CN102214801A - Organic light-emitting diode of double P-type doped layer - Google Patents
Organic light-emitting diode of double P-type doped layer Download PDFInfo
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Abstract
The invention discloses an organic light-emitting diode of a double P-type doped layer. In the organic light-emitting diode, hole injection is enhanced by using a double-layer P-type doped film. The organic light-emitting diode consists of a layer of anode on a glass substrate, an organic P-type doped hole transport layer deposited on the anode, an organic P-type doped hole transport auxiliary layer deposited on the organic P-type doped hole transport layer, an organic hole transport layer deposited on the organic P-type doped hole transport auxiliary layer, an organic light-emitting layer deposited on the organic hole transport layer, an electron injection layer deposited on the organic light-emitting layer and a layer of cathode deposited on the electron injection layer. Compared with the conventional single-layer P-type doped film, the organic light-emitting diode has the advantages of increase in the current density by about 70 times, remarkable increase in the performance of a device, wide application market and extremely high commercial value.
Description
Technical field
Technical scheme of the present invention includes OLED, specifically adopts double-deck P type doping film to strengthen the Organic Light Emitting Diode that the hole is injected.
Background technology
In Organic Light Emitting Diode, the generation of light is from the right composite attenuation of electrically excited tight beam electrons and hole.Therefore, the size of hole current has directly determined device performance in the Organic Light Emitting Diode.How strengthening hole current is to improve the key subjects that organic flat panel display and white-light illuminating technology must solve when taking a step forward.
In Organic Light Emitting Diode, the size of hole current depends on the hole injection and transmits two processes.The hole injection process is meant that the hole is injected into the organic cavity transmission layer from positive pole, and its efficient is decided by anodal and organic cavity transmission layer Schottky barrier (hole injection barrier) at the interface.Use high work content positive electrode generally can reduce the hole injection barrier, but because the pinning effect of Fermi level, high work content positive pole and unadulterated organic cavity transmission layer Schottky barrier at the interface generally are not less than 0.5eV, therefore, the hole injection efficiency of traditional hole injection technique is relatively poor.But, when using P type doping organic material as hole transmission layer, hole current can be greatly improved, this is that the hole can be injected in the organic cavity transmission layer with the mode high efficiency of tunnelling because (1) P type doping organic material can form very thin depletion layer at the contact interface place with positive pole; (2) P type organic conductivity of electrolyte materials of mixing is very high, can significantly reduce the ohmic loss in the hole-conductive process.At present, the organic P type doping hole transport layer material that often uses have 4,4 ', 4 " mix 2,3,5 in three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine; 6-tetrafluoro-7,7 ', 8; 8 '-four cyanogen dimethyl 1,4-benzoquinone; N4, N4, N4 '; and N4 '-four (4-methoxyphenyl)-[1,1 '-biphenyl]-4,4 '-mix 2 in the diamines; 3,5,6-tetrafluoro-7,7 ', 8,8 '-four cyanogen dimethyl 1,4-benzoquinone, mix three [1 in 4,4 '-two (9-carbazole) biphenyl, 2-two (trifluoromethyl) ethane-1,2-two thiol-ene] molybdenum, 4,4 ', 4 " tungstic acid mixes in three (carbazole-9-yl) triphenylamine; N; N '-diphenyl-N; molybdenum trioxide mixes in N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines.But, current organic P type doping hole injection technique also exists sizable problem, promptly exist bigger transmission potential barrier at the interface in the organic P type doping hole transmission layer and the organic cavity transmission layer of not mixing, thereby suppressed the raising of hole current greatly, for example, 4,4 ', 4 " mix 2,3 in three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine; 5; 6-tetrafluoro-7,7 ', 8; the hole transport potential barrier at the interface of 8 '-four cyanogen dimethyl 1,4-benzoquinone and 4,4 '-two (9-carbazole) biphenyl is approximately 0.70eV.Therefore, how reducing the transmission potential barrier in the injection technique of organic P type doping hole, is to improve the key subjects that current organic light emission Technology Need solves.
For this reason, we have proposed the design philosophy of the Organic Light Emitting Diode of double-P type doped layer, reduce the hole transport potential barrier by between the organic P type doping hole transmission layer and the organic cavity transmission layer of not mixing, adding the organic P type of one deck doping hole transport auxiliary layer, can significantly improve device performance.
Summary of the invention
Technical problem to be solved by this invention is: the Organic Light Emitting Diode that the double-P type doped layer is provided, be a kind of Organic Light Emitting Diode that adopts double-deck P type doping film to strengthen the hole injection, its performance significantly is better than the Organic Light Emitting Diode that the organic P type of existing employing individual layer doping hole transmission layer realizes that the hole is injected.
The present invention solves this technical problem the technical scheme that is adopted:
A kind of Organic Light Emitting Diode of double-P type doped layer, it is a kind of Organic Light Emitting Diode that uses double-deck P type doping film to strengthen the hole injection, by one deck anode on the glass substrate, one is deposited upon the organic P type doping hole transmission layer on the anode, one is deposited upon the organic P type doping hole transport auxiliary layer on organic P type doping hole transmission layer, one is deposited upon the organic cavity transmission layer on organic P type doping hole transport auxiliary layer, one is deposited upon the organic luminous layer on the organic cavity transmission layer, and an electron injecting layer that is deposited upon on the organic luminous layer is formed with one deck negative electrode that is deposited on the electron injecting layer.
The Organic Light Emitting Diode of above-mentioned double-P type doped layer, described anode are that thickness is the electric conductive oxidation indium tin thin film of 100nm, or the thick noble metal film of 20nm, and described noble metal is a gold or silver-colored.
The Organic Light Emitting Diode of above-mentioned double-P type doped layer, the face resistance of described tin indium oxide conductive film is less than 10 ohm/per 4 * 4cm
2Square.
The Organic Light Emitting Diode of above-mentioned double-P type doped layer, the described material that is deposited on the organic P type doping hole transmission layer on the anode be 4,4 ', 4 " mix 2 in three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine; 3,5,6-tetrafluoro-7; 7 ', 8,8 '-four cyanogen dimethyl 1,4-benzoquinone; its quality proportioning is 4,4 ', 4 " three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamines: 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-four cyanogen dimethyl 1,4-benzoquinone=1: 0.01～0.5; Or at N4, N4, N4 ', N4 '-four (4-methoxyphenyl)-[1,1 '-biphenyl]-4,4 '-mix 2,3,5 in the diamines, 6-tetrafluoro-7,7 ', 8,8 '-four cyanogen dimethyl 1,4-benzoquinone, its quality proportioning is N4, N4, N4 ', N4 '-four (4-methoxyphenyl)-[1,1 '-biphenyl]-4,4 '-diamines: 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-four cyanogen dimethyl 1,4-benzoquinone=1: 0.01～0.5.
The Organic Light Emitting Diode of above-mentioned double-P type doped layer, the described material that is deposited on the organic P type doping hole transport auxiliary layer on organic P type doping hole transmission layer is 4, mix three [1 in 4 '-two (9-carbazole) biphenyl, 2-two (trifluoromethyl) ethane-1,2-two thiol-ene] molybdenum, its quality proportioning is 4,4 '-two (9-carbazole) biphenyl: three [1,2-two (trifluoromethyl) ethane-1,2-two thiol-ene] molybdenum=1: 0.01～0.5; Or 4,4 ', 4 " tungstic acid that mixes in three (carbazole-9-yl) triphenylamine, its quality proportioning be 4,4 ', 4 " three (carbazole-9-yl) triphenylamines: tungstic acid=1: 0.01～0.5.
The Organic Light Emitting Diode of above-mentioned double-P type doped layer, the material of the described organic hole transmission that is deposited on organic P type doping hole transport auxiliary layer be 4,4 '-two (9-carbazole) biphenyl or 4,4 ', 4 " three (carbazole-9-yl) triphenylamines.
The Organic Light Emitting Diode of above-mentioned double-P type doped layer, the described material that is deposited on the organic luminous layer of organic cavity transmission layer are three (oxine) aluminium (III).
The Organic Light Emitting Diode of above-mentioned double-P type doped layer, the described material that is deposited on the electron injecting layer on the organic luminous layer is a lithium fluoride.
The Organic Light Emitting Diode of above-mentioned double-P type doped layer, the described material that is deposited on the negative electrode on the electron injecting layer is an aluminium.
The Organic Light Emitting Diode of above-mentioned double-P type doped layer, described material all can be by commercially available.
In order to save space, to list the english abbreviation of following compound, and all represent corresponding compounds hereinafter with english abbreviation.
4,4 ', 4 " three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine: m-MTDATA; 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-four cyanogen dimethyl 1,4-benzoquinone: F
4TCNQ; N4, N4, N4 ', N4 '-four (4-methoxyphenyl)-[1,1 '-biphenyl]-4,4 '-diamines: MeO-TPD; 4,4 '-two (9-carbazole) biphenyl: CBP; Three [1,2-two (trifluoromethyl) ethane-1,2-two thiol-ene] molybdenum: Mo (tfd)
34,4 ', 4 " three (carbazole-9-yl) triphenylamine: TCTA; Three (oxine) aluminium (III): Alq3; Lithium fluoride: LiF; Tungstic acid: WO
3Aluminium: Al; Gold: Au; Silver: Ag.
The preparation method of the Organic Light Emitting Diode of above-mentioned double-P type doped layer, its step is as follows:
The first step, the processing of the anode on the substrate
The glass substrate that covers with anode is called anode substrate, and this layer anode can be gold, silver or tin indium oxide conductive film; This anode substrate is cut into 4 * 4cm
2Fritter, in the ultrasonic cleaner that fills acetone, ethanol and deionized water, clean successively, clean respectively twice with aforementioned every kind of solvent, each 10 minutes, dry up with nitrogen afterwards, put into then and steam empty coating machine, steaming empty coating machine, to be extracted into background vacuum pressure be 4 * 10
-4Pa;
Second step, the organic P type doping hole transmission layer of deposition on anode
Adopt the thermal evaporation mode, doped F among the deposition m-MTDATA on the anode that the first step was handled
4The film of TCNQ is as organic P type doping hole transmission layer, and thickness is 7-200nm, and the doping mass ratio is: m-MTDATA: F
4TCNQ=1: 0.01～1: 0.5; Or depositing doped F among the MeO-TPD on the anode of handling in the first step
4The film of TCNQ is as organic P type doping hole transmission layer, and thickness is 7-200nm, and the doping mass ratio is: MeO-TPD: F
4TCNQ=1: 0.01～1: 0.5;
The 3rd step, the organic P type doping hole transport auxiliary layer of deposition on organic P type doping hole transmission layer
Adopt the thermal evaporation mode, on organic P type doping hole transmission layer of the second step deposition, deposit the Mo (tfd) that mixes among the CBP again
3Film as organic P type doping hole transport auxiliary layer, thickness is 1-3nm, the doping mass ratio is: CBP: Mo (tfd)
3=1: 0.01～0.5; Or on organic P type doping hole transmission layer of the second step deposition, deposit the WO that mixes among the TCTA again
3Film as organic P type doping hole transport auxiliary layer, thickness is 1-3nm, the doping mass ratio is: TCTA: WO
3=1: 0.01～0.5.
In the 4th step, on organic P type doping hole transport auxiliary layer, deposit organic cavity transmission layer
Adopt the thermal evaporation mode, deposit TCTA or CBP film again as organic cavity transmission layer on organic P type doping hole transport auxiliary layer of the 3rd step deposition, thickness is 10-50nm, and deposition rate is
In the 5th step, on organic cavity transmission layer, deposit organic luminous layer
Adopt the thermal evaporation mode, depositing Al q3 film organic luminous layer on the organic cavity transmission layer of the 4th step deposition, thickness is 60nm, deposition rate is
In the 6th step, on organic luminous layer, deposit electron injecting layer
Adopt the thermal evaporation mode, deposit the LiF film again as electron injecting layer on the organic luminous layer of the 5th step deposition, thickness is 1nm, and deposition rate is
The 7th step, deposition cathode on electron injecting layer
Adopt the thermal evaporation mode, on the electron injecting layer of the 6th step deposition the deposition of aluminum film as negative electrode, thickness 100nm, deposition rate is
Thus, finally making the Organic Light Emitting Diode of above-mentioned double-P type doped layer, is a kind of Organic Light Emitting Diode that adopts double-deck P type doping film to strengthen the hole injection.
Among the preparation method of the Organic Light Emitting Diode of above-mentioned double-P type doped layer, related equipment, technology all are that those skilled in the art are known, and related material all can be commercially available.
The invention has the beneficial effects as follows:
(1) substantive distinguishing features given prominence to of the present invention is:
The Organic Light Emitting Diode of double-P type doped layer proposed by the invention uses double-deck P type doping film, the design of ground floor P type doping film only need consider whether the conductivity of organic film can meet the demands, and do not need to consider it follows the energy level of organic cavity transmission layer whether to mate, the design of second layer P type doping film only need consider how the hole high efficiency is injected in the organic cavity transmission layer, and the conductivity that does not need to consider it has much.Hole transport shared different organic P type doped layers with injecting, such be configured as designs and the material design provides great flexibility, also to have created great space for the device performance lifting; And current widely used individual layer P type doping film technology wants balance to consider conductivity and energy level coupling factor in the material design, and this has just greatly limited the raising of hole current.Therefore, the present invention has outstanding substantive distinguishing features.
(2) marked improvement of the present invention is:
1, the organic cavity transmission layer material that often uses at present is m-MTDATA, TCTA, CBP, NPB etc., so the research that current P type mixes is also just carried out around these materials, this has greatly limited the development of P type dopant material and technology.The proposition of double-P type doping film structure is that opportunity has been created in the development of high-performance P type dopant material, and novel high-performance P type dopant material also can greatly improve device performance conversely.2, compare with traditional use individual layer P type doping film, use double-P type doping film structure the hole transport energy barrier can be reduced by 0.7～1.5eV.According to the heat emission model, the every reduction of hole transport energy barrier 0.1eV, hole current increases by 50 times, and corresponding device brightness increases more than 50 times.As can be seen, use double-deck P type doping film structure can significantly improve device performance, have wide application market and great commercial value.
This also has further narration in the following embodiments.
Description of drawings
Fig. 1 is the structural representation of the Organic Light Emitting Diode of double-P type doped layer of the present invention.
The Organic Light Emitting Diode of the double-P type doped layer that Fig. 2 makes for the embodiment of the invention 1 and existing employing individual layer P type doping film are realized the photoelectric properties comparison diagram of the Organic Light Emitting Diode that the hole is injected.Wherein, Fig. 2 a is a voltage-to-current density relationship curve chart; Fig. 2 b is voltage-brightness relationship curve chart.
The photoelectric properties figure of the Organic Light Emitting Diode of the double-P type doped layer that Fig. 3 makes for the embodiment of the invention 2, wherein, Fig. 3 a is a voltage-to-current density relationship curve chart; Fig. 3 b is voltage-brightness relationship curve chart.
Embodiment
Embodiment illustrated in fig. 1 showing, the Organic Light Emitting Diode of double-P type doped layer of the present invention is by one deck anode i on substrate, one is deposited upon the organic P type doping hole transmission layer ii on the anode, one is deposited upon the organic P type doping hole transport auxiliary layer iii on organic P type doping hole transmission layer, one is deposited upon the organic cavity transmission layer iv on organic P type doping hole transport auxiliary layer, one is deposited upon the organic luminous layer v on the organic cavity transmission layer, one is deposited upon the negative electrode that electron injecting layer vi and on the organic luminous layer is deposited upon on the electron injecting layer forms vii.
Embodiment 1
The preparation structure is ITO/m-MTDATA: F
4TCNQ=1: 0.01 thickness 7nm/CBP: Mo (tfd)
3The Organic Light Emitting Diode of=1: 0.01 thickness 3nm/CBP thickness 50nm/Alq3 thickness 60nm/LiF thickness 1nm/Al thickness 100nm.
This Organic Light Emitting Diode is that the thickness that is deposited upon on the ito anode by one deck ito anode, on the glass substrate is the m-MTDATA of 7nm: F
4The organic P type of TCNQ film doping hole transmission layer, one is deposited upon m-MTDATA: F
4Thickness on the organic P type of the TCNQ film doping hole transmission layer is the CBP of 3nm: Mo (tfd)
3The organic P type of film doping hole transport auxiliary layer, one is deposited upon CBP: Mo (tfd)
3Thickness on the organic P type of the film doping hole transport auxiliary layer is that the thickness that the CBP film organic cavity transmission layer, of 50nm is deposited upon on the CBP film organic cavity transmission layer is the Alq3 film organic luminous layer of 60nm, and one to be deposited upon thickness on the Alq3 film organic luminous layer be the Organic Light Emitting Diode that the LiF thin film electronic implanted layer and of 1nm is deposited upon the double-P type doped layer that the Al negative electrode on the LiF thin film electronic implanted layer forms.
Above-mentioned ITO is the abbreviation of indium tin oxide films, and ito anode abbreviates the ito anode substrate as attached on the glass substrate.The thickness of tin indium oxide conductive film is 100nm, and face resistance is less than 10 ohm/per 4 * 4cm
2Square.The ito anode substrate of present embodiment is produced by Nan Bo company.
The preparation method of the Organic Light Emitting Diode of above-mentioned double-P type doped layer is:
The first step, the processing of ito anode substrate
With the thickness of tin indium oxide conductive film is that 100nm, size are 4 * 4cm
2, face resistance is less than 10 ohm/per 4 * 4cm
2The ito anode substrate square of square in filling the ultrasonic cleaner of acetone, clean earlier twice, filling in the ultrasonic cleaner of ethanol and cleaning twice again, in filling the ultrasonic cleaner of deionized water, clean twice at last, each 10 minutes, dry up with nitrogen afterwards, put into afterwards and steam empty coating machine, steaming empty coating machine, to be extracted into background vacuum pressure be 4 * 10
-4Pa.
Second step, the organic P type doping hole transmission layer of deposition on anode
In vacuum coating equipment, adopt the thermal evaporation mode, doped F among the deposition m-MTDATA on the anode that the first step was handled
4The film of TCNQ is as organic P type doping hole transmission layer, and thickness is 7nm, and the doping mass ratio is: m-MTDATA: F
4TCNQ=1: 0.01;
The 3rd step, the organic P type doping hole transport auxiliary layer of deposition on organic P type doping hole transmission layer
In vacuum coating equipment, adopt the thermal evaporation mode, on organic P type doping hole transmission layer of the second step deposition, deposit the Mo (tfd) that mixes among the CBP again
3Film as organic P type doping hole transport auxiliary layer, thickness is 3nm, the doping mass ratio is: CBP: Mo (tfd)
3=1: 0.01.
In the 4th step, on organic P type doping hole transport auxiliary layer, deposit organic cavity transmission layer
In vacuum coating equipment, adopt the thermal evaporation mode, on organic P type doping hole transport auxiliary layer of the 3rd step deposition, deposit the CBP film again as organic cavity transmission layer, thickness is 50nm, deposition rate is
In the 5th step, on organic cavity transmission layer, deposit organic luminous layer
In vacuum coating equipment, adopt the thermal evaporation mode, depositing Al q3 film is as organic luminous layer again on the organic cavity transmission layer of the 4th step deposition, and thickness is 60nm, and deposition rate is
In the 6th step, on organic luminous layer, deposit electron injecting layer
In vacuum coating equipment, adopt the thermal evaporation mode, on the organic luminous layer of the 5th step deposition, deposit the LiF film again as electron injecting layer, thickness is 1nm, deposition rate is
The 7th step, deposition cathode on electron injecting layer
In vacuum coating equipment, adopt the thermal evaporation mode, on the electron injecting layer of the 6th step deposition the deposition of aluminum film as negative electrode, thickness 100nm, deposition rate is
Thus, finally making the Organic Light Emitting Diode of above-mentioned double-P type doped layer, is a kind of Organic Light Emitting Diode that adopts double-deck P type doping film to strengthen the hole injection.
The comparative example 1
The preparation structure is ITO/m-MTDATA: F
4TCNQ=1: the Organic Light Emitting Diode of 0.01 thickness 10nm/CBP thickness 50nm/Alq3 thickness 60nm/LiF thickness 1nm/Al thickness 100nm.
This Organic Light Emitting Diode is that the thickness that is deposited upon on the ito anode by one deck ito anode, on the glass substrate is the m-MTDATA of 10nm: F
4The organic P type of TCNQ film doping hole transmission layer, one is deposited upon m-MTDATA: F
4Thickness on the organic P type of the TCNQ film doping hole transmission layer is that the thickness that the CBP film organic cavity transmission layer, of 50nm is deposited upon on the CBP film organic cavity transmission layer is the Alq3 film organic luminous layer of 60nm, and one to be deposited upon thickness on the Alq3 film organic luminous layer be the Organic Light Emitting Diode that the LiF thin film electronic implanted layer and of 1nm is deposited upon the double-P type doped layer that the Al negative electrode on the LiF thin film electronic implanted layer forms.
This employing individual layer P type doping organic film realizes that the preparation method of the Organic Light Emitting Diode that the hole is injected is:
Remove outside " the 3rd step is at the organic P type doping hole transport auxiliary layer of deposition on organic P type doping hole transmission layer " that does not have among the embodiment 1, other process are all with embodiment 1.
If: the Organic Light Emitting Diode of embodiment 1 prepared double-P type doped layer is device A, and the Organic Light Emitting Diode of comparative example's 1 prepared traditional structure is device B.
Among Fig. 2 a, the square curve is the voltage-to-current density relationship curve of device A, and the circle curve is the voltage-to-current density relationship curve of device B.(the voltage-to-current density curve among the present invention is recorded by a keithley2400 DC digital source table)
Among Fig. 2 b, the square curve is voltage-brightness relationship curve of device A, and the circle curve is voltage-brightness relationship curve chart of device B.
From Fig. 2 a as can be seen, under same voltage, the current density of device A is significantly higher than device B, from Fig. 2 b as can be seen, under same voltage, the brightness of device A also is significantly higher than device B: when driving voltage is 9.4 volts, the brightness of device A is 7324 nits, current density is 241 milliamperes every square centimeter, and the brightness of device B is 103.2 nits, and current density is 3.6 milliamperes every square centimeter; When current density was 111.5 milliamperes every square centimeter, the maximum current efficient of device A reached every ampere of 3.1 candela, and the maximum current efficient of device B is every ampere of 3.0 candela.It mainly is than having reduced by 0.07 electron-volt among the device B because of the hole transport energy barrier among the device A that the performance of device A significantly is better than device B.Therefore, the Organic Light Emitting Diode of double-P type doped layer provided by the present invention has high efficiency hole function of injecting and can significantly improve device performance, and cheap, preparation is simple.
The preparation structure is Au 20nm/MeO-TPD: F
4TCNQ=1: 0.5 thickness 200nm/TCTA: MoO
3The Organic Light Emitting Diode of=1: 0.5 thickness 1nm/TCTA thickness 10nm/Alq3 thickness 60nm/LiF thickness 1nm/Al thickness 100nm.
This Organic Light Emitting Diode is to be that the thickness that the Au anode, of 20nm is deposited upon on the Au anode is the MeO-TPD of 200nm: F by the layer thickness on the glass substrate
4The organic P type of TCNQ film doping hole transmission layer, one is deposited upon MeO-TPD: F
4Thickness on the organic P type of the TCNQ film doping hole transmission layer is the TCTA of 1nm: MoO
3The organic P type of film doping hole transport auxiliary layer, one is deposited upon TCTA: MoO
3Thickness on the organic P type of the film doping hole transport auxiliary layer is that the thickness that the TCTA film organic cavity transmission layer, of 10nm is deposited upon on the TCTA film organic cavity transmission layer is the Alq3 film organic luminous layer of 60nm, and one to be deposited upon thickness on the Alq3 film organic luminous layer be the Organic Light Emitting Diode that the LiF thin film electronic implanted layer and of 1nm is deposited upon the double-P type doped layer that the Al negative electrode on the LiF thin film electronic implanted layer forms.
The preparation method of the Organic Light Emitting Diode of above-mentioned double-P type doped layer is:
The first step, the processing of the anode A u on the glass substrate
With size is 4 * 4cm
2Glass as substrate, with this substrate in filling the ultrasonic cleaner of acetone, clean earlier twice, filling in the ultrasonic cleaner of ethanol and cleaning twice again, in filling the ultrasonic cleaner of deionized water, clean twice at last, each 10 minutes, dry up with nitrogen afterwards, put into then and steam empty coating machine, steaming empty coating machine, to be extracted into background vacuum pressure be 4 * 10
-4Pa, deposition one layer thickness is the Au anode of 20nm on glass substrate;
Second step, the organic P type doping hole transmission layer of deposition on anode
In vacuum coating equipment, adopt the thermal evaporation mode, doped F among the deposition MeO-TPD on the anode that the first step was handled
4The film of TCNQ is as organic P type doping hole transmission layer, and thickness is 200nm, and the doping mass ratio is: MeO-TPD: F
4TCNQ=1: 0.5;
The 3rd step, the organic P type doping hole transport auxiliary layer of deposition on organic P type doping hole transmission layer
In vacuum coating equipment, adopt the thermal evaporation mode, on organic P type doping hole transmission layer of the second step deposition, deposit the WO that mixes among the TCTA again
3Film as organic P type doping hole transport auxiliary layer, thickness is 1nm, the doping mass ratio is: TCTA: WO
3=1: 0.5.
In the 4th step, on organic P type doping hole transport auxiliary layer, deposit organic cavity transmission layer
In vacuum coating equipment, adopt the thermal evaporation mode, on organic P type doping hole transport auxiliary layer of the 3rd step deposition, deposit the TCTA film again as organic cavity transmission layer, thickness is 10nm, deposition rate is
In the 5th step, on organic cavity transmission layer, deposit organic luminous layer
In vacuum coating equipment, adopt the thermal evaporation mode, depositing Al q3 film is as organic luminous layer again on the organic cavity transmission layer of the 4th step deposition, and thickness is 60nm, and deposition rate is
In the 6th step, on organic luminous layer, deposit electron injecting layer
In vacuum coating equipment, adopt the thermal evaporation mode, on the organic luminous layer of the 5th step deposition, deposit the LiF film again as electron injecting layer, thickness is 1nm, deposition rate is
The 7th step, deposition cathode on electron injecting layer
In vacuum coating equipment, adopt the thermal evaporation mode, on the electron injecting layer of the 6th step deposition the deposition of aluminum film as negative electrode, thickness 100nm, deposition rate is
Thus, finally making the Organic Light Emitting Diode of above-mentioned double-P type doped layer, is a kind of Organic Light Emitting Diode that adopts double-deck P type doping film to strengthen the hole injection.
Fig. 3 has provided the photoelectric properties of the Organic Light Emitting Diode of double-P type doped layer among the embodiment 2.Wherein, Fig. 3 a is a voltage-to-current density relationship curve chart, illustrates that the current density of this device in the time of 9 volts is 584.5 milliamperes every square centimeter; Fig. 3 b is voltage-brightness relationship curve chart, illustrates that the brightness of this device in the time of 9 volts reaches 11714 nits.When current density was 111.5 milliamperes every square centimeter, the maximum current efficient of this device reached every ampere of 3.4 candela, and device performance is good.
The preparation structure is Ag 20nm/MeO-TPD: F
4TCNQ=1: 0.01 thickness 200nm/TCTA: MoO
3The Organic Light Emitting Diode of=1: 0.01 thickness 1nm/TCTA thickness 10nm/Alq3 thickness 60nm/LiF thickness 1nm/Al thickness 100nm.
This Organic Light Emitting Diode is to be that the thickness that the Ag anode, of 20nm is deposited upon on the Ag anode is the MeO-TPD of 200nm: F by the layer thickness on the glass substrate
4The organic P type of TCNQ film doping hole transmission layer, one is deposited upon MeO-TPD: F
4Thickness on the organic P type of the TCNQ film doping hole transmission layer is the TCTA of 1nm: MoO
3The organic P type of film doping hole transport auxiliary layer, one is deposited upon TCTA: MoO
3Thickness on the organic P type of the film doping hole transport auxiliary layer is that the thickness that the TCTA film organic cavity transmission layer, of 10nm is deposited upon on the TCTA film organic cavity transmission layer is the Alq3 film organic luminous layer of 60nm, and one to be deposited upon thickness on the Alq3 film organic luminous layer be the Organic Light Emitting Diode that the LiF thin film electronic implanted layer and of 1nm is deposited upon the double-P type doped layer that the Al negative electrode on the LiF thin film electronic implanted layer forms.
The preparation method of the Organic Light Emitting Diode of above-mentioned double-P type doped layer is:
The first step, the processing of the anode A g on the glass substrate
With size is 4 * 4cm
2Glass as substrate, with this substrate in filling the ultrasonic cleaner of acetone, clean earlier twice, filling in the ultrasonic cleaner of ethanol and cleaning twice again, in filling the ultrasonic cleaner of deionized water, clean twice at last, each 10 minutes, dry up with nitrogen afterwards, put into then and steam empty coating machine, steaming empty coating machine, to be extracted into background vacuum pressure be 4 * 10
-4Pa, deposition one layer thickness is the Ag anode of 20nm on glass substrate;
Second step, the organic P type doping hole transmission layer of deposition on anode
In vacuum coating equipment, adopt the thermal evaporation mode, doped F among the deposition MeO-TPD on the anode that the first step was handled
4The film of TCNQ is as organic P type doping hole transmission layer, and thickness is 200nm, and the doping mass ratio is: MeO-TPD: F
4TCNQ=1: 0.01;
The 3rd step, the organic P type doping hole transport auxiliary layer of deposition on organic P type doping hole transmission layer
In vacuum coating equipment, adopt the thermal evaporation mode, on organic P type doping hole transmission layer of the second step deposition, deposit the WO that mixes among the TCTA again
3Film as organic P type doping hole transport auxiliary layer, thickness is 1nm, the doping mass ratio is: TCTA: WO
3=1: 0.01.
In the 4th step, on organic P type doping hole transport auxiliary layer, deposit organic cavity transmission layer
In vacuum coating equipment, adopt the thermal evaporation mode, on organic P type doping hole transport auxiliary layer of the 3rd step deposition, deposit the TCTA film again as organic cavity transmission layer, thickness is 10nm, deposition rate is
In the 5th step, on organic cavity transmission layer, deposit organic luminous layer
In vacuum coating equipment, adopt the thermal evaporation mode, depositing Al q3 film is as organic luminous layer again on the organic cavity transmission layer of the 4th step deposition, and thickness is 60nm, and deposition rate is
In the 6th step, on organic luminous layer, deposit electron injecting layer
In vacuum coating equipment, adopt the thermal evaporation mode, on the organic luminous layer of the 5th step deposition, deposit the LiF film again as electron injecting layer, thickness is 1nm, deposition rate is
The 7th step, deposition cathode on electron injecting layer
In vacuum coating equipment, adopt the thermal evaporation mode, on the electron injecting layer of the 6th step deposition the deposition of aluminum film as negative electrode, thickness 100nm, deposition rate is
Thus, finally making the Organic Light Emitting Diode of above-mentioned double-P type doped layer, is a kind of Organic Light Emitting Diode that adopts double-deck P type doping film to strengthen the hole injection.
Can find out advantage of the present invention from embodiment 1 and comparative example's 1 comparison.In embodiment 1, we adopt 7nmm-MTDATA: F
4TCNQ (1: 0.01) film transporting holes, use 3nm CBP: Mo (tfd)
3(1: 0.01) film with the hole from m-MTDATA: F
4The TCNQ film is injected in the CBP film; In comparative example 1, we adopt 10nmm-MTDATA: F
4TCNQ (1: 0.01) film is transporting holes but also be responsible for the hole is injected in the CBP film not only.Though CBP: Mo (tfd)
3The conductivity of (1: 0.01) significantly is lower than m-MTDATA: F
4TCNQ (1: 0.01), but from CBP: Mo (tfd)
3(1: 0.01) film injects energy barrier to the hole of CBP film and is significantly less than from m-MTDATA: F
4TCNQ (1: 0.01) film injects energy barrier to the hole of CBP film, and as seen in Figure 2, the current density ratio comparative example 1 of embodiment 1 in the time of 9.4 volts exceeds nearly 70 times.Therefore, double-deck P type doping film technology will significantly be better than current individual layer P type doping film technology.
Claims (10)
1. the Organic Light Emitting Diode of a double-P type doped layer, it is characterized by this diode is a kind of Organic Light Emitting Diode that uses double-deck P type doping film to strengthen the hole injection, by one deck anode on the glass substrate, one is deposited upon the organic P type doping hole transmission layer on the anode, one is deposited upon the organic P type doping hole transport auxiliary layer on organic P type doping hole transmission layer, one is deposited upon the organic cavity transmission layer on organic P type doping hole transport auxiliary layer, one is deposited upon the organic luminous layer on the organic cavity transmission layer, and an electron injecting layer that is deposited upon on the organic luminous layer is formed with one deck negative electrode that is deposited on the electron injecting layer.
2. the Organic Light Emitting Diode of double-P type doped layer as claimed in claim 1, it is characterized by described anode is that thickness is the electric conductive oxidation indium tin thin film of 100nm, or the thick noble metal film of 20nm, described noble metal is a gold or silver-colored.
3. the Organic Light Emitting Diode of double-P type doped layer as claimed in claim 2, the face resistance that it is characterized by described tin indium oxide conductive film is less than 10 ohm/per 4 * 4cm
2Square.
4. the Organic Light Emitting Diode of double-P type doped layer as claimed in claim 1, it is characterized by the described material that is deposited on the organic P type doping hole transmission layer on the anode is 4,4 ', 4 " mix 2,3 in three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine; 5; 6-tetrafluoro-7,7 ', 8; 8 '-four cyanogen dimethyl 1,4-benzoquinone; and its quality proportioning is 4,4 ', 4 " three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamines: 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-four cyanogen dimethyl 1,4-benzoquinone=1: 0.01～0.5; Or at N4, N4, N4 ', N4 '-four (4-methoxyphenyl)-[1,1 '-biphenyl]-4,4 '-mix 2,3,5 in the diamines, 6-tetrafluoro-7,7 ', 8,8 '-four cyanogen dimethyl 1,4-benzoquinone, its quality proportioning is N4, N4, N4 ', N4 '-four (4-methoxyphenyl)-[1,1 '-biphenyl]-4,4 '-diamines: 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-four cyanogen dimethyl 1,4-benzoquinone=1: 0.01～0.5.
5. the Organic Light Emitting Diode of double-P type doped layer as claimed in claim 1, it is characterized by the described material that is deposited on the organic P type doping hole transport auxiliary layer on organic P type doping hole transmission layer is 4, mix three [1 in 4 '-two (9-carbazole) biphenyl, 2-two (trifluoromethyl) ethane-1,2-two thiol-ene] molybdenum, its quality proportioning is 4,4 '-two (9-carbazole) biphenyl: three [1,2-two (trifluoromethyl) ethane-1,2-two thiol-ene] molybdenum=1: 0.01～0.5; Or 4,4 ', 4 " tungstic acid that mixes in three (carbazole-9-yl) triphenylamine, its quality proportioning be 4,4 ', 4 " three (carbazole-9-yl) triphenylamines: tungstic acid=1: 0.01～0.5.
6. the Organic Light Emitting Diode of double-P type doped layer as claimed in claim 1, it is characterized by the described material that is deposited on the organic cavity transmission layer of organic P type doping hole transport auxiliary layer is 4,4 '-two (9-carbazole) biphenyl or 4,4 ', 4 " three (carbazole-9-yl) triphenylamines.
7. the Organic Light Emitting Diode of double-P type doped layer as claimed in claim 1, it is characterized by the described material that is deposited on the organic luminous layer of organic cavity transmission layer is three (oxine) aluminium (III).
8. the Organic Light Emitting Diode of double-P type doped layer as claimed in claim 1, it is characterized by the described material that is deposited on the electron injecting layer on the organic luminous layer is lithium fluoride.
9. the Organic Light Emitting Diode of double-P type doped layer as claimed in claim 1, it is characterized by the described material that is deposited on the negative electrode on the electron injecting layer is aluminium.
10. the preparation method of the Organic Light Emitting Diode of double-P type doped layer as claimed in claim 1, it is as follows to it is characterized by step:
The first step, the processing of the anode on the substrate
The glass substrate that covers with anode is called anode substrate, and this layer anode can be gold, silver or tin indium oxide conductive film; This anode substrate is cut into 4 * 4cm
2Fritter, in the ultrasonic cleaner that fills acetone, ethanol and deionized water, clean successively, clean respectively twice with aforementioned every kind of solvent, each 10 minutes, dry up with nitrogen afterwards, put into then and steam empty coating machine, steaming empty coating machine, to be extracted into background vacuum pressure be 4 * 10
-4Pa;
Second step, the organic P type doping hole transmission layer of deposition on anode
Adopt the thermal evaporation mode, doped F among the deposition m-MTDATA on the anode that the first step was handled
4The film of TCNQ is as organic P type doping hole transmission layer, and thickness is 7-200nm, and the doping mass ratio is: m-MTDATA: F
4TCNQ=1: 0.01～1: 0.5; Or depositing doped F among the MeO-TPD on the anode of handling in the first step
4The film of TCNQ is as organic P type doping hole transmission layer, and thickness is 7-200nm, and the doping mass ratio is: MeO-TPD: F
4TCNQ=1: 0.01～1: 0.5;
The 3rd step, the organic P type doping hole transport auxiliary layer of deposition on organic P type doping hole transmission layer
Adopt the thermal evaporation mode, on organic P type doping hole transmission layer of the second step deposition, deposit the Mo (tfd) that mixes among the CBP again
3Film as organic P type doping hole transport auxiliary layer, thickness is 1-3nm, the doping mass ratio is: CBP: Mo (tfd)
3=1: 0.01～0.5; Or on organic P type doping hole transmission layer of the second step deposition, deposit the WO that mixes among the TCTA again
3Film as organic P type doping hole transport auxiliary layer, thickness is 1-3nm, the doping mass ratio is: TCTA: WO
3=1: 0.01～0.5;
In the 4th step, on organic P type doping hole transport auxiliary layer, deposit organic cavity transmission layer
Adopt the thermal evaporation mode, deposit CBP or TCTA film again as organic cavity transmission layer on organic P type doping hole transport auxiliary layer of the 3rd step deposition, thickness is 10-50nm, and deposition rate is
In the 5th step, on organic cavity transmission layer, deposit organic luminous layer
Adopt the thermal evaporation mode, depositing Al q3 film organic luminous layer on the organic cavity transmission layer of the 4th step deposition, thickness is 60nm, deposition rate is
In the 6th step, on organic luminous layer, deposit electron injecting layer
Adopt the thermal evaporation mode, deposit the LiF film again as electron injecting layer on the organic luminous layer of the 5th step deposition, thickness is 1nm, and deposition rate is
The 7th step, deposition cathode on electron injecting layer
Adopt the thermal evaporation mode, on the electron injecting layer of the 6th step deposition the deposition of aluminum film as negative electrode, thickness 100nm, deposition rate is
Thus, finally making the Organic Light Emitting Diode of above-mentioned double-P type doped layer, is a kind of Organic Light Emitting Diode that adopts double-deck P type doping film to strengthen the hole injection.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103633111A (en) * | 2012-08-24 | 2014-03-12 | 乐金显示有限公司 | Organic light-emitting diode and method of fabricating the same |
| CN105470404A (en) * | 2015-11-23 | 2016-04-06 | 北京大学 | Energy-saving and environment-friendly organic light-emitting element |
| CN109216565A (en) * | 2017-06-30 | 2019-01-15 | 昆山国显光电有限公司 | Organic electroluminescence device and preparation method thereof |
| CN109509840A (en) * | 2017-09-14 | 2019-03-22 | 上海和辉光电有限公司 | A kind of structure of OLED device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1761084A (en) * | 2005-10-12 | 2006-04-19 | 友达光电股份有限公司 | Organic light-emitting diode, and display unit containing the organic light-emitting diode |
| US20060099448A1 (en) * | 2003-04-28 | 2006-05-11 | Zheng-Hong Lu | Top light-emitting devices with fullerene layer |
| CN101359721A (en) * | 2008-09-23 | 2009-02-04 | 吉林大学 | Top radiation organic EL part with optical spectrum adjustable |
| CN101383400A (en) * | 2008-10-07 | 2009-03-11 | 中国科学院长春应用化学研究所 | Organic light emitting device using high conductive hole transport material as hole transport layer |
| WO2010079051A1 (en) * | 2009-01-07 | 2010-07-15 | Basf Se | Silyl and heteroatom substituted compounds selected from carbazoles, dibenzofurans, dibenzothiophenes and dibenzo phospholes and the application thereof in organic electronics |
-
2011
- 2011-06-09 CN CN 201110153287 patent/CN102214801B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060099448A1 (en) * | 2003-04-28 | 2006-05-11 | Zheng-Hong Lu | Top light-emitting devices with fullerene layer |
| CN1761084A (en) * | 2005-10-12 | 2006-04-19 | 友达光电股份有限公司 | Organic light-emitting diode, and display unit containing the organic light-emitting diode |
| CN101359721A (en) * | 2008-09-23 | 2009-02-04 | 吉林大学 | Top radiation organic EL part with optical spectrum adjustable |
| CN101383400A (en) * | 2008-10-07 | 2009-03-11 | 中国科学院长春应用化学研究所 | Organic light emitting device using high conductive hole transport material as hole transport layer |
| WO2010079051A1 (en) * | 2009-01-07 | 2010-07-15 | Basf Se | Silyl and heteroatom substituted compounds selected from carbazoles, dibenzofurans, dibenzothiophenes and dibenzo phospholes and the application thereof in organic electronics |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103633111A (en) * | 2012-08-24 | 2014-03-12 | 乐金显示有限公司 | Organic light-emitting diode and method of fabricating the same |
| CN105470404A (en) * | 2015-11-23 | 2016-04-06 | 北京大学 | Energy-saving and environment-friendly organic light-emitting element |
| CN105470404B (en) * | 2015-11-23 | 2017-05-17 | 北京大学 | Energy-saving and environment-friendly organic light-emitting element |
| CN109216565A (en) * | 2017-06-30 | 2019-01-15 | 昆山国显光电有限公司 | Organic electroluminescence device and preparation method thereof |
| US11233201B2 (en) | 2017-06-30 | 2022-01-25 | Kunshan Go-Visionox Opto-Electronics Co., Ltd. | Organic electroluminescent devices and preparation methods thereof |
| CN109509840A (en) * | 2017-09-14 | 2019-03-22 | 上海和辉光电有限公司 | A kind of structure of OLED device |
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