in Figure 4, than the Teflon single layer device of optimizing, the efficient of the PFA single layer device of optimization is higher, for example at electric current 1000A/m
2The time, be that the efficient of the device of resilient coating is 4.40cd/A with 10nmPFA, and be that the efficient of the device of resilient coating is 2.50cd/A with 6nmTeflon.
(1) is carved with the cleaning of the glass substrate of ITO in advance: utilize the ultrasonic and ultrasonic method of deionized water of the washing agent of heat that the transparent conduction base sheet ito glass is cleaned, place it in after the cleaning infrared lamp under and dry.Wherein the ITO film above the conductive substrate is as the anode layer of device, and the square resistance of ITO film is 50 Ω, and thickness is 150nm;
(2) preparation of organic luminous layer: place in the vacuum chamber with above-mentioned cleaning, drying and through pretreated ito glass, be evacuated to 8 * 10
-3Pa, evaporation FEP buffer thin film, evaporation speed is 0.03nm/s, chamber pressure is 3.0 * 10 during evaporation
-2Pa, film thickness are 10nm.Continue evaporating Al q3 film, evaporation speed is 0.3nm/S, and evaporation air pressure is 8 * 10
-3Pa, film thickness are 60nm.Continue evaporation magnesium alloy silver electrode in vacuum chamber, evaporation speed is about 2nm/S, Mg: Ag=10: 1, and evaporation air pressure 8 * 10
-3Pa, film thickness 100nm, and then evaporation silver, evaporation speed 0.3nm/S, evaporation air pressure 8 * 10
-3Pa, film thickness 100nm.
Embodiment 7 preparation process are with embodiment 1, and just the thickness of PFA is 2nm.
Embodiment 9 preparation process are with embodiment 1, and just the thickness of PFA is 14nm.
As shown in Figure 5, than the Alq3 single layer device, add after the FEP resilient coating, current density reduces, and along with the increase of FEP buffer layer thickness, and current density is and reduces trend.As shown in Figure 6, than the Alq3 single layer device, behind the adding FEP resilient coating, brightness obviously improves.For example, when voltage was 13.6V, the brightness of Alq3 single layer device was 224cd/m
2, the device brightness with 10nmFEP resilient coating is 3427cd/m
2
As shown in Figure 7, than the Alq3 single layer device, add the FEP resilient coating after, efficient obviously improves, along with the increase of FEP buffer layer thickness, efficient improves earlier, when 2nm was increased to 10nm, efficient was brought up to 3.21cd/A (1000A/m by 1.77cd/A as FEP thickness
2The time); When FEP thickness continues to increase, decrease in efficiency.
(1) is carved with the cleaning of the glass substrate of ITO in advance: utilize the ultrasonic and ultrasonic method of deionized water of the washing agent of heat that the transparent conduction base sheet ito glass is cleaned, place it in after the cleaning infrared lamp under and dry.Wherein the ITO film above the conductive substrate is as the anode layer of device, and the square resistance of ITO film is 50 Ω, and thickness is 150nm;
(2) preparation of organic luminous layer: place in the vacuum chamber with above-mentioned cleaning, drying and through pretreated ito glass, be evacuated to 8 * 10
-3Pa, evaporation PVDF buffer thin film, evaporation speed is 0.1nm/s, chamber pressure is 2.0 * 10 during evaporation
-2Pa, film thickness are 6nm.Continue evaporating Al q3 film, evaporation speed is 0.3nm/S, and evaporation air pressure is 8 * 10
-3Pa, film thickness are 60nm.Continue evaporation magnesium alloy silver electrode in vacuum chamber, evaporation speed is about 2nm/S, Mg: Ag=10: 1, and evaporation air pressure 8 * 10
-3Pa, film thickness 100nm, and then evaporation silver, evaporation speed 0.3nm/S, evaporation air pressure 8 * 10
-3Pa, film thickness 100nm.As shown in Figure 8, than the Alq3 single layer device, add after the PVDF resilient coating, current density reduces.As shown in Figure 9, than the Alq3 single layer device, add after the PVDF resilient coating, brightness obviously improves.For example, when voltage 13.6V, the brightness of Alq3 single layer device is 224cd/m
2, the device brightness with 6nmPVDF resilient coating is 1961cd/m
2
As shown in figure 10, than the Alq3 single layer device, add after the PVDF resilient coating, efficient obviously improves.The efficient that has the device of 6nmPVDF resilient coating when electric current 1000A/m2 is 0.95cd/A.
Table 1
| Resilient coating | ????Teflon | ????PFA | ????PVDF | ????FEP |
| Fusing point (℃) | ????327 | ????306 | ????156 | ????275 |
| Melt viscosity (PaS) | ????10 10 | ????10 3-10 4 | ????10 3-10 4 | ????10 2-10 4 |
As can be seen from Table 1, the fusing point of PFA, PVDF, FEP and melt viscosity be all less than Teflon, evaporation the time form runny molten condition, thereby be easy to evaporation.From being not difficult to find out by embodiment, fusible fluoropolymers such as PFA, FEP and PVDF are low than Teflon evaporation air pressure, evaporation speed is fast, easier evaporation film-forming.
What embodiment provided is the organic electroluminescence device that contains anode layer, luminescent layer, cathode layer device architecture, what will be understood by those skilled in the art that is, one or more layers the organic electroluminescence device that further contains in the functional layers such as hole transmission layer, electron transfer layer, hole blocking layer, electron injecting layer also is fine, or adopts the device architecture of top outgoing also to be fine.Thought of the present invention is to add the anode buffer layer structure that the fusible fluorinated polymer material of one deck constitutes between anode and organic layer, can effectively regulate the injection in hole, thereby improved the performances such as efficient of device, reduced evaporation air pressure simultaneously, improved evaporation speed.Although describe the present invention in conjunction with the embodiments, the present invention is not limited to the foregoing description and accompanying drawing, and 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 (6)
1, a kind of organic electroluminescence device contains anode buffer layer, it is characterized in that described anode buffer layer is fusible fluoropolymer.
2, organic electroluminescence device as claimed in claim 1, the fusing point that it is characterized in that described fusible fluoropolymer is less than 327 ℃, and melt viscosity is less than 10
10Pas.
3, the described organic electroluminescence device of claim 1 is characterized in that the fusing point of described fusible fluoropolymer is less than or equal to 306 ℃, and melt viscosity is less than or equal to 10
4Pas.
4, organic electroluminescence device as claimed in claim 1 or 2 is characterized in that described melting fluoropolymer is polytetrafluoroethylene-perfluoroalkyl vinyl ether.
5, organic electroluminescence device as claimed in claim 1 or 2 is characterized in that described melting fluoropolymer is a perfluoroethylene-propylene.
6, organic electroluminescence device as claimed in claim 1 or 2 is characterized in that described melting fluoropolymer is polytrifluorochloroethylene-vinylidene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100723730A CN100557852C (en) | 2005-05-31 | 2005-05-31 | A kind of organic electroluminescence device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100723730A CN100557852C (en) | 2005-05-31 | 2005-05-31 | A kind of organic electroluminescence device |
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| Publication Number | Publication Date |
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| CN1700824A true CN1700824A (en) | 2005-11-23 |
| CN100557852C CN100557852C (en) | 2009-11-04 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101447644B (en) * | 2007-11-28 | 2010-11-10 | 中国科学院长春光学精密机械与物理研究所 | Electric pump surface-emitting coupled organic laser device with microcavity |
| CN106803546A (en) * | 2017-02-20 | 2017-06-06 | 厦门世纳芯科技有限公司 | A kind of light emitting diode with quantum dots and preparation method thereof |
| CN109307907A (en) * | 2018-10-17 | 2019-02-05 | 深圳市华星光电半导体显示技术有限公司 | The preparation method of anti-reflection coating and backlight module with the anti-reflection coating |
| CN111029485A (en) * | 2019-12-26 | 2020-04-17 | 南京邮电大学 | Polymer-modified graphene film and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102360093B1 (en) * | 2015-07-22 | 2022-02-09 | 삼성디스플레이 주식회사 | Organic light-emitting display apparatus and the method for manufacturing of the organic light-emitting display apparatus |
| WO2021172369A1 (en) | 2020-02-26 | 2021-09-02 | Ａｇｃ株式会社 | Fluorine-containing polymer, film, film manufacturing method, and organic opto-electronic element |
-
2005
- 2005-05-31 CN CNB2005100723730A patent/CN100557852C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101447644B (en) * | 2007-11-28 | 2010-11-10 | 中国科学院长春光学精密机械与物理研究所 | Electric pump surface-emitting coupled organic laser device with microcavity |
| CN106803546A (en) * | 2017-02-20 | 2017-06-06 | 厦门世纳芯科技有限公司 | A kind of light emitting diode with quantum dots and preparation method thereof |
| CN109307907A (en) * | 2018-10-17 | 2019-02-05 | 深圳市华星光电半导体显示技术有限公司 | The preparation method of anti-reflection coating and backlight module with the anti-reflection coating |
| CN111029485A (en) * | 2019-12-26 | 2020-04-17 | 南京邮电大学 | Polymer-modified graphene film and preparation method and application thereof |
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| CN100557852C (en) | 2009-11-04 |
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