WO2008035501A1 - Solution de revêtement pour élément électroluminescent organique, cet élément et son procédé de production - Google Patents
Solution de revêtement pour élément électroluminescent organique, cet élément et son procédé de production Download PDFInfo
- Publication number
- WO2008035501A1 WO2008035501A1 PCT/JP2007/063825 JP2007063825W WO2008035501A1 WO 2008035501 A1 WO2008035501 A1 WO 2008035501A1 JP 2007063825 W JP2007063825 W JP 2007063825W WO 2008035501 A1 WO2008035501 A1 WO 2008035501A1
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- WO
- WIPO (PCT)
- Prior art keywords
- coating liquid
- organic electroluminescent
- organic
- organic electroluminescence
- carbitol
- Prior art date
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 167
- 238000000576 coating method Methods 0.000 title claims abstract description 167
- 238000005401 electroluminescence Methods 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims description 131
- 238000009835 boiling Methods 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 29
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 27
- 238000002347 injection Methods 0.000 claims description 27
- 239000007924 injection Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 4
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims 1
- 238000003892 spreading Methods 0.000 abstract description 11
- 239000000976 ink Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920000291 Poly(9,9-dioctylfluorene) Polymers 0.000 description 1
- 229920000285 Polydioctylfluorene Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- OCLXJTCGWSSVOE-UHFFFAOYSA-N ethanol etoh Chemical compound CCO.CCO OCLXJTCGWSSVOE-UHFFFAOYSA-N 0.000 description 1
- FQMCMHQTSGVJIP-UHFFFAOYSA-N ethanol;2-(2-hydroxyethoxy)ethanol Chemical compound CCO.OCCOCCO FQMCMHQTSGVJIP-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
Definitions
- Coating liquid for organic electroluminescent element organic electroluminescent element, and method for producing organic electroluminescent element
- the present invention relates to a coating liquid for an organic electroluminescent element, an organic electroluminescent element
- a coating liquid for an organic electroluminescent element, an organic electroluminescent element, and an organic electroluminescent element suitable for forming a hole injecting and transporting layer using an ejection device such as an ink jet device It relates to a manufacturing method.
- Organic electroluminescence (EL) displays are excellent in visibility and responsiveness, and can be reduced in power consumption, thin and light, and flexible in the display body. Get the attention as (FPD)!
- organic EL element Such an organic EL display is also referred to as an organic electroluminescence element (hereinafter referred to as “organic EL element”) which is a light-emitting element disposed for each pixel on a transparent insulating substrate made of glass, resin, or the like. ) Is emitted to display an image.
- organic EL element for example, on a patterned anode made of indium tin oxide (ITO), a hole injecting and transporting layer made of a hole injecting and transporting material, a light emitting layer having a light emitting material force, and a vacuum
- ITO indium tin oxide
- a hole injecting and transporting layer made of a hole injecting and transporting material
- a light emitting layer having a light emitting material force and a vacuum
- a cathode formed by vapor deposition is laminated in this order.
- the light emitting layer emits light by recombining charges (holes and electrons) supplied from the anode and the cathode.
- the hole injecting and transporting layer is provided between the anode and the light emitting layer in order to improve the light emitting efficiency and durability of the organic EL element. Since the characteristics of the light emitting layer and the hole injecting and transporting layer are important in the spread of organic EL displays, how to form a light emitting layer and a hole injecting and transporting layer with excellent performance is required.
- a method for forming the light emitting layer and the hole injecting and transporting layer As a method for forming the light emitting layer and the hole injecting and transporting layer, a vapor deposition method, a wet method and the like can be mentioned, and a wet method is often used from the viewpoint of manufacturing cost.
- a light emitting material and a hole injecting and transporting material for forming a light emitting layer and a hole injecting and transporting layer by a wet method In general, a polymer material is used.
- a spin coating method is an example of a wet method using a polymer material. However, the spin coating method uses red (R), green (G), and blue (B) luminescent materials, which have poor material utilization efficiency and are difficult to control the layer thickness. Since it has the disadvantages that it cannot be painted separately, it is not suitable for practical use and mass production.
- a coating liquid (ink) in which the light emitting material or the hole injecting and transporting material is dispersed or dissolved in water or an organic solvent is applied to the substrate by an ink jet device.
- a method of discharging into a bank (a partition wall for partitioning between pixels) formed on the substrate According to this, since precise discharge control is possible, highly accurate patterning can be performed. In addition, since it is possible to directly discharge the required amount of material into the bank, the material utilization efficiency can be made extremely high.
- Patent Document 1 Japanese Unexamined Patent Publication No. 2000-106278
- Patent Document 2 Japanese Patent Application Laid-Open No. 2004-204114
- the present invention has been made in view of the above-described situation, and it is possible to improve the spread of the coating liquid in the bank, the coating liquid for organic electroluminescent elements, the organic electroluminescent element, and the organic
- An object of the present invention is to provide a method for producing an electroluminescent element.
- the present inventors have made various studies on coating liquids for organic electo-luminescence elements that can improve the spreading of the coating liquid in the bank.
- the layer is a material for forming the hole injecting and transporting layer. Attention was focused on solvents that can dissolve or disperse the forming material.
- the coating liquid for organic electroluminescent elements comprises a layer forming material and a carbitol-based compound as an essential solvent, so that when coating is performed using a discharge device or the like, The inventors have found that the coating liquid can easily spread in the bank and have conceived that the above-mentioned problems can be solved brilliantly, and have reached the present invention.
- the present invention is an organic electroluminescent element coating liquid used for forming a hole injecting and transporting layer of an organic electroluminescent element, wherein the organic electoluminescent element coating liquid comprises: An organic electroluminescent device coating liquid comprising a layer forming material and a carbitol-based compound as an essential solvent.
- the coating liquid for organic electroluminescence elements of the present invention (hereinafter also referred to as "organic EL coating liquid”) is used for forming a hole injection transport layer of an organic EL element. Therefore, the organic EL coating liquid of the present invention is suitable for producing a hole injection transport layer by a wet method using a discharge device or the like.
- the hole injecting and transporting layer has a function of injecting and / or transporting holes (holes) supplied from the anode to the light emitting layer. Therefore, the hole injection transport layer may be an injection hole injection layer having a function of injecting holes into the light emitting layer, or a hole transport layer having a function of transporting holes to the light emitting layer. Moyo! /
- the coating liquid may be called ink.
- the organic electroluminescent element coating liquid includes a layer forming material.
- the layer forming material is a material for forming a hole injecting and transporting layer. It is an injection transport material.
- the hole injecting and transporting material is a material that can exhibit the function as the hole injecting and transporting layer. Therefore, the hole injection / transport material may be a hole injection material or a hole transport material.
- the hole injecting and transporting material is usually a polymer material in the present invention.
- PEDOT poly (3,4-ethylenedioxythiophene)
- PES polystyrene sulphonic acid
- the coating liquid for organic electroluminescence elements contains poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid as the layer forming material.
- PEDOT—PSS has excellent properties as a hole injecting and transporting layer, and can use water as the main solvent.
- the coating liquid for an organic electroluminescence device includes a carbitol-based compound as an essential solvent.
- the carbitol-based compound has a property of making the coating liquid easily spread in the bank. Therefore, the spread of the coating liquid in the bank can be improved.
- carbitol compounds are not extremely high in viscosity, they can be easily adjusted to inks suitable for coating.
- the carbitol-based compound is a compound represented by the following chemical formula (1) or (2).
- j, k, n, m and 1 are arbitrary natural numbers.
- j 1 to 3
- k l is more preferable.
- the solvent is for dissolving or dispersing the layer forming material. Therefore, the solvent may be a dispersion medium.
- the solvent is usually a liquid at normal temperature and pressure. Further, from the viewpoint of improving the light emission efficiency of the organic EL device, it is preferable that the solvent does not remain in the hole injecting and transporting layer after the formation of the hole injecting and transporting layer. Les.
- the solvent may contain water, or may contain water and a solvent other than water.
- composition of the coating liquid for an organic electroluminescent device of the present invention may or may not contain other elements as long as such elements are essential. It is not limited.
- the carbitol-based compound preferably has a boiling point of 180 ° C or higher under the condition of 1.0 X 10 5 Pa.
- the carbitol-based compound is preferably 1. a high boiling point solvent having a boiling point of 180 ° C. or higher under the condition of OX 10 5 Pa.
- the carbitol-based compound preferably has a boiling point of 250 ° C or lower under the condition of 1.0 X 10 5 Pa. Accordingly, it is possible to effectively suppress the solvent remaining in the hole injecting and transporting layer, so that the light emission characteristics of the organic EL element can be improved. Also, the coating liquid Since the drying after coating can be easily performed, the throughput can be shortened.
- the carbitol-based compound is preferably water-soluble.
- PEDOT-PSS which is particularly suitable as a hole injecting and transporting material, is usually marketed in a state of being dispersed in water. This makes it easy to disperse PEDOT-PSS in a coating liquid containing a carbitol-based compound. Become
- the carbitol-based compound those having a viscosity under a condition of 20 ° C of 2.5 mPa's or more are preferable. If the viscosity is less than 2.5 mPa's, the boiling point is lowered and the volatility is increased, so that it may be difficult to use as a solvent.
- the carbitol-based compound those having a viscosity under a condition of 20 ° C of 7. OmPa's or less are preferable. When the viscosity exceeds 7. OmPa's, the coating liquid is difficult to spread, and it may be difficult to control the physical properties of the entire coating liquid.
- the carbitol-based compound preferably has a viscosity at 20 ° C of 2.5 mPa's or more and 7. OmPa's or less.
- a carbitol-based compound is particularly suitable as a substance that makes the coating liquid easily spread in the bank.
- carbitol compounds having such a viscosity include diethylene glycol monoethyl ether (4.5 mPa's), diethylene glycol monomono butylenoate ethere (6.5 mPa 's), diethylene glycol monoethanolate. And tenoleacetate (2.8 mPa's), diethyleneglycolenobutinoleatenoleacetate (3.6 mPa's), and the like.
- the carbitol-based compound preferably has a surface tension of 27. OmN / m or more and 32. OmN / m or less at 25 ° C.
- a carbitol-based compound is suitable as a substance that facilitates spreading of the coating liquid in the bank.
- Examples of carbitol compounds having such surface tension include diethylene glycol monoethyl ether (31.8 mN / m), diethylene glycol monomono butylenoate ethere (30. OmN / m), diethylene glycol monoethanolo diol.
- Examples include etherol acetate (27.4 mN / m) and diethylene glycolol monobutinole ether acetate (29 ⁇ 9 mN / m).
- the surface tension is 27 ⁇ OmN / When or exceed 32. OMN / m or less than m, the case of ejecting the coating liquid in the bank by the discharge device of the ink jet device, a droplet (coating liquid) is that force s is not discharged from the head unit.
- the carbitol-based compound is at least one ether selected from the group consisting of diethylene glycol monoethyl ether, polyethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.
- a compound is preferred.
- These carbitol compounds are suitable as substances that make the coating liquid easily spread in the bank, and the physical properties (contact angle, viscosity, surface tension, etc.) of the coating liquid are easily adjusted to those suitable for coating. can do.
- the coating liquid for an organic electroluminescence device is 1.0.
- a form containing at least one high-boiling solvent having a boiling point of 180 ° C. or higher under the condition of X 10 5 Pa (hereinafter also referred to as “first form”) is preferable.
- the organic EL coating liquid contains a carbitol-based compound as a solvent
- the coating liquid spreads too much inside the bank and overflows from the bank, and hole injection that exhibits characteristics that can be used as an organic EL element. It may be difficult to form a transport layer. Therefore, in addition to the carbitol-based compound, as a substance for suppressing the coating liquid from spreading too much in the bank, at least one kind of boiling point force S of 180 ° C or higher under the condition of 1.0 X 10 5 Pa is used.
- the organic EL coating liquid of the present invention preferably contains a solvent that makes the coating liquid easily spread in the bank and a solvent that suppresses the coating liquid from spreading too much in the bank.
- the organic EL coating liquid of the present invention contains the carbitol-based compound and the high-boiling solvent
- the ratio of the carbitol-based compound and the high-boiling solvent is not particularly limited and may be set as appropriate. That's fine.
- the high boiling point solvent preferably has a boiling point of 250 ° C or less under the condition of 1.0X10 5 Pa, and is water-soluble. Is preferred.
- the coating liquid for an organic electroluminescence element comprises at least a water dispersion of a layer forming material containing mass% of the layer forming material, a carbitol-based compound, and a high-boiling point solvent.
- the ratio of the solvent with a boiling point of 180 ° C or higher under the condition of 1.0X10 5 Pa to the total coating liquid (solution) is defined as volume%, and the total coating liquid of water dispersion of the layer forming material
- the conversion ratio y / (x X z) when the ratio to (solution) is 2 % by volume is preferably 0.7 or less.
- the solvent boiling point at conditions of 1.0 ⁇ 10 5 Pa is 180 ° C or higher
- carbitol-based compound having a boiling point under the conditions of 1.0 ⁇ 10 5 Pa is 180 ° C or more
- the high-boiling solvent preferably includes a dihydric alcohol.
- Bivalent alcohol has the property of suppressing the coating liquid from spreading too much in the bank. Therefore, it is suitable as the above high boiling point solvent.
- the dihydric alcohol preferably has a viscosity of 40. OmPa's or more at 20 ° C. When the viscosity is less than 40.OmPa's, the boiling point is lowered and the volatility is increased, so that it may be difficult to use as a solvent.
- the dihydric alcohol those having a viscosity at 20 ° C of 50. OmPa's or less are preferable. If the viscosity exceeds 50.OmPa's, the coating liquid may not easily spread, and it may be difficult to control the physical properties of the entire coating liquid.
- the dihydric alcohol preferably has a viscosity of 40. OmPa's or more and 50.0 mPa's or less at 20 ° C. Such a dihydric alcohol is particularly suitable as a substance that prevents the coating liquid from spreading too much in the bank.
- Examples of the dihydric alcohol having such a viscosity include ethylene glycol (45.5 mPa's), diethylene glycol (48.5 mPa's), 1,2-propanediol (40.4 mPa's), triethylene glycol (45.2 mPa's), and the like. Can be mentioned.
- the viscosity is less than 40. OmPa's or 50. OmPa's If exceeded, in addition to the above case, when the coating liquid is ejected into the bank by an ejection device such as an ink jet device, droplets (coating fluid) may not be ejected from the head portion.
- the dihydric alcohol preferably has a surface tension of 30. OmN / m or more and 50.0 mN / m or less at 25 ° C.
- a dihydric alcohol is particularly suitable as a substance that prevents the coating liquid from spreading too much in the bank.
- Dihydric alcohols with such surface tension include ethylene glycol (48. OmN / m), diethylene glycol (35.7 mN / m), 1,2-propanediol (40 ⁇ lmN / m), triethylene glycol ( 40. OmN / m). If the surface tension is less than 30. OmN / m or exceeds 50. OmN / m, when the coating liquid is ejected into the bank by an ejection device such as an ink jet device, the liquid droplets (coating fluid) May not be discharged.
- the dihydric alcohol is preferably ethylene glycol and / or diethylene glycol. These dihydric alcohols are particularly suitable as substances that suppress the coating liquid from spreading too much in the bank. Moreover, since these are easily available, the coating liquid for organic EL of the present invention can be easily prepared. As a result, it is possible to easily form a hole injection / transport layer.
- the coating liquid for an organic electroluminescent element preferably contains at least one lower alcohol.
- the physical property values (contact angle, viscosity, surface tension, etc.) of the coating liquid can be easily adjusted to those suitable for coating.
- the surface tension of water is large, so that the coating liquid may hang around the nozzles of the head unit of the discharge device and the coating liquid may not be discharged.
- the surface tension of the lower alcohol is usually smaller than that of water, the occurrence of such a discharge failure can be suppressed.
- the lower alcohol means an alcohol having carbon atoms of ! to 8, preferably an alcohol having 1 to 4 carbon atoms.
- a water-soluble alcohol can be used as the at least one lower alcohol.
- the ratio of all the lower alcohols to the total volume of the organic EL coating liquid is 60% by volume or less.
- the boiling point of lower alcohols is usually higher than that of water. Due to its low level, if the proportion of lower alcohol exceeds 60% by volume, clogging may occur at the head of the discharge device.
- the lower alcohol is preferably at least one alcohol selected from the group consisting of methanol, ethanol, and isopropyl alcohol. Since these lower alcohols are easily available, it is possible to easily prepare the organic EL coating liquid of the present invention. As a result, the hole injecting and transporting layer can be easily formed. Moreover, since these have similar physical property values (contact angle, viscosity, surface tension, etc.), they can be selected as appropriate.
- the present invention is also an organic electroluminescent element in which a hole injecting and transporting layer is formed using the organic electroluminescent coating solution.
- a hole injecting and transporting layer is formed using the organic electroluminescent coating solution.
- the present invention further relates to a method for producing an organic electoluminescence element using the coating liquid for an organic electroluminescence element, wherein the production method comprises a pattern coating of the coating liquid for an organic electroluminescence element.
- This is also a method for producing an organic electroluminescent element including a step of forming a hole injecting and transporting layer (a hole injecting and transporting layer forming step). According to this, the hole injection transport layer can be formed up to the edge of the bank, and an organic EL element excellent in film uniformity and light emission efficiency can be produced.
- Examples of the pattern application include a method using a printing device, a discharge device, and the like, and among these, it is preferable to use a discharge device.
- the coating liquid is applied in a predetermined pattern shape to the substrate on which the concave portion to which the coating liquid is to be applied according to a predetermined pattern shape is formed by continuous discharge means using the discharge device. be able to. Therefore, it is possible to use a force S to form a hole injecting and transporting layer having a fine pattern shape easily at low cost.
- an ink jet device As the discharge device, an ink jet device, a nozzle coater, a force S that can be used as a dispenser, and the like, among them, an ink jet device is preferably used. According to the ink jet apparatus, it is possible to accurately eject the coating liquid into a predetermined fine pattern shape to be coated. Therefore, it is possible to inject holes with a fine pattern shape at a lower cost and more easily. A transport layer can be formed.
- the organic electroluminescent element coating liquid is applied, and then natural drying, heating, pressurizing and depressurizing, or a combination thereof is performed.
- a uniform and homogeneous hole injecting and transporting layer can be formed while preventing film thickness unevenness, solute phase separation, and the like.
- the flatness of the hole injecting and transporting layer can be controlled by the method for removing the solvent contained in the coating liquid.
- the present invention is also an organic electroluminescent device in which a hole injecting and transporting layer is formed using the method for manufacturing an organic electroluminescent device.
- the hole injection / transport layer can be formed up to the edge of the bank, and an organic EL element excellent in film uniformity and luminous efficiency can be realized.
- the coating liquid for organic electroluminescence elements of the present invention it is possible to improve the spread in the bank. As a result, it is possible to realize an organic EL element that is excellent in the uniformity and luminous efficiency of the hole injecting and transporting layer.
- a glass substrate on which ITO (Indium Tin Oxide) was formed to a film thickness of 150 nm was patterned by a photolithography method to produce a glass substrate with an ITO transparent stripe electrode.
- the ITO transparent stripe electrode serves as the anode of the organic EL element.
- a liquid-repellent bank material is patterned so as to fill the space between the stripe-shaped ITO.
- a bank of 140 ⁇ m square (140 ⁇ m in both height and width) was formed.
- this substrate was subjected to a wet process using isopropyl alcohol, acetone, pure water or the like. It was cleaned by a cleaning method using a cleaning process and a cleaning process using a dry process such as UV / ozone treatment or plasma treatment.
- an organic EL coating solution containing PEDOT—PSS was prepared. Specifically, 10% 1% by weight aqueous dispersion of PEDOT-PSS, a hole injecting and transporting material, 58.0% ethanol ethanol, 25.0% water, diethylene glycol monopropyl ether 1 A coating liquid for a hole injection / transport layer (coating liquid 1) having a composition of 4% and ethylene glycol 5.6% was prepared. Note that the 1% by weight aqueous dispersion of PEDOT-PSS has a weight ratio of PEDOT and PSS of 1:20, and the total content of PEDOT and PSS is 1% by weight with respect to the entire aqueous dispersion. It is a solution.
- a coating solution is used using an ink jet apparatus having a head portion of 8 pl discharged at a time.
- PDF Poly (9,9-dioctylfluorene); polydioctylfluorene
- inkjet apparatus having a head portion of 8 pl discharged at a time.
- the substrate on which the light emitting material has been discharged is dried at room temperature (25 ° C) and reduced pressure (lOOPa) for 60 minutes, followed by heat treatment at 200 ° C for 60 minutes to remove the solvent and form a light emitting layer. did.
- Example 2 An organic electo-luminescence element was produced in the same manner as in Example 1 except that the composition of the coating liquid for hole injection transport layer was different.
- the coating solutions for the hole injection / transport layer in each of Examples 2 to 11 are designated as Coating solutions 2 to 11 respectively, and Table 1 shows each composition together with Example 1.
- DEGMPE represents diethylene glycol monopropyl ether
- EG represents ethylene glycol
- DEGMBE represents diethylene glycol monobutyl ether
- DEG represents diethylene glycol.
- force S using a 1% by mass aqueous dispersion of PEDOT-PSS was used.
- Example 11 2.5% by mass of PEDOT-PSS water
- PEDOT—PSS 2.5 mass% aqueous dispersion has a weight ratio of PEDOT to PSS of 1:20, and the total content of PE DOT and PSS is 2 . 5% by weight solution
- Table 2 shows the physical property values (1. boiling point under the condition of OX 10 5 Pa, viscosity under the condition of 20 ° C, and surface tension under the condition of 20 ° C) of each high boiling point solvent. It is the table shown.
- DEGM PE, DEGMBE, EG and DEG are all high boiling solvents having a boiling point of 180 ° C. or higher under the condition of 1 ⁇ 0 ⁇ 10 5 Pa.
- An organic electo-luminescence element was produced in the same manner as in Example 1 except that the composition of the coating liquid for hole injection transport layer was different.
- the coating liquids for hole injection / transport layers in Comparative Examples 1 and 2 are designated as Coating liquids 21 and 22, respectively.
- the mixing ratio of each composition is shown in Table 1 together with the examples. As shown in Table 1, Comparative Examples 1 and 2 do not contain a carbitol compound.
- the conversion ratio of the high boiling point solvent is, for each coating solution, the mass% of PEDOT-PSS in the aqueous dispersion of PEDOT-PS S is X, and the total volume% of all high boiling point solvents with respect to the total coating solution is y.
- PEDOT Calculated from y / (xXz), where z is the volume% of the total aqueous dispersion of PSS.
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
La présente invention concerne : une solution de revêtement d'un élément d'électroluminescence organique, qui est améliorée dans une propriété de répartition dans une barre ; un élément d'électroluminescence organique ; et un procédé de production d'élément d'électroluminescence organique. La solution de revêtement d'un élément d'électroluminescence organique peut s'utiliser pour former une couche transporteuse de trous pour un élément électroluminescent organique et elle comprend une matière formatrice de couche et un composé de carbitol en tant que solvant essentiel.
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JP2006257759 | 2006-09-22 | ||
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PCT/JP2007/063825 WO2008035501A1 (fr) | 2006-09-22 | 2007-07-11 | Solution de revêtement pour élément électroluminescent organique, cet élément et son procédé de production |
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US7651741B2 (en) * | 2002-04-01 | 2010-01-26 | Konica Corporation | Processes for forming a support and organic electroluminescence element including the support |
EP2391186A4 (fr) * | 2009-01-22 | 2013-09-25 | Sumitomo Chemical Co | Encre d'impression à jet d'encre pour élément électroluminescent organique, et procédé de fabrication d'un élément électroluminescent organique |
WO2015141151A1 (fr) * | 2014-03-17 | 2015-09-24 | 株式会社Joled | Solution pour former une couche fonctionnelle contenue dans un élément électroluminescent organique et procédé de fabrication d'élément électroluminescent organique |
US20220056291A1 (en) * | 2020-08-18 | 2022-02-24 | Samsung Display Co., Ltd. | Ink composition for light-emitting device and light emitting device manufactured using same |
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EP2391186A4 (fr) * | 2009-01-22 | 2013-09-25 | Sumitomo Chemical Co | Encre d'impression à jet d'encre pour élément électroluminescent organique, et procédé de fabrication d'un élément électroluminescent organique |
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