CN105789459A - Red organic light emitting diode and fabrication method thereof - Google Patents
Red organic light emitting diode and fabrication method thereof Download PDFInfo
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- CN105789459A CN105789459A CN201410765474.5A CN201410765474A CN105789459A CN 105789459 A CN105789459 A CN 105789459A CN 201410765474 A CN201410765474 A CN 201410765474A CN 105789459 A CN105789459 A CN 105789459A
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Abstract
The invention discloses a red organic light emitting diode. The red organic light emitting diode comprises a substrate, an anode, a hole injection layer, a light emitting layer, an electron transmission layer, a buffer layer and a cathode which are sequentially arranged from bottom to top. An iridium complex is taken as a light emitting material, the light emitting material has favorable solubility and can present high dispersibility in a main body material, concentration quenching effect and non-uniform dispersing phenomenon caused by high concentration doping are reduced, and high quantum efficiency is achieved. Meanwhile, the embodiment of the invention also provides a fabrication method of the red organic light emitting diode. The method is simple, and a complicated evaporation process and the expensive device cost are avoided; a hole material PVK is taken as a framework, OXD-7 is doped and CBP is mixed to form a composite main body, the CBP and the PVK have hole transmission characteristics, the OXD-7 has the electron transmission characteristic, thus, electron and hole balance is effectively adjusted, the recombination of holes and electrons on the light emitting layer is facilitated, and the diode efficiency is greatly improved.
Description
Technical field
The present invention relates to organic electroluminescence device technical field, be specifically related to a kind of red organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (organiclightemittingdiode, OLED) is a kind of to utilize carrier to be entered, by positive and negative electrode, the device that the phenomenon of organic solid layer compound and luminescence is made under electric field action.
Compared with LCD, OLED has all solid state, self-luminous, wide viewing angle, high-resolution, high brightness, high-contrast, high response speed, ultra-thin, low-power consumption, low temperature resistant, antidetonation, can realize the feature such as Flexible Displays and double-sided display.Given this advantage, OLED has broad application prospects.
Organic electroluminescence device structure includes: negative electrode, anode, hole injection layer, luminescent layer, electron transfer layer.
Red organic luminescent device is substantially using the coordination compound of iridium as luminescent material.Common red emitting material has (btp)2Ir(acac)、(fbi)2Ir(acac)、(DMQ)2Ir (acac), generally prepares organic electroluminescence device by the method that itself and fluorescent host double source steam altogether, and device architecture is generally bilayer, multilamellar, complicated process of preparation, adds the process costs of device, is unfavorable for that industrialization produces.
Summary of the invention
For solving the technical problem of existing existence, the embodiment of the present invention provides a kind of red organic electroluminescence device and preparation method thereof.
For reaching above-mentioned purpose, the technical scheme of the embodiment of the present invention is achieved in that
The embodiment of the present invention provides a kind of red organic electroluminescence device, and this red organic electroluminescence device includes: the substrate that sets gradually from top to bottom, anode, hole injection layer, luminescent layer, electron transfer layer, cushion, negative electrode；Described luminescent layer is complex of iridium and organic hybrid agent material mixing forms, and its mass ratio is (8 ~ 16): 100；Described complex of iridium molecular formula is；Described organic hybrid agent material is poly-(9-VCz) (PVK), 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-diazole] (OXD-7), 4,4'-bis-(9-carbazole) biphenyl (CBP).
In such scheme, described hole injection layer is PEDOT:PSS.
In such scheme, described electron transfer layer is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi).
In such scheme, the thickness of described luminescent layer is 30 ~ 50nm.
The preparation method that the embodiment of the present invention provides a kind of red organic electroluminescence device, this preparation method is realized by following steps:
Step 101: the substrate that surface is coated with anode material carries out plasma treatment；
Step 102: at described anode surface successively spin coating hole injection layer, luminescent layer；
Step 103: be deposited with electron injecting layer, cushion and negative electrode successively on described luminescent layer surface, prepares red organic electroluminescence device.
In such scheme, in described step 101, the vacuum of plasma treatment is 15 ~ 45Pa, and power is 150 ~ 350w.
In such scheme, described step 102 is particularly as follows: under pure air environment, at described transparent anode surface spin coating hole injection layer；Under high pure nitrogen environment, at described hole injection layer surface spin coating luminescent layer.
In such scheme, described step 103 is particularly as follows: at (1 ~ 8) x10-7When Torr, carry out evaporation electron injecting layer on the surface of described luminescent layer；At (1 ~ 5) x10-6When Torr, carry out evaporation cushion and negative electrode on described electron injecting layer surface.
Compared with prior art, beneficial effects of the present invention:
The embodiment of the present invention provides a kind of red organic electroluminescence device, including the substrate set gradually from top to bottom, anode, hole injection layer, luminescent layer, electron transfer layer, cushion and negative electrode；Adopt complex of iridium as luminescent material by the present invention, there is good solubility, polymolecularity can be presented in material of main part, decrease the concentration quenching effect owing to high-concentration dopant causes and dispersion uneven phenomenon and high-quantum efficiency；The preparation method that the embodiment of the present invention also provides for a kind of red organic electroluminescence device simultaneously, method is simple, avoid the evaporation process of complexity and the equipment cost of costliness thereof, using cavity type material PVK as skeleton, OXD-7 and the CBP compound main body of blended formation of adulterating, CBP and PVK has hole transporting properties, and OXD-7 has electron transport property, effectively have adjusted electronics and hole balance, thus being conducive to hole and electronics in luminescent layer compound, substantially increasing device efficiency.
Accompanying drawing explanation
The structural representation of a kind of red organic electroluminescence device that Fig. 1 provides for the embodiment of the present invention；
Fig. 2 is the voltage-current density-luminosity response of red organic electroluminescence device prepared by the embodiment of the present invention；
Red organic electroluminescence device prepared by Fig. 3 embodiment is 1000cd/m in brightness2Time spectrogram.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The embodiment of the present invention provides a kind of red organic electroluminescence device, as it is shown in figure 1, this red organic electroluminescence device includes: the substrate 1 that sets gradually from top to bottom, anode 2, hole injection layer 3, luminescent layer 4, electron transfer layer 5, cushion 6, negative electrode 7；Described luminescent layer 4 forms for complex of iridium and organic hybrid agent material mixing, and its mass ratio is (8 ~ 16): 100；Described complex of iridium molecular formula is；Described organic hybrid agent material is poly-(9-VCz) (PVK), 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-diazole] (OXD-7), 4,4'-bis-(9-carbazole) biphenyl (CBP).
Described hole injection layer 3 is PEDOT:PSS, and this layer has the function of hole injection, hole transport and electronic blocking concurrently, and the thickness of hole transmission layer 3 is preferably 25 ~ 60nm.
Described electron transfer layer 5 is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi), and this layer has the function of hole barrier, electric transmission and injection concurrently, reduces the running voltage of device, simplifies the structure of device simultaneously.Hole barrier layer thickness is preferably 15 ~ 40nm.
The thickness of described luminescent layer 4 is 30 ~ 50nm.
The present invention adopts complex of iridium as luminescent material, and it is that three (1-(4-n-hexyl phenyl)-isoquinolin-C2, N) close iridium (III), hereinafter referred to as Hex-Ir (piq)3, this complex of iridium has good solubility, can present polymolecularity in material of main part, decreases the concentration quenching effect owing to high-concentration dopant causes and dispersion uneven phenomenon and high-quantum efficiency.
In addition, material of main part adopts using cavity type material PVK as skeleton, doping OXD-7 and the CBP compound main body of blended formation, CBP and PVK has hole transporting properties, and OXD-7 has electron transport property, effectively have adjusted electronics and hole balance, thus being conducive to hole and electronics in luminescent layer compound, substantially increasing device efficiency, its luminous efficiency is stable.
The luminous efficiency of device is had large effect, the Weight control of complex of iridium of the present invention and material of main part to be (8 ~ 16) by above-mentioned luminescent layer 4 complex of iridium and material of main part mass ratio: 100, and ratio is excessive or too low all can cause that device light emitting efficiency reduces.
The present invention provides the substrate 1 in red organic electroluminescence device, anode 2, hole injection layer 3, electron transfer layer 5, cushion 6 and negative electrode 7 can adopt the respective material of existing red organic electroluminescence device.
The described preferred glass of substrate 1 is as substrate, and the tin indium oxide (ITO) that anode 2 is preferably commonly used, its resistance is preferably 8 ~ 20 Ω/■；Preferred its thickness of metallic aluminium (Al) of described negative electrode 7 is preferably 60 ~ 150nm；Described cushion 6 preferred fluorinated lithium (LiF), its thickness is preferably 0.5 ~ 1nm, and the effect of described cushion 6 is in that to reduce interface potential barrier, improves electronics injectability.
The operation principle of red organic electroluminescence device provided by the invention is as follows:
Load forward bias voltage at device two ends, hole and electronics inject from anode and negative electrode respectively, form carrier, through transmission, arrive luminescent layer and are compounded to form exciton, and exciton moves back state of activation radioluminescence.
By such scheme it can be seen that the present invention initially with complex of iridium as luminescent material, this material has good solubility, can present polymolecularity and high-quantum efficiency in material of main part.Meanwhile, the present invention adopts solwution method to prepare luminescent layer, and method is simple, it is to avoid complicated evaporation process and the equipment cost of costliness thereof.
The preparation method that the embodiment of the present invention also provides for a kind of red organic electroluminescence device, this preparation method is realized by following steps:
Step 101: the substrate 1 that surface is coated with anode material carries out plasma treatment；
Step 102: at described anode 2 surface spin coating hole injection layer 3 successively, luminescent layer 4；
Step 103: be deposited with electron injecting layer 5, cushion 6 and negative electrode 7 successively on described luminescent layer 4 surface, prepares red organic electroluminescence device.
In described step 101, the vacuum of plasma treatment is 15 ~ 45Pa, and power is 150 ~ 350w.
Under pure air environment, at described transparent anode surface spin coating hole injection layer 3；Under high pure nitrogen environment, at described hole injection layer surface spin coating luminescent layer 4.
Described step 103 is particularly as follows: at (1 ~ 8) x10-7When Torr, carry out evaporation electron injecting layer 5 on the surface of described luminescent layer；At (1 ~ 5) x10-6When Torr, carry out evaporation cushion 6 and negative electrode 7 on described electron injecting layer 5 surface.
First the present invention carries out solution cleaning in antianode 2 surface, preferably employ ultrasonic cleaning, be dried after cleaning, then carry out oxygen plasma treatment, purpose is in that to clean anode surface, reduce surface roughness, delivery of supplemental oxygen content, improve Hole injection capacity, in processing procedure, vacuum is preferably 15 ~ 45Pa, and power is 150 ~ 350w, and the process time is preferably 10 ~ 15min.
In the present invention, spin coating operation preferably carries out as follows:
In the step that described anode 2 surface utilizes spin-coating method to prepare hole injection layer 3, spin-coating method prepares luminescent layer 4；
Described spin-coating method prepare hole injection layer 3 and luminescent layer 4 particularly as follows:
Spin coating process medium speed is chosen as 2000rpm ~ 4000rpm；
In the present invention, the material of main part of described luminescent layer 4 is PVK, OXD-7, CBP；Hole-injecting material preferably employs PEDOT:PSS；Electron injection material TPBi, Libpp, B3PyMPM, B4PyMPM, Alq3, Tm3PyPB etc., evaporation rate preferably controls to be 0.03 ~ 0.8nm/s.Described cushion 6 preferably employs LiF, and evaporation rate is preferably 0.01 ~ 0.02nm/s.Described negative electrode 7 preferably employs metallic aluminium, and evaporation rate is preferably 0.1 ~ 0.2nm/s.
The red organic electroluminescence device prepared according to the present invention has higher luminous efficiency and brightness, and running voltage is low.
Embodiment:
Ito anode layer laser ablation on ito glass becoming the square-shaped electrode of 50mm, then uses cleanout fluid, deionized water ultrasonic cleaning 15 minutes successively, after process completes, high pure nitrogen dries up.
Substrate after drying up is put into plasma, carries out evacuation, when vacuum values reaches the scope of 30Pa, with 150w power, ito anode is carried out the oxygen plasma treatment of 5min.
Carrying out the preparation of hole injection layer PEDOT:PSS in clean atmospheric environment, spin coating parameters is chosen as rotating speed 4000rpm, spin-coating time 60s, puts into nitrogen glove box and carry out 150 DEG C of annealings after having prepared.
Spin coating luminescent layer on hole transmission layer, the organic hybrid agent material of luminescent layer is PVK, OXD-7, CBP, and phosphorescence dopant material is Hex-Ir(piq)3, select chlorobenzene, dichloro-benzenes or toluene as solvent, solution total concentration is 15mg/mL.Spin coating parameters is rotating speed 3000rpm, and spin-coating time is 60s, then carries out 100 DEG C of annealings.
Device is transferred to organic vapor deposition room, at (1 ~ 8) x10-7Under the vacuum condition of Torr, carry out the thick TPBi electron injecting layer of evaporation 30nm on the surface of luminescent layer；
Device is transferred to metal evaporation room, at (1 ~ 5) x10-6Under the vacuum condition of Torr, the LiF cushion that evaporation 0.7nm is thick, being deposited with the thick metal aluminium electrode of 120nm on LiF layer by mask plate, preparing into structure is ITO/PEDOT:PSS/ (PVK (20%): OXD-7 (40%): CBP (40%)): the organic electroluminescence device of Hex-Ir (piq) 3 (16%)/TPBi/LiF/Al.The light-emitting area of this device is 2500 square millimeters.
In evaporation process:
In electron transfer layer, the evaporation rate of TPBi controls at 0.05nm/s；
The evaporation rate of cushion LiF controls at 0.001nm/s；
The evaporation rate of negative electrode aluminum controls at 0.1nm/s.
Fig. 2 is the voltage-current density-luminosity response of red organic electroluminescence device prepared by this example, and as can be seen from the figure the bright voltage that opens of device is 2.8v.
Fig. 3 is the red organic electroluminescence device brightness prepared of this example spectrogram when 1000cd/m2, and its emission peak is 612nm.
Claims (8)
1. a red organic electroluminescence device, it is characterized in that, this red organic electroluminescence device includes: the substrate (1) that sets gradually from top to bottom, anode (2), hole injection layer (3), luminescent layer (4), electron transfer layer (5), cushion (6), negative electrode (7)；Described luminescent layer (4) forms for complex of iridium and organic hybrid agent material mixing, and its mass ratio is (8 ~ 16): 100；Described complex of iridium molecular formula is；Described organic hybrid agent material is poly-(9-VCz) (PVK), 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-diazole] (OXD-7), 4,4'-bis-(9-carbazole) biphenyl (CBP).
2. red organic electroluminescence device according to claim 1, it is characterised in that: described hole injection layer (3) is PEDOT:PSS.
3. red organic electroluminescence device according to claim 1, it is characterised in that: described electron transfer layer (5) is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi).
4. red organic electroluminescence device according to claim 1, it is characterised in that: the thickness of described luminescent layer (4) is 30 ~ 50nm.
5. the preparation method of a red organic electroluminescence device, it is characterised in that this preparation method is realized by following steps:
Step 101: the substrate (1) that surface is coated with anode material carries out plasma treatment；
Step 102: on described anode (2) surface successively spin coating hole injection layer (3), luminescent layer (4)；
Step 103: be deposited with electron injecting layer (5), cushion (6) and negative electrode (7) on described luminescent layer (4) surface successively, prepares red organic electroluminescence device.
6. the preparation method of red organic electroluminescence device according to claim 5, it is characterised in that: in described step 101, the vacuum of plasma treatment is 15 ~ 45Pa, and power is 150 ~ 350w.
7. the preparation method of red organic electroluminescence device according to claim 5, it is characterised in that: described step 102 is particularly as follows: under pure air environment, in described transparent anode surface spin coating hole injection layer (3)；Under high pure nitrogen environment, in described hole injection layer surface spin coating luminescent layer (4).
8. the preparation method of red organic electroluminescence device according to claim 5, it is characterised in that: described step 103 is particularly as follows: at (1 ~ 8) x10-7When Torr, carry out evaporation electron injecting layer (5) on the surface of described luminescent layer；At (1 ~ 5) x10-6When Torr, carry out evaporation cushion (6) and negative electrode (7) on described electron injecting layer (5) surface.
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