CN101179114A - Flexible organic electroluminescent device and method of producing the same - Google Patents
Flexible organic electroluminescent device and method of producing the same Download PDFInfo
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- CN101179114A CN101179114A CNA2007101508410A CN200710150841A CN101179114A CN 101179114 A CN101179114 A CN 101179114A CN A2007101508410 A CNA2007101508410 A CN A2007101508410A CN 200710150841 A CN200710150841 A CN 200710150841A CN 101179114 A CN101179114 A CN 101179114A
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Abstract
The invention discloses a flexible organic light emitting device and the preparation method. The structure of flexible organic light emitting device includes flexible substrate, the silver film which is modified by self-assembled monolayer on flexible substrate, hole-transporting layer, emitting layer, electron transport layer and metal cathode. The invention takes the silver film which is modified by self-assembled monolayer as the anode of flexible organic light emitting device, brings down the interface barrier which is between anode and common hole-transporting layer materials effectively; solves the problems of high resistivity, intolerant of bending, easy stripping and relatively low work function of current flexible organic light emitting device ITO anode; improves luminous brightness and efficiency of device; simplifies manufacturing process of device; reduces manufacturing cost and is convenient for industrial production.
Description
[technical field]: the present invention relates to a kind of flexible organic electroluminescent device and preparation method thereof, belong to technical field of organic electroluminescence.
[background technology]: organic electroluminescent LED (OLED) is a kind of brand-new Display Technique, surpasses 1000cd/m since C.W.Tang in 1987 etc. have reported brightness
2Double-deck organic film luminescent device since, but plurality of advantages such as OLED is low with its cost of manufacture, low driving voltage, the panchromatic demonstration of high efficiency large tracts of land cause more and more researchers' interest.And in the potential using value of aspects such as flat panel display, illumination and organic laser and receive much concern, developed into international advanced subject and various countries' high-tech competition focal point of multidisciplinary intersection.As the display device of full curing, its prime advantage is to realize flexible the demonstration.Flexible organic electro-luminescence diode (F-OLED) device for preparing on flexible substrate is flexible, light weight, be easy to carry, and has widened the scope of application of OLED greatly, is the important development direction of OLED.The device that with glass is substrate has been obtained considerable progress in the year surplus short ten, but the progress of flexible device is slow relatively.This is because the change of substrate (substrate) has brought many new problems to preparation of devices.The key of flexible display device is the selection and the exploitation of flexible substrate.One of preparation main difficulty that flexible organic electroluminescent device faced is exactly the transparent anode that how to prepare low-resistivity on polymer matrix film.
At present the anode in flexible OLED research normally adopts indium and tin oxide film (ITO) as conductive layer.Adopt ITO to exist following problem as the transparent anode of flexible OLED:
1. most polymers all can't be born the annealing temperature about 200 ℃ in the ito thin film preparation process.And without annealing, the ito thin film resistivity that deposits on the polymer flexibility substrate under cryogenic conditions is higher.
2.ITO film exists the diffusion problem of indium during as the transparency electrode of device.The diffusion of indium can influence the photoelectric properties of device, reduces the stability of OLED device, has shortened useful life.And indium is rare metal at nature, and its price is very expensive, has further limited its industrialized process.And the magnetron sputtering method of oxygenation argon filling is adopted in the preparation of existing ito thin film mostly, and the technology cost is also very high.
3.ITO film is cracked easily when bending, thereby causes component failure.And the common polymer substrate is opposite with the hot expansibility of ITO, the difference of this hot exapnsion performance makes the ito thin film that deposits on the polymer flexibility substrate peel off easily, when electric current was big, the Joule heat that device work produces promptly may cause the ITO conductive layer to be peeled off.
4. even can obtain ito thin film preferably at the ultra-thin glass of thickness below 0.3mm.Because the work function of ito thin film is 4.7eV, and exist bigger potential barrier between the HOMO track of hole transport layer material (NPB, TPD etc.) commonly used, must between anode ITO and hole transmission layer, insert hole injection resilient coating usually and carry out modifying interface to reduce interface potential barrier.The complexity and the technology cost of device preparation when having increased industrialization.
1992, [Gustafsson G such as Gustafsson, Cao Y, Treacy G M, et a1.Flexible light emitting diodes madefrom soluble conducting polymers.Nature, 1992,357:477479] to have invented be the flexible organic polymer El element of substrate electrically conductive polyaniline (PAN) as anode with PET.Carter[Carter S A, Angelopoulos M, Karg S, et al.Polymericanodes for improved polyrner light-emitting diode performance.Appl.Phys.Lett., 1997,70 (16): 2067-2069] etc. find under study for action that PEDOT is better as the device stability of anode than ITO as the polymer El element of anode.Conductive polymer coating and PET substrate have good adhesive, have better flexibility, and cost is also lower.But because the conductivity of conducting polymer is lower, the brightness of device and efficient improve seldom.
Therefore, study novel nesa coating, seek the transparent conductive film that preparation technology relatively simply can substitute expensive ito thin film and just seem very necessary.
[summary of the invention]: the present invention seeks to solve the problem that existing flexible organic electroluminescent device exists, a kind of flexible organic electroluminescent device and preparation method thereof is provided.The argent that this method adopts self-assembled monolayer to modify is the anode preparation flexible organic electroluminescent device.
Metal material has good conductivity, ductility, heat conductivity, hot expansibility.In all metal materials, Ag has best conductivity and ductility.When the thickness of metal silverskin during less than 135nm, the Ag film presents good light transmission and suitable conductivity is arranged.But silverskin is separately as the anode of flexible organic electroluminescent device also defectiveness.(B de Boer according to the literature, et al.Advanced Materials, 2005,17 (5): 621-625), (Self-AssembledMonolayer, SAM) work function of the Ag film of Xiu Shiing can be brought up to 5.2eV through fluorine-containing mercaptan self-assembled monolayer.Therefore, the present invention proposes: will be applied in the device architecture through the ultrathin metallic film of the fluorine-containing mercaptan modification anode as flexible organic electroluminescent device.Because the work function through the silverskin after the self assembly molecule modification can be brought up to 5.2eV, will help the injection in hole, thereby can save the step that adds hole injection layer, improve the luminosity of device, simplify the manufacturing process of device and reduced manufacturing cost.
Flexible luminescent device concrete structure provided by the invention comprises as shown in Figure 1 successively:
1), flexible substrate 1;
2), be positioned at the metal silverskin 2 that the self-assembled monolayer on the above-mentioned flexible substrate 1 is modified;
3), be positioned at hole transmission layer 3 on the metal silverskin 2 that above-mentioned self-composed monomolecular modifies;
5), be positioned at luminescent layer 4 on the above-mentioned hole transmission layer 3;
6), be positioned at electron transfer layer 5 on the above-mentioned luminescent layer 4;
7), be positioned at metallic cathode 6 on the above-mentioned electron transfer layer 5.
Above-mentioned flexible substrate can be polyethylene (PE), polypropylene (PP), polystyrene (PS), PETG (PET), polysulfones ether (PES), poly-to (ethylene naphthalate) (PEN) transparent polymer of etc.ing or the transparent polymer material that prepared by above-mentioned transparent polymer blend.Also can be the ultra-thin glass of thickness below 0.3mm.
Self-assembled monolayer is the mercaptan that contains electron withdraw group, electron withdraw group is-F ,-CN or-CF
3Self-assembled monolayer is by chemical bond and metal silverskin keyed jointing.
The preparation method of above-mentioned organic electroluminescence device may further comprise the steps:
The first, the transparent flexible substrate is cleaned in cleaning agent repeatedly after, soak and ultrasonic cleaning through isopropyl alcohol, in nitrogen current, dry up stand-by at last;
The second, at the transparent flexible substrate surface, by the way formation silverskin of vacuum thermal evaporation or electron beam evaporation; The thickness of silverskin is 25-150nm;
Three, by infusion method or fumigating system, with the self assembly molecule that contains electron withdraw group the metal silverskin is modified, formed the metal silverskin 2 that self-assembled monolayer is modified, wherein, electron withdraw group is-F ,-CN or-CF3, this self assembly molecule is by chemical bond and metal silverskin keyed jointing;
Four, on the metal silverskin 2 that above-mentioned self-assembled monolayer is modified, form hole transmission layer by evaporation or spin-coating method;
Five, on above-mentioned hole transmission layer, form luminescent layer by evaporation;
Six, on above-mentioned luminescent layer, form electron transfer layer by evaporation;
Seven, on above-mentioned electron transfer layer, form the metallic cathode layer, make organic electroluminescence device by evaporation.
Advantage of the present invention and good effect:
The ultrathin metallic film that to modify through fluorine-containing mercaptan is applied in the device architecture as the anode of flexible organic electroluminescent device, will help the injection in hole, thereby improve the luminosity and the efficient of device.Simplify the manufacturing process of device, be beneficial to suitability for industrialized production.
[description of drawings]:
Fig. 1 is the device architecture schematic diagram;
[embodiment]:
Embodiment 1
(1) polyester (PET) sheet of 30mm * 30mm is cleaned in cleaning agent repeatedly after, soak and ultrasonic cleaning through isopropyl alcohol, in nitrogen current, dry up stand-by at last;
(2) utilizing polyester (PET) the sheet surface evaporation thickness of vacuum vapour deposition after above-mentioned cleaning is the Ag film of 135nm.
(3) above-mentioned evaporation being had the PET sheet of 135nmAg film put into concentration is 1 * 10
-3Take out after soaking 0.5h in the ethanol solution of the 4-fluorobenzene mercaptan of mol/L, clean 3 times, and dry up with nitrogen current with absolute ethyl alcohol.Utilize vacuum vapour deposition NPB, the Alq of 70nm of evaporation 60nm successively
3, the LiF of 0.7nm and the Al of 100nm, in 4～8V scope, can obtain stable electroluminescence, the brightness when 8V reaches 27600cd/m
2Maximum luminous efficiency is 5.6cd/A (7V).
Embodiment 2
(1) polyester (PET) sheet of 30mm * 30mm is cleaned in cleaning agent repeatedly after, soak and ultrasonic cleaning through isopropyl alcohol, in nitrogen current, dry up stand-by at last;
(2) utilizing polyester (PET) the sheet surface evaporation thickness of vacuum vapour deposition after above-mentioned cleaning is the Ag film of 150nm.
(3) above-mentioned evaporation being had the PET sheet of 150nmAg film put into concentration is 1 * 10
-3Take out after soaking 0.5h in the ethanol solution of the 3-trifluoromethyl benzyl mercaptan of mol/L, clean 3 times, and dry up with nitrogen current with absolute ethyl alcohol.
(4) PVK and TPD are pressed mass ratio and mixed in 1: 1～1: 2, and be dissolved in and be made into the solution that concentration is 2mg/ml in the chloroform.Adopt the spin-coating method film forming.Be placed on after finishing in the drier and treat solvent evaporates more than 2 hours.
(5) utilize vacuum vapour deposition that hole transmission layer NPB is made the film of thickness for 20nm.
(6) utilize vacuum vapour deposition to prepare the hold concurrently film of electron transfer layer Alq3 (8-hydroxyquinoline aluminum) of luminescent layer on hole transmission layer NPB, thickness is 60nm.
(7) at luminescent layer Alq
3On LiF and the Al of 3nm, the silver of 135nm of vacuum evaporation 1nm do negative electrode.Thereby make can double-side flexible organic electroluminescent device, device architecture:
Ag(SAM)/PVK:TPD/NPB(20nm)/Alq
3(60nm)/LiF(1nm)/Al(3nm)/Ag(135nm)。
(8) after the device preparation is finished, between 3.5～9V, can obtain stable two-sided electroluminescence, the maximum brightness at top reaches 1500cd/m when 8V
2, the brightness of bottom-emission is 3155cd/m
2
Claims (7)
1. flexible organic electroluminescent device is characterized in that this luminescent device comprises:
1), flexible substrate (1);
2), be positioned at the metal silverskin (2) that the self-assembled monolayer on the above-mentioned flexible substrate (1) is modified;
3), be positioned at hole transmission layer (3) on the metal silverskin (2) that above-mentioned self-composed monomolecular modifies;
5), be positioned at luminescent layer (4) on the above-mentioned hole transmission layer (3);
6), be positioned at electron transfer layer (5) on the above-mentioned luminescent layer (4);
7), be positioned at metallic cathode (6) on the above-mentioned electron transfer layer (5).
2. flexible organic electroluminescent device according to claim 1, it is characterized in that flexible substrate (1) is transparent polymer, specifically is polyethylene (PE), polypropylene (PP), polystyrene (PS), PETG (PET), polysulfones ether (PES), poly-to (ethylene naphthalate) (PEN) or by the transparent polymer material of above-mentioned transparent polymer blend preparation.
3. flexible organic electroluminescent device according to claim 1 is characterized in that flexible substrate (1) is the ultra-thin glass of thickness below 0.3mm.
4. according to claim 1 or 2 or 3 described flexible organic electroluminescent devices, it is characterized in that self-assembled monolayer is the mercaptan that contains electron withdraw group, and self-assembled monolayer is by chemical bond and metal silverskin keyed jointing.
5. flexible organic electroluminescent device according to claim 4 is characterized in that self assembly molecule modifies the metal silverskin by infusion method or fumigating system.
6. flexible organic electroluminescent device according to claim 5, it is characterized in that electron withdraw group be-F ,-CN or-CF
3
7. the preparation method of the described flexible organic electroluminescent device of claim 1 is characterized in that this method may further comprise the steps:
The first, the transparent flexible substrate is cleaned in cleaning agent repeatedly after, soak and ultrasonic cleaning through isopropyl alcohol, in nitrogen current, dry up stand-by at last;
The second, at the transparent flexible substrate surface, by the way formation silverskin of vacuum thermal evaporation or electron beam evaporation; The thickness of silverskin is 25-150nm;
Three, by infusion method or fumigating system, with the self assembly molecule that contains electron withdraw group the metal silverskin is modified, form the metal silverskin (2) that self-assembled monolayer is modified, wherein, electron withdraw group is-F ,-CN or-CF3, this self assembly molecule is by chemical bond and metal silverskin keyed jointing;
Four, the metal silverskin of modifying at above-mentioned self-assembled monolayer (2) is gone up by evaporation or spin-coating method and is formed hole transmission layer;
Five, on above-mentioned hole transmission layer, form luminescent layer by evaporation;
Six, on above-mentioned luminescent layer, form electron transfer layer by evaporation;
Seven, on above-mentioned electron transfer layer, form the metallic cathode layer, make organic electroluminescence device by evaporation.
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