CN104009190A - Method for processing flexible OLED - Google Patents
Method for processing flexible OLED Download PDFInfo
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- CN104009190A CN104009190A CN201410271295.6A CN201410271295A CN104009190A CN 104009190 A CN104009190 A CN 104009190A CN 201410271295 A CN201410271295 A CN 201410271295A CN 104009190 A CN104009190 A CN 104009190A
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Abstract
The invention relates to a method for processing a flexible OLED. The method comprises the steps that a hole injection layer, a hole transmission layer, a light emitting layer and a cathode are prepared on an anode substrate material, and the hole injection layer is prepared on the anode substrate material in an ink-jet printing mode by adopting hydrophilic PEDOT:PSS particle ink; lipophilic cross-linkable resin and an arylamine compound are adopted to be dissolved in an aromatic solvent to serve as the ink, and then the hole transmission layer is printed on the hole injection layer with the ink-jet printing mode; high triplet state phosphorescence micromolecule materials host 1 and host 2 are adopted as the light-emitting body material, dopant dye matched with the body material is adopted, the body material and the dopant dye are mixed in a solvent without chlorine together to serve as a light-emitting micromolecule ink material, and the light-emitting layer is prepared on the hole transmission layer in the ink-jet printing mode.
Description
Technical field
The present invention relates to organic elctroluminescent device (OLED), particularly relate to a kind of method of printing little molecular ink method processing flexibility OLED.
Background technology
Organic electroluminescent technology (OLED) is as Display Technique of new generation, compare with the current lcd technology that accounts for main flow, there is ultra-thin, active illuminating, high brightness, high-contrast, visual angle is wide, response is fast, luminous efficiency is high, thermal adaptability is good, production technology is simple, driving voltage is low, energy consumption is low, the flexible advantage such as folding, be subject to the extensive concern of industrial circle, be considered to one of the most competitive flat panel display of new generation, become the hot topic of current flat panel display research.
Organic EL display panel can be divided into two class one classes for the display screen based on macromolecule (Polymer) luminescent material, is called for short PLED, and such display screen mainly adopts the preparation of solution processing mode.Another kind of is display screen based on organic molecule (Small Molecule) luminescent material, is called for short SmOLED, and such display screen mainly adopts the mode of vacuum evaporation to process preparation; On market, business-like OLED material is little mulecular luminescence material now, because only have the luminous efficiency of little Molecule OLEDs material and life-span can meet the required technical parameter of user.The phosphor material that little mulecular luminescence material be take with metal core is as main, because phosphor material is unstable and material melting point is lower, and NPD for example, Alq3 etc., so general all with the method evaporation of vacuum coating, plated film will not have 10-20 layer not etc.Small molecule material plated film all must be realized in a vacuum at present, huge production equipment completes very complicated procedures of forming of plated film in ultra-clean space, and large-sized vaporization coating template shadow mask makes that the production time is elongated, output is extremely low, as long as there is the failure of one deck plated film, whole device is just scrapped, cause the yields of product to be very difficult to guarantee, so the holding at high price of OLED display on existing market.Than vacuum evaporation technology, solution processing technology possess equipment investment relatively cheap,, processing technology is simple, save material, be easy to realize large scale, can realize the advantages such as flexible demonstration.What use in the past solution processing technology is mainly macromolecular material, and the solution processing technology research of solubility small molecule material is just increasingly mature at present.Pluses and minuses in macromolecule and small molecule material and technique, the method that the present invention proposes to print is processed little Molecule OLEDs phosphor material, solves a difficult problem for existing efficiency, life-span and cost in OLED device production, is a brand-new invention.Wherein luminescent layer solubility small molecule material is basis.Little molecular ink coating material is that to take the phosphorescence of the high triplet of series (triplet harvesting) be main body, the luminous little mulecular luminescence ink material printed of being applicable to that redgreenblue dyestuff (dopant) is matched and mixes altogether and make.Simultaneously, in order not make solution between OLED multicoating mix/mix (intermixing), we propose a kind of hydrophily, dissolubility (solubility) and bridging property (cross-linking) of printing ink solvent of utilizing and build a kind of " seemingly-quadrature " similar macromolecule OLED system solution system (quasi-orthogonal), thereby prepare and control the method for OLED device organic function layer.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, and the processing method of a kind of flexible OLED is provided.
Technical scheme of the present invention is: the processing method of a kind of flexible OLED, be included in and on anode substrate material, prepare hole injection layer, hole transmission layer, luminescent layer and negative electrode, adopt the laser null method in contactless slot coated and later stage or the mode of inkjet printing, adopt hydrophilic PEDOT:PSS particle ink on anode material, to prepare hole injection layer; Adopting lipophile crosslinkable resin and aromatic amine compound to be dissolved in aromatic solvent adopts inkjet printing mode on hole injection layer, to print hole transmission layer as ink again; Adopt high triplet state phosphorescent small molecule material host1 and host2 as luminous material of main part, and the dopant dyestuff that mates with material of main part of employing, mix altogether in not chloride solvent and in inkjet printing mode, on hole transmission layer, prepare luminescent layer as luminous little molecular ink material, described host1 is that PPO21, described host2 are 35DCzPPy, and described dopant is FCNIrPic.
Wherein, the ratio mass ratio of described PEDOT:PSS ink doping water is 1:99, and the quality proportion of PEDOT:PSS is from 2:5 to 1:20.
The molecular weight of the lipophile crosslinkable resin of described hole transmission layer is Mw=1,000 to 80,000.
The described process of preparing hole transmission layer is contactless printing process, and the crosslinking temperature of ink, at 160 ℃～200 ℃ temperature, keeps solidifying for 0.5～2 hour.
Described high triplet state material of main part and the concentration of dyestuff are respectively: host1:host2:dopant=3:3:1～7:7:4.
Described aromatic amine compound structural formula is:
The described process of preparing luminescent layer is the direct ink-jet printing process of noncontact: by shower nozzle, droplet is positioned on the position of substrate accurately.
Beneficial effect:
The present invention filters out the particularly preferred host1 of dissolubility and host2, special proportioning has improved the solubility of small molecule material in solvent, the solubility in aromatic solvent particularly, little Molecule OLEDs processing technology is simplified, can directly use ink processing, do not re-use the manufacturing process of tradition distillation, simple printing processing technology easy to use.
OLED device simple in structure: be present 3 layers from original multilayer (>3 layer).
Use above-mentioned luminescent layer, improved luminous efficiency and the life-span of traditional polymer OLED.
Use the ink processing can be on flexible carrier, be not subject to the restriction that traditional sublimation process carrier bearing temperature can not be too high.(be less than PET, PEN glass transition temperature 180 ℃).
Embodiment
Below the present invention is further illustrated, but embodiment does not form the restriction to the claimed scope of the present invention.
The invention provides the preparation method of hole injection layer in a kind of organic function layer.Described hole injection layer, adopts hydrophilic PEDOT:PSS particle ink to prepare as raw material.
Wherein, the ratio of described PEDOT:PSS ink doping water is 1:99 (quality proportion), and the ratio of PEDOT:PSS (quality proportion) is for 2:5 is to 1:20; For the PEDOT:PSS of inkjet printing, owing to need to controlling uniformity after coating and need adjust the rheological parameter of PEDOT:PSS, the adjusting of described rheological parameter, can realize by adding surfactant.The kind of described surfactant is XX, its shared PEDOT:PSS ink gross mass ratio be XX%-XX%.Being set as of described rheological parameter, surface tension: 25-40mN/m, apparent viscosity is 10-14mPas, density 1000kg/m3, the average-size of PEDOT:PSS particle is 25-35nm.Because OLED shows, need specific coating patterns, adopt the laser null method (laser ablation) in contactless slot coated (slot die coating) and later stage or the direct method of printing of inkjet printing (inkjet printing) to generate coating patterns.
The invention provides the preparation method of hole transmission layer in a kind of organic function layer.Described hole transmission layer, adopts lipophile crosslinkable resin, arylamine material, aromatic solvent collocation (aromatic solvents) to prepare as ink such as (toluene etc.).
Wherein, described crosslinkable resin material molecule amount is Mw=1000 to 80000, and optimally, molecular weight is chosen as Mw=20,000 to 40,000; Bridging property, at 160 ℃～200 ℃ temperature, keeps solidifying for 0.5～2 hour, and optimally, temperature is chosen as 180 ℃, is chosen as 1 hour curing time; The described process of preparing hole transmission layer is for example inkjet printing of contactless printing process.
The invention provides the preparation method of luminescent layer in a kind of organic function layer.Described luminescent layer, adopt high triplet state phosphorescent small molecule material as luminous material of main part, and employing and the dyestuff that material of main part (suitable band width's) mates, mix altogether in not chloride solvent and prepare luminescent layer as luminous little molecular ink material.
Wherein, to may be selected to be described host1 be that PPO21 structural formula is to the high triplet state phosphorescent small molecule material of main part of described luminescent layer ink
described host2 is that 35DCzPPy structural formula is
described dopant is that FCNIrPic structural formula is
material of main part and dye strength ratio are respectively: host1:host2:dopant=3:3:1～7:7:4, and optimally, concentration ratio is chosen as host1:host2:dopant=5:5:2; The described process of preparing luminescent layer is the direct inkjet technology of noncontact: by shower nozzle, droplet is positioned on the position of substrate accurately.
The present invention utilizes hydrophily, dissolubility (solubility) and the bridging property (cross-linking) of printing ink solvent to build a kind of " seemingly-quadrature " similar macromolecule OLED system solution-treated system (quasi-orthogonal).Between two adjacent functional layers, adopt hydrophilic and hydrophobic to control, dissolubility is controlled, and in bridging property control, one of any means or its Combination of Methods, control or stop to adulterate between adjacent two layers, mix, permeate, dissolve.
In order to utilize upper strata printing ink solvent, to the close and distant water Characteristics Control at subsurface material interface, it infiltrates, dissolves the doping of subsurface material, mixing in the hydrophilic and hydrophobic control of printing ink solvent, and the filming performance of this layer.
The dissolubility of printing ink solvent is controlled and is comprised: by modified with functional group, and pH value, temperature, pressure, magnetic field, electric field adjusting is controlled ink raw materials in the dissolubility of printing ink solvent, and the dissolubility of upper strata printing ink solvent to lower membrane.
The bridging property of printing ink solvent is controlled as utilizing crosslinkable polymeric oil ink material, under heat, the effect of UV light reaction factor, solidify to form the film that is insoluble to upper strata printing ink solvent.Described crosslinkable polymer resin can be selected hot curing cross-linking type phenolic resins or organic siliconresin.
In order further to realize the present invention, the selection of flexible substrate can be the flexible materials such as macromolecular material, paper and fiber material, cloth and textile material, natural or dermatine.
OLED is generally typical sandwich-type " sandwich " structure, i.e. anode (Anode), negative electrode (Cathode), and the organic function layer being clipped between anode and negative electrode forms.
For the present invention, in order to realize flexible demonstration.Available anode material may be selected to be Graphene, carbon nano-tube, metal grill, metal nanometer line, zinc oxide nanowire; Cathode material comprises active metal Mg, Ag, Ba, Ca, Al, Cs etc., alloy MgAg, LiAl etc.
The present invention can also prepare other layers in organic function layer according to a conventional method; Set up corresponding seemingly quadrature system and mix, mix from the solution of controlling between the multilayer film organic function layer, wherein like quadrature system, utilize hydrophily, dissolubility and the bridging property of printing ink solvent to build.
Aromatic amine compound in hole transmission layer, structural formula is:
Specifically referring to the Materials Science Forum Vols.514-516 such as Novel Organic Hole Transport Layers for Molecular Electronic Systems H.D.Burrows, 8-12.
Other materials is commercially available.
Embodiment 1
A processing method of flexible OLED, flexible OLED comprises by the 30 * 30mm that is coated with nano silver wire
2pET plate is as anode, hole injection layer, and hole transmission layer, luminescent layer and LiF/Al negative electrode stack gradually formation.
Hole injection layer: the ratio of PEDOT:PSS aqueous solution doping water is 1:99, and the ratio of PEDOT:PSS is 1:15.Add appropriate surfactant 3,4-ethylidene dioxy thiophene, regulates its rheological parameter, surface tension: 25-40mN/m, apparent viscosity is 10-14mPas.The mode that adopts inkjet printing by PEDOT:PSS ink deposition on substrate.Using Spectra Galaxy PH 256/50 AAA ink gun .Nozzle pitch is 254 microns, and droplet volume is 50pl.By regulating electric pulse and driving voltage to form the stable drop without satellite.Hole injection layer thickness is 100nm.
Hole transmission layer: lipophile crosslinkable phenolic resins and aromatic amine compound that molecular weight is 30000
be dissolved in toluene and prepare as ink, concentration is 5mg/ml.Adopt the Dimatix DMP2800 printer of 10pl ink gun, on hole injection layer, print, temperature is chosen as 180 ℃, is chosen as 1 hour curing time.The thickness of hole transmission layer is 60nm.
Luminescent layer: by high triplet state little phosphorescent molecule material of main part host1 and host2, and the dyestuff dopant matching is with it dissolved in toluene, wherein, it is that PPO21, described host2 are 35DCzPPy that the high triplet state phosphorescent small molecule material of main part of described luminescent layer ink may be selected to be described host1, and described dopant is FCNIrPic; Concentration is respectively 5mg/ml, 5mg/ml, 2mg/ml, adopts the mode of inkjet printing to prepare, and light emitting layer thickness is 80nm.
Embodiment 2
A processing method of flexible OLED, step at least comprises prepares hole injection layer, hole transmission layer and luminescent layer, and order is: PEDOT:PSS before this, is then hole transmission layer, then is luminescent layer.According to a conventional method, at the tow sides of film, prepare again negative electrode and anode.
Wherein, the preparation of hole injection layer:
Step 1.1, employing hydrophily PEDOT:PSS particle ink are that raw material requires and water doping in proportion, and the rheological parameter of adding surfactant adjustment mixed solution is to prepare the ink material of hole injection layer;
Step 1.2, because OLED show to need specific coating patterns, adopt contactless coating in early stage and the laser null method in later stage or directly the method for inkjet printing generate hole injection layer coating patterns.
Surfactant, for the rheological parameter of solution, meets it: surface tension is 25-40mN/m, and apparent viscosity is 8-14mPas, and density is 1000kg/m3.
The preparation of hole transmission layer:
Step 2.1, with the hole mobile material of lipophile crosslinkable polymer collocation benzene, prepare the ink material of hole transmission layer;
Step 2.2, adopt the method for direct inkjet printing to generate hole transmission layer plated film;
Step 2.3 utilizes bridging property to be cured processing to the ink material of hole transmission layer.Solidify to process and carry out at 160 ℃～200 ℃ temperature, keep curing time 0.5～2 hour.
The preparation of luminescent layer:
Step 3.1, using high triplet state phosphorescent small molecule material as luminous material of main part, adopt the dyestuff with luminous material of main part bandwidth match, require in proportion host1:host2:dopant=3:3:1～7:7:4 for example to mix altogether, in not chloride organic (veratrol veratrole, concentration 12mg/ml) solvent and prepare little mulecular luminescence ink material.
Step 3.2, adopt non-contacting inkjet printing mode, the shower nozzle by ink jet printing device is positioned at little mulecular luminescence ink material drop accurately and on OLED substrate, generates luminescent layer plated film.
Claims (7)
1. the processing method of a flexible OLED, be included in and on anode substrate material, prepare hole injection layer, hole transmission layer, luminescent layer and negative electrode, it is characterized in that: adopt the laser null method in contactless slot coated and later stage or the mode of inkjet printing, adopt hydrophilic PEDOT:PSS particle ink on anode material, to prepare hole injection layer; Adopting lipophile crosslinkable resin and aromatic amine compound to be dissolved in aromatic solvent adopts inkjet printing mode on hole injection layer, to print hole transmission layer as ink again; Adopt high triplet state phosphorescent small molecule material host1 and host2 as luminous material of main part, and the dopant dyestuff that mates with material of main part of employing, mix altogether in not chloride solvent and in inkjet printing mode, on hole transmission layer, prepare luminescent layer as luminous little molecular ink material, described host1 is that PPO21, described host2 are 35DCzPPy, and described dopant is FCNIrPic.
2. the processing method of flexible OLED according to claim 1, is characterized in that: wherein, the ratio mass ratio of described PEDOT:PSS ink doping water is 1:99, and the quality proportion of PEDOT:PSS is from 2:5 to 1:20.
3. the processing method of flexible OLED according to claim 1, is characterized in that: the molecular weight of the lipophile crosslinkable resin of described hole transmission layer is Mw=1 000 to 80,000.
4. the processing method of flexible OLED according to claim 1, is characterized in that: the described process of preparing hole transmission layer is contactless printing process, and the crosslinking temperature of ink, at 160 ℃～200 ℃ temperature, keeps solidifying for 0.5～2 hour.
5. the processing method of flexible OLED according to claim 1, is characterized in that: described high triplet state material of main part and the concentration of dyestuff are respectively: host1:host2:dopant=3:3:1～7:7:4.
6. the processing method of flexible OLED according to claim 1, is characterized in that: described aromatic amine compound structural formula is:
7. the processing method of flexible OLED according to claim 1, is characterized in that: the described process of preparing luminescent layer is the direct ink-jet printing process of noncontact: by shower nozzle, droplet is positioned on the position of substrate accurately.
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| CN201410271295.6A CN104009190A (en) | 2014-06-17 | 2014-06-17 | Method for processing flexible OLED |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114068826A (en) * | 2020-08-03 | 2022-02-18 | 湖南鼎一致远科技发展有限公司 | Hole transport layer, color band and preparation method thereof |
Citations (4)
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|---|---|---|---|---|
| CN1780019A (en) * | 2004-11-17 | 2006-05-31 | 三星Sdi株式会社 | Small molecular organic electroluminescent display device and method of fabricating the same |
| US20070020395A1 (en) * | 2005-06-27 | 2007-01-25 | Lang Charles D | Process for making an electronic device |
| CN101965651A (en) * | 2008-03-03 | 2011-02-02 | 剑桥显示技术有限公司 | Solvent for a Printing Composition |
| CN102347455A (en) * | 2010-07-30 | 2012-02-08 | 株式会社东芝 | Method for manufacturing organic light emitting device and solution for organic light emitting device |
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2014
- 2014-06-17 CN CN201410271295.6A patent/CN104009190A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1780019A (en) * | 2004-11-17 | 2006-05-31 | 三星Sdi株式会社 | Small molecular organic electroluminescent display device and method of fabricating the same |
| US20070020395A1 (en) * | 2005-06-27 | 2007-01-25 | Lang Charles D | Process for making an electronic device |
| CN101965651A (en) * | 2008-03-03 | 2011-02-02 | 剑桥显示技术有限公司 | Solvent for a Printing Composition |
| CN102347455A (en) * | 2010-07-30 | 2012-02-08 | 株式会社东芝 | Method for manufacturing organic light emitting device and solution for organic light emitting device |
Non-Patent Citations (1)
| Title |
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| HUGH D BURROWS ET AL: "Novel Organic Hole Transport Layers for Molecular Electronic Systems", 《MATERIALS SCIENCE FORUM》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114068826A (en) * | 2020-08-03 | 2022-02-18 | 湖南鼎一致远科技发展有限公司 | Hole transport layer, color band and preparation method thereof |
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Application publication date: 20140827 |