JP5109513B2 - Pattern film forming device - Google Patents

Description

  The present invention relates to a pattern film forming method and a pattern film forming apparatus. Specifically, an organic functional film, which is mainly an organic thin film composed of a carrier transport material, a light emitting material, a charge generation material, etc. used in organic solar cells and organic EL displays, is applied on a substrate by a wet method such as a coating printing method. The present invention relates to a pattern film forming method and a pattern film forming apparatus for forming a patterned film by removing an unnecessary portion after forming an organic functional film on one surface of a substrate when forming multiple faces.

  In recent years, a carrier transport material made of a polymer having high conductivity and light emission and a light-emitting material made of a conjugated polymer soluble in an organic solvent have been actively developed. Regarding the organic EL element, Non-Patent Documents 1, 2, 3, and 4 disclose an inkjet method that can easily form a film on a large-area substrate and has high material use efficiency. Non-Patent Document 5 discloses a technique for separately painting subpixels made of red, blue, and green of a light emitting layer using a relief printing method.

  The light-emitting layer can be formed separately by using the printing method, and the manufacturing equipment can be manufactured at a lower cost than the vacuum vapor deposition method, and the film formation speed is high, which is advantageous for realizing a large-area organic EL color display. It is done.

  In an organic EL element formed by a wet method, a composite of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (hereinafter abbreviated as PEDOT: PSS) as a hole injection layer. An aqueous dispersion of a polythiophene-based or polyaniline-based conductive polymer is used. These hole injection layers can be formed using an ink jet method or a relief printing method. Film formation by the inkjet method has a problem in productivity. In the film formation by the relief printing method, the resin relief printing plate is deformed because it absorbs water-based ink, so that the ink is easily repelled and a problem in the smoothness of the film is likely to occur.

  Further, when the coating is performed by a method such as a spin coating method or a slit coating method, the smoothness of the film is higher than that of the relief printing method, and the film formation time is shorter than that of the ink jet method. In the spin coat method and the slit coat method, since ink is applied all over the substrate, unnecessary portions such as a bonding margin for bonding a sealing glass plate or a sealing can and a portion for forming an electrode terminal are removed. Needed to be removed. Conventionally, a solvent is applied to a cotton swab or cloth tape to wipe away unnecessary portions. In addition, laser ablation, oxygen plasma cleaning, ozone cleaning, and the like have been performed to remove unnecessary portions. However, there is a problem that time is required and an expensive apparatus is required.

  Especially when producing organic EL elements on a large substrate with multiple surfaces, the time and labor required for wiping and removing unnecessary parts in the conventional method is extremely large, which is a cause of reducing the productivity of organic EL elements by the wet method. It was.

In addition, organic solar cells (see Non-Patent Document 6) and photovoltaic cells also have the same problems as in the case where an organic EL element is produced using a conductive polymer such as PEDOT: PSS for the hole transport layer.
T.FUNAMOTO, Y. Matsueda, O. Yokoyama, A. Tsuda, H. Takeshita, A. Miyashita, SID 02 DIGEST, 27.5L (2002). T. Shimoda, SID 03 DIGEST, 39.1 (2003). David Albertalli, SID 05 DIGEST, 30.3 (2005). Tadashi Gohda, Yuhki Kobayashi, Kiyoshi Okano, Satoshi Inoue, Ken Okamoto, Satoshi Hashimoto, Emi Yamamoto, Haruyuki Morita, Seiichi Mitsui and Mitsuhiro Koden, SID 06 DIGEST, 58.3 (2006). E. Kitazume, K. Takeshita, K. Murata, Y. Qian, Y. Abe, M. Yokoo, K. Oota, T. Taguchi, SID06DIGEST, 41.2 (2006). Chu-Jung Ko, Yi-Kai Lin, Fang-Chung Chen and Chi-Wei Chu, Appl. Phys. Lett., 90, 063509-1 (2007).

  In the present invention, it is combined with a method of forming a film by coating all over a substrate such as a spin coat method, a slit coat method, a slit and spin coat method, etc., which is not practical because it takes time and effort to wipe an unnecessary part of the film. And providing a pattern film forming method and a pattern film forming apparatus.

  In the present invention, when an organic functional film such as an organic solar battery and an organic EL display is formed on a substrate by a wet method such as coating printing, a film removal process for removing unnecessary films is reduced in cost. To provide a pattern film forming method and a pattern film forming apparatus which can be speeded up.

According to a first aspect of the present invention, there is provided a pattern film forming apparatus that patterns an organic functional film formed on one surface of a substrate into a desired shape. A plurality of rubber-like rings arranged in a shape, a plurality of heater unit blocks arranged at a certain interval on the other surface of the cap plate, and a plurality of heater unit blocks on one end A plurality of suction pipes extending in between and having at least one opening disposed as a second end in each of a plurality of regions surrounded by a plurality of rubber-like rings, and a plurality of one end portions A plurality of cleaning and ventilation drying tubes extending between the heater unit blocks and having at least one opening disposed at the other end in a plurality of regions other than a region surrounded by a plurality of rubber rings. And the base And it has a mechanism for adhering the organic functional film into a plurality of rubber rings, a mechanism for adhering the substrate and the organic functional film into a plurality of rubber rings fixed to the cap plate the substrate on a substrate support and it is opposed, one of the cap plate or the substrate support, aligning the cap plate or the substrate support opposite, between a plurality of closed space formed by the cap plate and the substrate and a plurality of rubber rings by enclosed Mukoto each brought into close contact with the substrate and a plurality of rubber rings under reduced pressure to a plurality of washing and air drying tube opening is arranged in each of the plurality of areas other than the area surrounded by the plurality of rubber rings, The pattern film forming apparatus is characterized in that it is a pipe that supplies the cleaning liquid and the drying air in common.

The invention according to claim 2 of the present invention is the pattern film forming apparatus according to claim 1, wherein the cross-sectional shape of the rubber ring is polygonal or circular.

The invention according to claim 3 of the present invention, the width of the rubber rings, the claim 1 or characterized is obtained by the pattern film forming apparatus according to claim 2 that is 0.5mm~4mm .

  According to the present invention, when an organic functional film such as an organic solar cell and an organic EL display is formed on a substrate by a wet method such as coating printing, a film removal process for removing unnecessary films is reduced in cost. A pattern film forming method and a pattern film forming apparatus can be provided which can be made faster and faster.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the embodiments, the same components are denoted by the same reference numerals, and redundant description among the embodiments is omitted.

  As shown in FIG. 9, the pattern film forming apparatus 100 according to the embodiment of the present invention includes a cap plate 2 provided with a rubber-like ring 1 arranged on one surface having one or more desired shapes. (See FIG. 1 and FIG. 2). The heater unit block 9 and the heater unit block are arranged with a certain distance between the other surface of the cap plate 2 and the surface of the substrate support 3 where the substrate 5 is not fixed. 9 are provided with suction pipes 7 and cleaning and ventilation drying pipes 8 arranged alternately.

The heater unit block 9 is for drying, and hot water, an electric heater, or the like can be used. In addition, in order to dry rapidly, the Peltier device which can adjust heating and cooling can be used. The suction pipe 7 can bring the cap plate 2 and the substrate 5 into close contact with each other by suction and pressure reduction. The cleaning and ventilation drying tube 8 can be provided with a tube for flowing the cleaning liquid and a ventilation drying tube simultaneously or separately.

  As shown in FIG. 1, a cap plate 2 is provided around a rubber-like ring 1 having a desired shape. As shown in FIG. 2, the cap board 2 provided with the rubber-like ring 1 arrange | positioned by having one or more desired shapes on one surface is provided.

  The rubber ring 1 can be made of an organic solvent-resistant, acid-resistant fluorine-based rubber, ethylene-propylene-based rubber, or the like, but when an organic solvent is used as a cleaning solvent, a fluorine-based crosslinked rubber that is difficult to swell is preferably used.

  In the embodiment of the present invention, as shown in FIG. 2, a rubber ring 1 having a circular cross section on one surface of the cap plate 2 or a rubber ring 1 having a substantially triangular shape as shown in FIG. A cap plate 2 that is bent into an arbitrary shape such as a circle or a triangle and fixed one by one in a row can be used.

  The width of the cross section of the rubber ring 1 is 4 mm or less. More preferably, it is 0.5 mm to 4 mm. If it is thinner than 0.5 mm, the strength of the rubber-like ring 1 is insufficient, the watertight sealability is insufficient, the distance between the substrate 5 and the cap plate 2 is too narrow, and it is difficult for the cleaning solvent to spread or difficult to dry. There is a case. Further, if the width is larger than 4 mm, there is a problem that the frame area of the display panel becomes large. In order to reduce the contact area with the substrate 5 and increase the strength of the rubber ring 1, it is more desirable to use a triangular shape.

  The rubber ring 1 can be grooved and fitted into the cap plate 2, and can be bonded and fixed with an adhesive.

  The cap plate 2 is manufactured using a material resistant to a cleaning solvent such as a stainless plate, a titanium plate, a ceramic plate, and a resin plate.

  Hereinafter, a pattern film forming method according to an embodiment of the present invention will be described in detail with reference to FIGS. As shown in FIG. 2, a cap plate 2 provided with a rubber-like ring 1 disposed on one surface having one or more desired shapes is prepared.

  As shown in FIG. 3, the rubber-like ring 1 formed on one surface of the prepared cap plate 2 and the organic functional film 4 formed on one surface of the substrate 5 are fixed to the substrate support 3. They are placed facing each other. Here, the solvent-soluble organic functional film 4 is mainly an organic thin film composed of a carrier transport layer, a light emitting layer, a charge generation layer, and the like used for an organic solar cell and an organic EL display.

  The substrate 5 can be made of metal, thin glass or plastic, but the present invention is not limited to this. The board | substrate 5 is fixed to the board | substrate support stand 3, and the board | substrate 5 and the rubber-like ring 1 are contact | adhered by pressurizing the cap board 2 and the board | substrate support stand 3 which oppose.

  As another contact method of the present invention, the substrate 5 is fixed on the substrate support 3, is opposed to the cap plate 2 having the rubber-like ring 1, and is placed in alignment to be patterned into a desired shape, The rubber-like ring 1, the cap plate 2, and the substrate 5 with the organic functional film 4 may be brought into close contact with the rubber-like ring 1 by reducing the pressure of the closed space surrounded by the substrate.

  The substrate support 3 is made of a metal or ceramic having good corrosion resistance and good heat conduction for fixing the substrate 5 so that the substrate 5 can be fixed by suction or the like.

  As shown in FIG. 4, after the rubber-like ring 1 formed on one surface of the cap plate 2 is brought into close contact with the substrate 5, the rubber-like ring 1 is formed with a soluble solvent or a dispersible solvent of the organic functional film 4. The outer organic functional film 4 is removed by washing.

  When the solvent-soluble organic functional film 4 is a water-soluble or water-dispersible film, an organic function outside the range surrounded by the rubber ring 1 is obtained by using a solvent containing water and alcohol as a dissolving or dispersing solvent. The pattern of the organic functional film 4 can be formed by washing and removing the functional film 4 and drying.

  When the solvent-soluble organic functional film 4 is an aromatic organic solvent-soluble film such as toluene, the solvent-containing organic functional film 4 is surrounded by the rubber ring 1 by using a solvent containing an aromatic organic solvent as a dissolving or dispersing solvent. The pattern of the organic functional film 4 can be formed by washing and removing the organic functional film 4 outside the range and drying.

  When the solvent-soluble organic functional film 4 is a water-soluble or water-dispersible film, the composition of the solvent at the time of cleaning and removal is increased in order to speed up the drying time of the substrate 5 after the organic functional film 4 is cleaned and removed. Alternatively, it is possible to use a cleaning solvent in which the composition is changed by increasing the water concentration first and then increasing the alcohol concentration.

  In the case where the solvent-soluble organic functional film 4 is a laminated film of a water-soluble film and an organic solvent-soluble film, cleaning is performed by alternately using a solvent containing water and alcohol and an aromatic organic solvent solvent. Drying time can be shortened by washing with an aromatic organic solvent having a lower vapor pressure than water.

  When the solvent-soluble organic functional film 4 is cleaned, the substrate 5 and the cap plate 2 are made of rubber to prevent the cleaning solvent from entering the range surrounded by the rubber ring 1 and dissolving the organic functional film 4. It is necessary to closely contact via the ring 1.

  As shown in FIG. 5, the organic functional film 4 outside the range of the rubber-like ring 1 is dried.

  When drying, as shown in FIG. 9, the cap plate 2, the substrate 5, and the substrate support 3 are heated and dried by the heater unit block 9 attached to the cap plate 2 or the substrate support 5, and then the substrate 5 to the cap plate 2. Release time can speed up drying time.

  Furthermore, when drying, portions other than the range surrounded by the cap plate 2 and the rubber ring 1 can be washed and ventilated by using the washing and ventilation drying tube 8. The drying time can be further accelerated by separating the cap plate 2 from the substrate 5 after ventilation drying.

  At that time, the cleaning and ventilation drying tube 8 may be provided with a tube for flowing the cleaning liquid and a tube for ventilation drying separately or may be used in common.

  The heater unit block 9 is a substrate heating mechanism for drying, and it is possible to use a Peltier element capable of adjusting warm heating / cooling by flowing hot water, an electric heater, or the like, but the present invention is not limited to this. Absent.

  On the substrate 5 used in the present invention, a partition wall using a reverse taper resist for line separation at the time of cathode vapor deposition may be formed under the organic functional film 4. Further, a bank (bank) for preventing ink outflow may be formed around the light emitting region at the time of film formation using an ink jet method or a printing method. Further, a driving circuit such as a thin film transistor or a wiring may be formed.

  As shown in FIG. 6, when the cap plate 2 and the substrate 5 are separated, a pattern film having a desired shape as shown in FIG. 7 can be formed on the substrate 5.

  The pattern film forming method of the present invention is shown in FIGS. 1 and 2 when the solvent-soluble organic functional film 4 formed on one surface of a substrate 5 such as glass, metal or plastic is divided into a desired shape. As shown, it is possible to use a cap plate 2 provided with a rubber-like ring 1 arranged on one surface having one or more desired shapes. In the present invention, after the rubber ring 1 having one or more desired shapes on one surface of the cap plate 2 is brought into close contact with the organic functional film 4 formed on the substrate 5, The organic functional film 4 outside the range surrounded by each rubber ring 1 can be washed and removed with a solvent for dissolving or dispersing the film 4 and dried.

  Examples of the present invention will be described below.

  A transparent conductive film made of indium tin oxide is formed on a 360 mm × 460 mm square glass substrate by a sputtering method, and etching is performed with a mixed solution of ferric chloride (III) aqueous solution and hydrochloric acid. Diagonal 5 inch diagonal anodes for simple matrix displays corresponding to 480 (scan lines) × 640 × red, blue, and green lines (data lines) were formed in a 6-plane arrangement of 2 rows × 3 columns.

  A bank made of a resist using polyimide was formed on the stripe electrode to a thickness of 2 μm by photolithography, and then ultraviolet ozone cleaning was performed. Thereafter, PEDOT: PSS (BAYTRON P CH8000) was formed as a hole injection layer by die coating on one surface of the substrate 5 with a thickness of 50 nm using an ink appropriately diluted with water and isopropyl alcohol.

  The cap plate 2 is manufactured by processing a stainless plate in a shape as shown in FIG. Corresponding to six diagonal 5 inch displays, a grooving ring 1 having a cross-sectional diameter of 2 mm was fitted and bonded in a square shape to a depth of 1 mm so as to be 3 mm outside the light emitting region.

  Next, the substrate 5 was fixed on the substrate support 3, and the cap plate 2 shown in FIG. Pure water was poured into the gap between the substrate 5 and the cap plate 2 for cleaning. Next, ethyl alcohol was washed and washed. When the substrate 5 and the cap plate 2 were separated after flowing compressed air and drying, the organic functional film 4 could be patterned as shown in FIG. The next light emitting layer could be printed on the patterned PEDOT: PSS film.

  The same process as in Example 1 was performed until a PEDOT: PSS film having a thickness of 50 nm was formed as the hole injection layer 10. Then, using the ink made of polyfluorene-based red, blue, and green light emitting materials in xylene as the light emitting layer 11, the light emitting layer stripe lines are aligned with the data lines by letterpress printing, and each color line is sequentially formed on the entire surface of the substrate 5. did.

  Next, the suction pipe 7, the cleaning and ventilation drying pipe 8, and the heater unit block 9 as shown in FIG. 9 are arranged on the other surface of the cap plate 2, and the flow channel of the cleaning section is dug and processed. The cap plate 2 fitted with the rubber ring 1 having a diameter of 2 mm was superposed, the suction tube 7 was sucked, and the cap plate 2 and the substrate 5 were brought into close contact with each other.

  Next, pure water and toluene were washed in order from the washing and ventilation drying tube 8, and the membrane outside the range sealed with the rubber ring 1 was washed out. Finally, when the substrate 5 is dried by heating the substrate support 3 and the cap plate 2 with the Peltier element-equipped heater unit block 9 to dry the substrate 5, and then separating the substrate 5 from the cap plate 2, water is dissolved as shown in FIG. 7. The organic functional film 4 in which the functional film and the organic solvent-soluble film are laminated can be patterned.

  After patterning, a cathode line made of a barium / aluminum laminated film was mask-deposited so as to be orthogonal to the data line, and then an organic EL display panel was obtained by adhering a sealing glass plate.

It is a perspective view of the example of the cap board used for the pattern film formation method of this invention. It is a schematic diagram of the cross section of the example of the cap board used for the pattern film formation method of this invention. It is a schematic diagram explaining the procedure which forms a pattern film with the pattern film formation method of this invention. It is a schematic diagram explaining the procedure which forms a pattern film with the pattern film formation method of this invention. It is a schematic diagram explaining the procedure which forms a pattern film with the pattern film formation method of this invention. It is a schematic diagram explaining the procedure which forms a pattern film with the pattern film formation method of this invention. It is a schematic diagram which shows the board | substrate which formed the pattern film in the pattern film formation method of this invention. It is a schematic diagram explaining the method of forming the pattern film of another aspect with the pattern film formation method of this invention. It is a schematic diagram explaining the pattern film forming apparatus of another aspect of the pattern film forming method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Rubber-like ring 2 Cap board 3 Substrate support stand 4 Organic functional film 5 Substrate 6 Organic functional film formed in stripes or dots 7 Suction tube 8 Washing and ventilation drying tube 9 Heater unit block 10 Organic positive Hole transport layer 11 Organic light emitting layer 100 Pattern film forming apparatus

Claims (3)

In a pattern film forming apparatus for patterning an organic functional film formed on one surface of a substrate into a desired shape,
A cap plate,
A plurality of rubber rings arranged to have a desired shape on one surface of the cap plate;
A plurality of heater unit blocks disposed at a predetermined interval on the other surface of the cap plate;
One end is extended between the plurality of heater unit blocks, and at least one opening that is the other end is disposed in each of a plurality of regions surrounded by the plurality of rubber rings. A plurality of suction pipes;
One end is extended between the plurality of heater unit blocks, and the opening that is the other end is disposed at least one in each of the plurality of regions other than the range surrounded by the plurality of rubber rings. A plurality of cleaning and ventilation drying tubes;
A mechanism for bringing the substrate and the organic functional film into close contact with the plurality of rubber-like rings;
Have
A mechanism for bringing the substrate and the organic functional film into close contact with the plurality of rubber-like rings,
The substrate is fixed on the substrate support and is opposed to the cap plate, and one of the cap plate or the substrate support is aligned with the opposing cap plate or the substrate support, and the plurality of rubber-like members brought into close contact with the plurality of rubber ring and the substrate by vacuum respectively between a plurality of closed spaces formed by the enclosed Mukoto in the substrate and the ring and the cap plate,
The plurality of cleaning and ventilation drying tubes in which openings are arranged in each of a plurality of regions other than the range surrounded by the plurality of rubber-like rings commonly supply cleaning liquid and supply ventilation for drying. A pattern film forming apparatus characterized by being a tube. The pattern film forming apparatus according to claim 1, wherein a cross-sectional shape of the rubber ring is a polygon or a circle. The pattern film forming apparatus according to claim 1, wherein a width of the rubber-like ring is 0.5 mm to 4 mm.

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