WO2013046608A1 - 薄膜形成方法 - Google Patents
薄膜形成方法 Download PDFInfo
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- WO2013046608A1 WO2013046608A1 PCT/JP2012/005985 JP2012005985W WO2013046608A1 WO 2013046608 A1 WO2013046608 A1 WO 2013046608A1 JP 2012005985 W JP2012005985 W JP 2012005985W WO 2013046608 A1 WO2013046608 A1 WO 2013046608A1
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- nozzles
- ink
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- line width
- nozzle
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/17—Ink jet characterised by ink handling
- B41J2/175—Ink supply systems ; Circuit parts therefor
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- 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
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
Definitions
- the present invention relates to a thin film forming method, and more particularly to a thin film forming method that can be used for forming a functional layer of an organic electroluminescence (EL) element.
- EL organic electroluminescence
- the ink jet method can discharge a minute amount of ink to a desired position according to the resolution of the head to be used, so that it is easy to form a fine pattern or a thin film having a desired film thickness. It has the feature. Taking advantage of this feature, the inkjet method is used for manufacturing organic EL elements and color filters that require fine coating. In addition, a technique has been proposed in which a paste-like functional material is continuously discharged from a nozzle having a single or a plurality of fine discharge ports to form a predetermined pattern on a substrate.
- the inkjet method or the nozzle method When the inkjet method or the nozzle method is applied to the manufacture of an organic EL element, a required amount of EL material is dispersed or dissolved in a predetermined solvent to form an ink, thereby making the EL more than the vapor deposition method or the sputtering method. There is an advantage that the utilization efficiency of the material can be improved.
- the tact time becomes longer as the substrate size becomes larger, so the productivity is lowered.
- the tact time can be shortened and productivity can be increased.
- the discharge amount of each nozzle varies, the thickness of the functional film to be formed varies. , Causing uneven emission.
- the functional liquid stored in a single supply source is branched and supplied to the plurality of nozzles, and simultaneously applied onto the substrate from each nozzle,
- a method of applying a functional liquid to a plurality of positions simultaneously In order to discharge an accurate discharge amount from the nozzle, it is necessary to measure and manage the actual discharge flow rate discharged from the nozzle. For example, the actual discharge flow rate discharged from the nozzle is discharged from the nozzle into a predetermined container, and is measured by the weight in the container with respect to the unit discharge time (see, for example, Patent Document 1).
- an object of the present invention is to provide a thin film forming method that makes it easy to adjust the discharge amount of liquid discharged from each of a plurality of nozzles.
- the present invention relates to a thin film forming method for forming a thin film by applying ink to a plurality of regions partitioned on a substrate using a plurality of nozzles.
- the discharge ports of the plurality of nozzles are brought close to the surface of the test substrate, and the ink is discharged from the plurality of nozzles while the test substrate and the plurality of nozzles are relatively moved.
- the discharge ports of the plurality of nozzles are brought close to the surface of the test substrate, and ink is discharged from the plurality of nozzles while the test substrate and the plurality of nozzles are relatively moved.
- the step of performing test coating the step of measuring the line width of the trajectory drawn by each of the plurality of nozzles at the time of test coating, while changing the relative movement speed of the plurality of nozzles and the test substrate, Repeating the test application step and the step of measuring the line width, obtaining a combination of relative movement speeds of the plurality of nozzles such that the line width of the trajectory drawn by each of the plurality of nozzles is the same, and While moving a plurality of nozzles and the substrate relative to each other at the relative movement speed obtained in the step of obtaining a combination of relative movement speeds by bringing a plurality of nozzles close to the surface of the substrate. And a step of ejecting ink from a plurality of nozzles onto a substrate.
- the discharge amount of each nozzle is adjusted based on the line width of the application mark applied to the test application part.
- the film thickness unevenness of the formed thin film can be reduced.
- FIG. 1 is a cross-sectional view of an organic EL element substrate according to an embodiment.
- FIG. 2 is a schematic view of a thin film shaper using a nozzle coating method.
- FIG. 3 is a detailed view of the cross section of the nozzle head.
- FIG. 4 is a schematic diagram of the test ejection device.
- FIG. 5 is a graph showing the relationship between the line width and the flow rate (before adjustment).
- FIG. 6 is a graph showing the relationship between the line width and the flow rate (after adjustment).
- FIG. 7 is a graph showing the relationship between the speed and the discharge amount.
- FIG. 8 is a graph showing the relationship between the line width and the flow rate (before adjustment).
- FIG. 9 is a graph showing the relationship between the line width and the flow rate (after adjustment).
- an organic EL element substrate is manufactured using a nozzle coating device.
- the present invention is not limited to an organic EL, and constitutes a display screen of another display display. It can be suitably used to form an optical component.
- optical components other than organic EL include color filters, circuit boards, thin film transistors, microlenses, and biochips.
- the pattern forming body of the hole injection layer, the hole transport layer, and the organic light emitting layer included in the organic EL element is collectively referred to as a functional layer, and this functional layer is formed using the coating apparatus according to the above embodiment. The case will be described with reference to FIG.
- the organic EL element is formed on the substrate.
- a translucent substrate 1 is preferably used as the substrate.
- a glass substrate or a plastic film or sheet can be used as the translucent substrate 1.
- a plastic film it is possible to wind up at the time of manufacturing a polymer EL element, and a display panel can be provided at a low cost.
- the plastic film that can be used include polyethylene terephthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, and polycarbonate.
- These films are composed of metal oxides such as silicon oxide that exhibit water vapor barrier properties and oxygen barrier properties, oxynitrides such as silicon nitride, polyvinylidene chloride, polyvinyl chloride, ethylene-vinyl acetate copolymer saponified products. It is preferable to provide a barrier layer as necessary.
- a patterned pixel electrode 2 is provided as an anode.
- transparent electrode materials such as ITO (indium tin composite oxide), IZO (indium zinc composite oxide), tin oxide, zinc oxide, indium oxide, and aluminum oxide composite oxide can be used. Of these electrode materials, ITO is preferably used because of its low resistance, solvent resistance, and transparency. ITO is formed on the translucent substrate by sputtering, and is patterned by photolithography to form line-shaped pixel electrodes 2.
- a partition wall 3 is formed between adjacent pixel electrodes 2.
- the partition walls 3 are provided in a lattice shape or a stripe shape on the substrate and the inspection substrate. Each region surrounded by the partition walls 3 becomes a discharge region that is a target for forming a thin film of ink by nozzle coating.
- the partition 3 is formed by a photolithography method using a photosensitive material.
- the photosensitive material for forming the partition wall 3 may be either a positive type resist or a negative type resist, but it must have insulating properties. If the partition 3 does not have sufficient insulation, a current flows to the adjacent pixel electrode through the partition and a display defect occurs.
- a light shielding material may be included in the photosensitive material.
- an ink repellent such as a fluorine-containing compound or a silicon-containing compound
- the thickness (height) of the partition wall 3 is preferably 0.5 to 5.0 ⁇ m.
- Hole injection materials include metal phthalocyanines such as copper phthalocyanine and tetra (t-butyl) copper phthalocyanine, metal-free phthalocyanines, quinacridone compounds, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N , N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine, N, N'-di (1-naphthyl) -N, N'- Aromatic amine low molecular hole injection / transport materials such as diphenyl-1,1'-biphenyl-4,4'-diamine, polymer hole injection materials
- Examples of the solvent for dissolving or dispersing the hole injection material include halogen solvents such as chloroform, dichloromethane, dichloroethane, trichloroethylene, ethylene chloride, tetrachloroethane, chlorobenzene, N-methyl-2-pyrrolidone (NMP), dimethyl Polar solvents such as aprotic polar solvents such as formamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and alkoxy alcohols such as propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether Etc.
- halogen solvents such as chloroform, dichloromethane, dichloroethane, trichloroethylene, ethylene chloride, tetrachloroethane, chlorobenzene, N-methyl-2-pyrrolidone (NMP), dimethyl Polar solvents such as a
- hole transporting substance examples include poly (N-vinylcarbazole) (hereinafter also referred to as PVK), poly (para-phenylene vinylene), carbazole biphenyl (hereinafter also referred to as CBP), N, N′—.
- NPD N-bis (1-naphthyl) -1,1′-biphenyl-4,4′-diamine
- TPD N-bis (3 -Methylphenyl) -1,1'-biphenyl-4,4'-diamine
- TPD 4,4'-bis (10-phenothiazinyl) biphenyl
- 1,3,5-triazole polyfluorene derivatives
- a copolymer of triphenylamine and fluorene 1,3,5-triazole, polyfluorene derivatives, and a copolymer of triphenylamine and fluorene.
- Examples of the solvent for the functional ink that forms the hole transport layer include siemen, tetralin, cumene, decalin, durene, cyclohexylbenzene, dihexylbenzene, tetramethylbenzene, and dibutylbenzene.
- the organic light emitting layer 6 is a layer that emits light when an electric current is applied.
- the organic light-emitting material for forming the organic light-emitting layer 6 include, for example, coumarin-based, perylene-based, pyran-based, anthrone-based, porphyrin-based, quinacridone-based, N, N′-dialkyl-substituted quinacridone-based, naphthalimide-based, N, N '-Diaryl-substituted pyrrolopyrrole, iridium complex and other luminescent dyes dispersed in polymers such as polystyrene, polymethylmethacrylate, polyvinylcarbazole, polyarylene, polyarylene vinylene and polyfluorene Examples include polymer materials.
- Examples of the solvent for the functional ink that forms the organic light emitting layer 6 include siemen, tetralin, cumene, decalin, durene, cyclohexylbenzene, dihexylbenzene, tetramethylbenzene, and dibutylbenzene.
- a functional ink containing a hole injection material is ejected to the substrate 1 on which the partition walls 3 are formed by a nozzle coating method described later, thereby forming a hole injection layer 4.
- the hole transport layer 5 is formed by discharging a functional ink containing a hole transport material by a nozzle coating method described later.
- the cathode layer 7 is formed in a line pattern orthogonal to the line pattern of the pixel electrode 2.
- a material corresponding to the light emission characteristics of the organic light emitting layer 6 can be used.
- a simple metal such as lithium, magnesium, calcium, ytterbium, and aluminum or a stable metal such as gold and silver can be used. And alloys thereof.
- a conductive oxide such as indium, zinc, or tin can be used.
- the method for forming the cathode layer include a method using a vacuum vapor deposition method using a mask.
- a glass cap 8 and an adhesive 9 are hermetically sealed to obtain an organic EL display panel.
- any method may be used as long as the organic EL structure can be protected from external oxygen and moisture.
- substrate 1 has flexibility, you may seal using a sealing agent and a flexible film.
- the hole injection layer 4, the hole transport layer 5, and the organic light emitting layer 6 are disposed between the pixel electrode 2 that is an anode and the cathode layer 7 in order from the anode layer side.
- layers such as a hole blocking layer, an electron transport layer, and an electron injection layer are provided as needed between the anode layer and the cathode layer.
- a laminated structure can be taken.
- the formation method similar to the organic light emitting layer 6 is applicable.
- the ink 11 filled in the ink supply tank 10 is supplied to the nozzle head 13 through the ink supply tube 12.
- Supply of the ink 11 to the nozzle head 13 is performed by pressurizing the inside of the ink supply tank 10 with the pressurizer 14 and pushing out the ink 11 from the ink supply tank 10.
- a flow rate control valve 15 for controlling the discharge amount of the ink 11
- a flow meter 16 for measuring the flow rate of the ink 11 supplied to the nozzle head 13.
- the flow rate control valve 15 is controlled based on information from the flow meter 16 (that is, ink flow rate) and can adjust the ink flow rate, a stable desired ink flow rate can be obtained.
- a plurality of nozzle heads 13 are provided in the nozzle coating device, a plurality of sets of configurations from the nozzle head 13 to the ink supply tank 10 are provided.
- the nozzle coating device includes a table 17 and an operation stage 19 which is disposed on the table 17 and is movable on the table 17 in the X direction and the Y direction perpendicular thereto.
- the movable stage 19 By moving the movable stage 19 in the Y direction or Y ′ direction (or X direction or X ′ direction) while discharging the ink 11 from the discharge port of the nozzle head 13, the nozzle 11 is continuously arranged on the movable stage 19.
- a coating film can be formed on the translucent substrate 18.
- a translucent substrate 18 in which a plurality of pixel formation regions extending in parallel to each other in the X direction are provided in a stripe shape is disposed on a movable stage 19, and the movable stage 19 and the nozzle head 13 are relative to each other in the Y direction.
- Move to based on the positional information of the movable stage 19 and the nozzle head 13, the movement of the movable stage 19 and the nozzle head 13 is synchronized, and R (Red), G (Green), or B (Blue) 1
- the ink 11 is continuously applied to the pixel formation region of the book to form a coating film.
- the movable stage 19 and the nozzle head 13 are relatively moved to a X direction, and a coating film is formed in the following pixel formation area .
- the ink 11 enters a cylindrical or cuboid case 22 made of SUS (stainless steel) or the like from the ink supply tube 12.
- the case 22 is generally made of metal, but any case having ink resistance may be used.
- the inside of the case 22 is a manifold, and the liquid column 25 is discharged from the nozzle 23 having a minute hole having a diameter of about 5 to 20 microns to the translucent substrate 18.
- the nozzle is generally a film of polyimide or the like, but any nozzle can be used as long as it can accurately make a hole.
- ink ejected from the nozzles be ejected continuously. For this reason, a portion that is not desired to be ejected may be masked or a dummy pattern may be provided, but any method may be used as long as there is no problem as a panel.
- FIG. 4 shows a schematic configuration of a test coating apparatus that performs the test coating of the present invention.
- the test coating apparatus shown in FIG. 4 includes an image receiving layer film 28, a line width inspection unit 34 for optically capturing information of an image for line width inspection recorded on the image receiving layer film 28, and a line width inspection unit 34.
- An image information processing unit 32 for inspecting the line width from the image information taken in, a film unit 36 for feeding and winding the image receiving layer film 28, and a control unit (not shown) for controlling these operations. At least).
- the image-receiving layer film 28 is a recording medium for line width inspection for producing a locus-like line width inspection image 35 drawn by ejecting ink from a plurality of nozzles.
- a commercially available ordinary film can be used as the image receiving layer film 28 .
- a PET (polyethylene terephthalate) film can be used as a transparent film, and an image-receiving layer provided with a coating layer in which fine pigments are uniformly dispersed can be used. What is necessary is just to select suitably according to conditions, such as.
- the line width inspection image 35 recorded on the image receiving layer film 28 is moved by the drive roller 37 to a place where the line width inspection section 34 is located.
- the line width inspection camera 27 captures the line width inspection image as image information and transfers the image information to the image information processing unit 32.
- the illumination 29 is turned on to illuminate the inspection image recorded on the image receiving layer film, thereby adding contrast and clearly recognizing the shape of the inspection image. Can be taken in.
- the illumination 29 can be installed on the camera side from the image receiving layer film, or the camera 27 can capture an image using only external light.
- the inspection image recorded on the image receiving layer film 28 is fine, it can be handled by appropriately selecting the resolution, viewing angle, etc. of the optical camera of the image information detection unit. It is.
- the gap between the image receiving layer film 28 and the nozzle is set to be equal to the gap between the substrate and the nozzle when the substrate is placed on the stage of the nozzle coating apparatus.
- the test coating device is installed so that the driving direction of the image receiving layer film is perpendicular to the driving direction of the nozzle of the nozzle coating device.
- the coating device and the test coating device are installed adjacent to each other. Moreover, when it is non-ejection when test-applying, it discharges again and it coats. That is, non-ejection inspection can be performed at the same time.
- the relationship between the line width and the flow rate is first grasped.
- a line width inspection image is created by aligning the flow rate of each nozzle, and line width data of each nozzle is acquired. By repeating it at a plurality of flow rates, the relationship between the flow rate of each nozzle and the line width is obtained.
- Fig. 5 shows the line width of each nozzle when three nozzles are used and the flow rate is applied at five levels a1 to a5. As shown in FIG. 5, the line width is usually different even if the flow rate is uniform for each nozzle.
- the flow rate is adjusted so that the target line width is obtained.
- an approximate straight line between the flow rate and the line width of each nozzle is obtained. From the approximate straight line, the flow rate is calculated so that the line widths of the nozzles 2 and 3 are the same as the line width of the nozzle 1.
- the line widths of the nozzles 2 and 3 can be matched with the line width of the nozzle 1 as shown in FIG. Since the line width and the discharge amount are in a proportional relationship, if the line width is equal, the discharge amount is equal.
- a method for adjusting the flow rate described above as a method for adjusting the line width and a method for adjusting at a speed at which the nozzle is moved relative to the substrate.
- the discharge amount and the speed indicate a power function relationship. Therefore, the line width can be adjusted by changing the speed, as in the case where the line width is adjusted by the flow rate.
- the relationship between speed and flow rate is shown in FIG.
- each of the plurality of nozzles is configured to be independently movable at a different speed.
- a plurality of line width inspection images are created while changing the relative movement speed of each nozzle, and the relationship between the relative speed of each nozzle and the line width as shown in FIG.
- the hole injection layer, the hole transport layer, and the organic light emitting layer are formed by the nozzle coating method, but it is not necessary to form all these layers by the nozzle coating method.
- a pixel electrode was formed by forming an ITO (indium-tin oxide) thin film on a 3-inch diagonal glass substrate by sputtering and patterning the ITO film by photolithography and etching with an acid solution. .
- the line pattern of the pixel electrode was a pattern in which about 590 lines were formed in about 7.6 mm square with a line width of 70 ⁇ m and a space of 60 ⁇ m.
- an insulating layer was formed as follows. First, a polyimide resist material was spin-coated on the entire surface of a glass substrate on which pixel electrodes were formed. The spin coating condition was rotated at 150 rpm for 5 seconds, and then rotated at 500 rpm for 20 seconds to form a single coating. The height of the insulating layer was 2.5 ⁇ m. A partition which is an insulating layer having a stripe pattern between pixel electrodes was formed by photolithography on the photoresist material applied to the entire surface. This partition has ink repellency.
- the hole injection ink using a mixture of polymer hole injection materials such as poly (p-phenylene vinylene) and polyaniline and propylene glycol monobutyl ether, the solid content concentration of the ink is 1.5%, the viscosity is An ink of 7 mPa ⁇ s was prepared.
- polymer hole injection materials such as poly (p-phenylene vinylene) and polyaniline and propylene glycol monobutyl ether
- the prepared hole injection ink was put in an ink supply tank.
- the hole injection ink in the ink supply tank is supplied to the nozzle head through the ink supply tube by pressurizing the ink supply tank.
- a flow rate control valve that controls the amount of ink ejected between the ink supply tank and the nozzle, and a flow meter for measuring the flow rate of ink flowing to the nozzle head are provided. Based on the information of the ink flow meter, By feeding back to the flow control valve and adjusting the flow rate, a stable desired ink flow rate can be obtained.
- the positions of the nozzle head and the table are relatively fixed, and the above-described translucent substrate having the stripe pattern partition walls imparted with ink repellency was fixed to a movable stage.
- the above-mentioned movable stage can move on the above-mentioned table in the direction of Y or Y ′ in the vertical direction.
- the nozzle head can move in the direction X or X ′ in the lateral direction orthogonal to the Y or Y ′ direction.
- the ink enters the rectangular nozzle head made of stainless steel from the ink supply tube.
- the inside of the nozzle head is a manifold, and can be discharged in a vertical direction with respect to the translucent substrate from a polyimide film nozzle having a minute hole with a diameter of 8 microns. In this example, three nozzles were used.
- FIG. 8 shows the relationship between the flow rate before adjustment and the line width
- FIG. 9 shows the relationship between the flow rate after adjustment and the line width
- Table 1 shows the flow rate and line width of each nozzle before and after adjustment.
- the hole injection layer was applied at the adjusted flow rate.
- the amount of ink ejected from the nozzles is maintained uniformly.
- the hole injection layer was formed by putting the board
- an ink having a solid content concentration of 4.0% and a viscosity of 10 mPa ⁇ s was prepared using a hole transport material made of a polyfluorene derivative and cyclohexylbenzene.
- hole transport layer discharging was performed on the substrate on which the hole injection layer was formed with the same apparatus and procedure as when the hole injection layer was formed. After discharging, it was confirmed that a hole transport layer having a desired film thickness was obtained by firing at 200 ° C. for 1 hour in a nitrogen atmosphere to form a hole transport layer.
- the solid content concentration of the ink is 7.0%
- the R ink has a viscosity of 30 mPa ⁇ s
- the solid content concentration is 5.0%.
- a G ink having a viscosity of 5 mPa ⁇ s, a B ink having a solid content concentration of 6.0% and a viscosity of 20 mPa ⁇ s were prepared.
- the organic light emitting layer discharging was performed on the substrate on which the hole transport layer was formed by the same apparatus and procedure as those for forming the hole injection layer described above. After discharge, an RGB organic light emitting layer was formed by baking at 130 ° C. for 30 minutes in a nitrogen atmosphere. Then, it confirmed that the organic light emitting layer of the desired film thickness was obtained by the film thickness measurement.
- a cathode layer made of Ca and Al was formed thereon by mask vapor deposition using a resistance heating vapor deposition method in a line pattern orthogonal to the pixel electrode line pattern. Finally, in order to protect these organic EL constituents from external oxygen and moisture, they were hermetically sealed using a glass cap and an adhesive to produce an organic EL display panel.
- anode side extraction electrode and a cathode side extraction electrode connected to each pixel electrode in the periphery of the display portion of the organic EL element substrate obtained in this way, and these are obtained by connecting them to a power source.
- the lighting display of the obtained organic EL element substrate was confirmed, and the light emission state was checked.
- an organic EL element substrate with a material utilization efficiency of 90% and no unevenness in light emission luminance could be obtained.
- Comparative Example 1 As a comparative example, when ink is applied with the discharge amount from each nozzle as the value before adjustment in Table 1, a difference in film thickness occurs due to the difference in discharge amount for each nozzle in the light emission region of the panel, resulting in uneven brightness of light emission However, a high-quality organic EL element substrate could not be obtained.
- the present invention can be used for manufacturing organic EL elements and the like.
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Abstract
Description
有機EL素子は基板上に形成される。基板としては透光性基板1が好適に用いられる。透光性基板1としては、ガラス基板やプラスチック製のフィルムまたはシートを用いることができる。プラスチック製のフィルムを用いる場合、高分子EL素子の製造時に巻き取りが可能となり、安価にディスプレイパネルを提供できる。プラスチック製のフィルムとしては、例えば、ポリエチレンテレフタレート、ポリプロピレン、シクロオレフィンポリマー、ポリアミド、ポリエーテルスルホン、ポリメタクリル酸メチル、ポリカーボネート等を用いることができる。また、これらのフィルムには、水蒸気バリア性、酸素バリア性を示す酸化ケイ素といった金属酸化物、窒化ケイ素といった酸化窒化物やポリ塩化ビニリデン、ポリ塩化ビニル、エチレン-酢酸ビニル共重合体鹸化物からなるバリア層を必要に応じて設けることが好ましい。
透光性基板1の上には、陽極として、パターニングされた画素電極2が設けられる。画素電極2の材料としては、ITO(インジウム錫複合酸化物)、IZO(インジウム亜鉛複合酸化物)、酸化錫、酸化亜鉛、酸化インジウム、酸化アルミニウム複合酸化物等の透明電極材料等が使用できる。なお、これらの電極材料の中でも、低抵抗であること、耐溶剤性があること、透明性があることなどからITOを用いることが好ましい。ITOはスパッタ法により透光性基板上に形成されて、フォトリソグラフィ法によりパターニングされライン状の画素電極2となる。
ライン状の画素電極2を形成後、隣接する画素電極2の間に隔壁3を形成する。隔壁3は、基板および検査用基板上に、格子状またはストライプ状に設けられる。隔壁3に囲まれた各領域は、ノズル塗布によってインクの薄膜を成膜する対象である吐出領域となる。隔壁3は、感光性材料を用いて、フォトリソグラフィ法により形成される。隔壁3を形成する感光性材料としてはポジ型レジスト、ネガ型レジストのどちらであってもよいが、絶縁性を備えている必要がある。隔壁3に十分な絶縁性がない場合には隔壁を通じて隣り合う画素電極に電流が流れてしまい表示不良が発生してしまう。具体的にはポリイミド系、アクリル樹脂系、ノボラック樹脂系、フルオレン系といったものが挙げられるが、これらに限定されるものではない。また、有機EL素子の表示品位を上げる目的で、光遮光性の材料を感光性材料に含有させても良い。また、隔壁材料に含フッ素化合物や含ケイ素化合物等の撥インク剤を適量添加することで、適度な撥インク性を持たせることができる。
正孔注入層4を形成するためのインク調整について説明する。形成される正孔注入層4の体積抵抗率は、発光効率の点から1×106Ω・cm以下であることが好ましい。正孔注入材料は、銅フタロシアニン、テトラ(t-ブチル)銅フタロシアニン等の金属フタロシアニン類や無金属フタロシアニン類、キナクリドン化合物、1,1-ビス(4-ジ-p-トリルアミノフェニル)シクロヘキサン、N,N’-ジフェニル-N,N’-ビス(3-メチルフェニル)-1,1’-ビフェニル-4,4’-ジアミン、N,N’-ジ(1‐ナフチル)-N,N’-ジフェニル-1,1’-ビフェニル-4,4’-ジアミン等の芳香族アミン系低分子正孔注入輸送材料や、ポリ(p-フェニレンビニレン)、ポリアニリン等の高分子正孔注入材料、ポリチオフェンオリゴマー材料、その他の既知の正孔注入材料の中から選ぶことができる。
正孔輸送層5を形成するためのインク調整について説明する。正孔輸送性物質としては、例えば、ポリ(N-ビニルカルバゾール)(以下、PVKともいう。)、ポリ(パラ-フェニレンビニレン)、カルバゾールビフェニル(以下、CBPとも言う。)、N,N’-ジフェニル-N,N’-ビス(1-ナフチル)―1,1’-ビフェニル-4,4’-ジアミン(以下NPDとも言う。)、N,N’-ジフェニル-N,N’-ビス(3-メチルフェニル)-1,1’-ビフェニル-4,4’-ジアミン(以下TPDともいう。)、4,4’-ビス(10-フェノチアジニル)ビフェニルや、2,4,6-トリフェニル-1,3,5-トリアゾール、ポリフルオレン誘導体、トリフェニルアミンとフルオレンの共重合体などを挙げることができる。
正孔輸送層を形成する機能性インクの溶媒としては、シメン、テトラリン、クメン、デカリン、ジュレン、シクロヘキシルベンゼン、ジヘキシルベンゼン、テトラメチルベンゼン、およびジブチルベンゼン等が挙げられる。
有機発光層6を形成するためのインク調整について説明する。有機発光層6は電流を流すことにより発光する層である。有機発光層6を形成する有機発光材料としては、例えば、クマリン系、ペリレン系、ピラン系、アンスロン系、ポルフィレン系、キナクリドン系、N,N’-ジアルキル置換キナクリドン系、ナフタルイミド系、N,N’―ジアリール置換ピロロピロール系、イリジウム錯体系等の発光性色素をポリスチレン、ポリメチルメタクリレート、ポリビニルカルバゾール等の高分子中に分散させたものや、ポリアリーレン系、ポリアリーレンビニレン系やポリフルオレン系の高分子材料が挙げられる。有機発光層6を形成する機能性インクの溶媒としては、シメン、テトラリン、クメン、デカリン、ジュレン、シクロヘキシルベンゼン、ジヘキシルベンゼン、テトラメチルベンゼン、およびジブチルベンゼン等が挙げられる。
隔壁3を形成した基板1に対して、後述のノズル塗布法により正孔注入材料を含んだ機能性インクを吐出し、正孔注入層4を形成する。
正孔注入層4形成後、後述のノズル塗布法により正孔輸送性物質を含む機能性インクを吐出して正孔輸送層5を形成する。
正孔輸送層5形成後、後述のノズル塗布法により有機発光材料を含む機能性インクを吐出して、有機発光層6を形成する。
有機発光層6形成後、陰極層7を画素電極2のラインパターンと直交するラインパターンで形成する。陰極層7の材料としては、有機発光層6の発光特性に応じたものを使用でき、例えば、リチウム、マグネシウム、カルシウム、イッテルビウム、アルミニウムなどの金属単体やこれらと金、銀などの安定な金属との合金などが挙げられる。また、インジウム、亜鉛、錫などの導電性酸化物を用いることもできる。陰極層の形成方法としてはマスクを用いた真空蒸着法による形成方法が挙げられる。
最後にこれらの有機EL構成体を、外部の酸素や水分から保護するために、ガラスキャップ8と接着剤9を用いて密閉封止し、有機ELディスプレイパネルを得ることが出来る。封止方式としては、有機EL構成体を外部の酸素や水分から保護できればどのような方法をとっても良い。また、透光性基板1が可撓性を有する場合は封止剤と可撓性フィルムとを用いて封止を行っても良い。
以下、正孔注入層、正孔輸送層、有機発光層の形成に用いるノズル塗布装置の構成例について、図2を参照しながら説明するが、本発明はこれに限定されるものではない。
図4に、本発明の試験塗布を行う試験塗布装置の概略の構成を示す。
次に、試験塗布装置での線幅測定結果から吐出量を調整する方法を説明する。複数ノズルから流量計の値を揃えて吐出した場合、実際に各ノズルから吐出される実吐出量はそれぞれ微妙に異なる。ノズルのノズル径が異なっていたり、流量計の精度が装置毎に異なっていたりするためである。
この隔壁は、撥インク性を有している。
比較例として、各ノズルからの吐出量を、表1の調整前の値としてインクを塗布した場合、パネルの発光領域においてノズル毎の吐出量の違いにより膜厚差が生じ、発光輝度ムラが発生し高品質な有機EL素子基板を得ることができなかった。
2 画素電極
3 隔壁
4 正孔注入層
5 正孔輸送層
6 有機発光層
7 陰極層
8 ガラスキャップ
9 接着剤
10 インク供給タンク
11 インク
12 インク供給チューブ
13 ノズルヘッド
14 加圧機
15 流量制御弁
16 流量計
17 テーブル
18 透光性基板
19 可動ステージ
22 ケース
23 ノズル
25 液柱
26 ヘッドユニット
27 カメラ
28 受像層フィルム(吐出検査用被記録体)
29 照明
30 繰り出しローラー
31 巻取りローラー
32 画像情報処理部
33 線幅表示機構
34 線幅検査部
35 線幅検査用画像
36 フィルム部
37 駆動ローラー
Claims (2)
- 複数のノズルを用いて、基材上に区画された複数の領域にインクを塗布して薄膜を形成する薄膜形成方法であって、
試験用基材の表面に前記複数のノズルの吐出口を近接させ、前記試験用基材と前記複数のノズルとを相対移動させながら、前記複数のノズルからインクを吐出させて、試験塗布を行うステップと、
前記試験塗布時に、前記複数のノズルの各々によって描かれた軌跡の線幅を測定するステップと、
前記複数のノズルの各々に供給するインクの流量を変化させながら、前記試験塗布を行うステップと、前記線幅を測定するステップとを繰り返し、前記複数のノズルの各々によって描かれる軌跡の線幅が同一となるような、前記複数のノズルの各々に供給するインクの流量の組み合わせを求めるステップと、
前記基材の表面に前記複数のノズルを近接させ、前記基材と前記複数のノズルを相対移動させながら、前記流量の組み合わせを求めるステップで求めた流量の組み合わせを用いて、前記複数のノズルから前記基材上にインクを吐出させるステップとを備える、薄膜形成方法。 - 複数のノズルを用いて、基材上に区画された複数の領域にインクを塗布して薄膜を形成する薄膜形成方法であって、
試験用基材の表面に前記複数のノズルの吐出口を近接させ、前記試験用基材と前記複数のノズルとを相対移動させながら、前記複数のノズルからインクを吐出させて、試験塗布を行うステップと、
前記試験塗布時に、前記複数のノズルの各々によって描かれた軌跡の線幅を測定するステップと、
前記複数のノズルと前記試験用基材との相対移動速度を変化させながら、前記試験塗布を行うステップと、前記線幅を測定するステップとを繰り返し、前記複数のノズルの各々によって描かれる軌跡の線幅が同一となるような、前記複数のノズルの相対移動速度の組み合わせを求めるステップと、
前記基材の表面に前記複数のノズルを近接させ、前記相対移動速度の組み合わせを求めるステップで求められた相対移動速度で、前記複数のノズルと前記基材とを相対移動させながら、前記複数のノズルから前記基材上にインクを吐出させるステップとを備える、薄膜形成方法。
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JP2001137756A (ja) * | 1999-11-10 | 2001-05-22 | Musashi Eng Co Ltd | 液体の塗布方法および装置 |
JP2006205024A (ja) * | 2005-01-27 | 2006-08-10 | Dainippon Screen Mfg Co Ltd | 塗布装置 |
JP2011104475A (ja) * | 2009-11-13 | 2011-06-02 | Seiko Epson Corp | 液滴吐出方法及び液滴吐出装置 |
JP2011235237A (ja) * | 2010-05-11 | 2011-11-24 | Olympus Corp | 塗布剤塗布方法および塗布剤塗布装置 |
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JP2006205024A (ja) * | 2005-01-27 | 2006-08-10 | Dainippon Screen Mfg Co Ltd | 塗布装置 |
JP2011104475A (ja) * | 2009-11-13 | 2011-06-02 | Seiko Epson Corp | 液滴吐出方法及び液滴吐出装置 |
JP2011235237A (ja) * | 2010-05-11 | 2011-11-24 | Olympus Corp | 塗布剤塗布方法および塗布剤塗布装置 |
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