KR20090030219A - Patterning method and display device - Google Patents

Abstract

A patterning method and a display device are provided to perform high precision pattering by performing a wet etching using the etchant of the weak acid or the weak base. The gas barrier layer comprises with at least one inorganic region and at least one organic region. The pKa of the weak acid or the weak base contained in the etchant is in range of 0.5 ~ 10. The etchant is selected among the oxalic acid solution, the acetate solution, the carbonate solution and phosphoric acid and their mixture of two or more kinds. The etchant is made of the aqueous solution of oxalic acid. The substrate for the display device has the transparent electrode. The substrate for the display device has the cathode film layer. The cathode film layer is patterned.

Description

Patterning method and display device {PATTERNING METHOD AND DISPLAY DEVICE}

The present invention provides a patterning method for a display element substrate, a display element substrate patterned using the patterning method, and a method of manufacturing a display element comprising patterning the substrate using the patterning method, and a method of manufacturing the display element. It relates to a display element manufactured by.

Conventionally, patterning is performed at the time of manufacture of an organic EL element. For example, Japanese Laid-Open Patent Publication No. 2004-146136 discloses etching a metal thin film layer with a mixed acid of phosphoric acid, nitric acid, and acetic acid, followed by etching with oxalic acid to pattern an anode thin film layer. However, the patterning in the organic EL element using the organic inorganic laminated gas barrier film for a board | substrate requires various examination because the gas barrier film is a complicated laminated constitution containing an organic area and an inorganic area.

On the other hand, Japanese Laid-Open Patent Publication No. 2007-76036 discloses etching a polyamide-based film obtained by laminating a transparent vapor deposition thin film layer made of an inorganic oxide and a gas barrier coating layer containing a water-soluble polymer. However, the etching is etching by plasma processing and has nothing to do with the organic EL element.

As mentioned above, the patterning method of the board | substrate for display elements which used the organic inorganic laminated type gas barrier film for the board | substrate is not examined at all. In particular, when a strong acid and a strong base, which are conventionally widely used as an etching solution, are employed in a gas barrier film, the gas barrier film is damaged and performance deterioration of the finally obtained display element is generated. An object of the present invention is to solve such a problem, and provides a patterning method capable of high-precision patterning without affecting the performance of a display element.

As a result of earnestly examining by the present inventors under the said subject, it turned out that the said subject can be solved by the following means.

(1) A method of patterning a substrate for display elements having a gas barrier layer consisting of at least one organic region and at least one inorganic region, wherein the patterning is performed by wet etching using a weak acid or weak base etching solution. Patterning method of the substrate.

(2) pKa of weak acid or weak base contained in said etching liquid exists in the range of 0.5-10, The patterning method as described in (1) characterized by the above-mentioned.

(3) The patterning method according to (1) or (2), wherein the etching solution is selected from an oxalic acid solution, an acetic acid solution, a carbonic acid solution and a phosphoric acid solution, and a mixture of two or more thereof.

(4) The patterning method according to (1) or (2), wherein the etching solution is an oxalic acid aqueous solution.

(5) The patterning method according to any one of (1) to (4), wherein the display element substrate has a transparent electrode, and the transparent electrode is patterned.

(6) The patterning method according to any one of (1) to (5), wherein the display element substrate has an anode thin film layer and patterns the anode thin film layer.

(7) The patterning method according to any one of (1) to (6), wherein the display element substrate has an ITO thin film layer, and the ITO thin film layer is patterned.

(8) The patterning method according to any one of (1) to (7), wherein the gas barrier layer has a structure in which at least one organic layer and at least one inorganic layer are laminated.

(9) The patterning method according to (8), wherein the organic layer of the at least one layer and the inorganic layer of the at least one layer are alternately laminated.

(10) Patterned using the patterning method in any one of (1)-(9), The display element board | substrate characterized by the above-mentioned.

(11) The manufacturing method of the display element containing patterning a board | substrate using the patterning method in any one of (1)-(9).

(12) The display element manufactured by the method as described in (11).

According to the present invention, the substrate for display element can be patterned without affecting the element performance.

EMBODIMENT OF THE INVENTION Below, the content of this invention is demonstrated in detail. In addition, it is used by the meaning which includes with "-" the numerical value described before and after that as a lower limit and an upper limit in this specification.

<< patterning method >>

The patterning method of the display element substrate of this invention WHEREIN: The display element substrate which has a gas barrier layer which consists of at least 1 organic area | region and at least 1 inorganic area | region is wet-etched, and the etching is weak acid or weak base. It is characterized by using an etchant.

(Etching liquid)

The etching liquid used in the patterning method of this invention is a weak acid or weak base, Preferably it is a case where pKa exists in the range of 0.5-10, More preferably, it is a case where pKa exists in the range of 1.0-9.5. By using such etching liquid, it can etch without damaging a board | substrate for display elements, and can pattern with high precision. The etching solution in the present invention is preferably selected from oxalic acid, acetic acid, carbonic acid and phosphoric acid, and a mixture of two or more thereof, and more preferably oxalic acid and acetic acid.

As for other detailed conditions regarding a wet etching and the other processing process at the time of patterning, a well-known technique can be employ | adopted, for example, Unexamined-Japanese-Patent No. 3-250583, Unexamined-Japanese-Patent No. 2006-59831, Kyodo The method described in Wedge Supervision "Organic EL Materials and Displays" by CMC (2001) or the like can be adopted.

<< board | substrate for display elements >>

(Gas barrier layer)

The display element substrate of this invention has the gas barrier layer which consists of at least 1 organic region and at least 1 inorganic region. The gas barrier layer may have a function of blocking oxygen and moisture in the atmosphere, and may have a structure in which at least one organic layer and at least one inorganic layer are alternately stacked, so-called inclination in which each region continuously changes in the film thickness direction. A material layer may be sufficient. Although there is no restriction | limiting in particular about the number of layers which comprise a gas barrier layer, Typically, 2-30 layers are preferable and 3-20 layers are more preferable. In addition, although a gas barrier layer is normally formed in a base film, it may be formed only in the single side | surface of the base film, and may be formed in both surfaces.

Examples of the inclined material layer include a paper by Kimura, `` Journal of Vacuum Science and Technology A Vol. 23 p971-977 (2005 American Vacuum Society) Journal of Vacuum Science and Technology A, Vol. 23, pages 971 to 977 (2005). And the continuous layer in which the organic layer and the inorganic layer do not have an interface as disclosed in US Patent Application Publication No. 2004-46497. Hereinafter, although the gas barrier layer in which the organic layer and the inorganic layer are laminated is described as an example, the case of the inclined material layer can be considered the same.

(Substrate film)

The base film in this invention is a plastic film normally. The plastic film to be used is not particularly limited as long as it is a film capable of holding a laminate such as an organic layer or an inorganic layer, and can be appropriately selected depending on the purpose of use and the like. Specific examples of the plastic film include polyester resins, methacrylic resins, methacrylic acid-maleic acid copolymers, polystyrene resins, transparent fluorine resins, polyimides, fluorinated polyimide resins, polyamide resins, polyamideimide resins, Polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene And thermoplastic resins such as ring-modified polycarbonate resins, alicyclic-modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

When using the display element substrate of this invention as a board | substrate of devices, such as an organic EL element mentioned later, it is preferable that a plastic film consists of a material which has heat resistance. Specifically, it is preferable that the glass transition temperature (Tg) is made of a transparent raw material having a high heat resistance and a thermal transition coefficient of 100 ° C or higher and / or 40 ppm / ° C or lower. Tg and the coefficient of linear thermal expansion can be adjusted by an additive or the like. As such a thermoplastic resin, for example, polyethylene naphthalate (PEN: 120 degreeC), polycarbonate (PC: 140 degreeC), alicyclic polyolefin (for example, Zeonoa 1600: 160 degreeC by Nippon Xeon Co., Ltd.), Polyarylate (PAr: 210 ° C), polyethersulfone (PES: 220 ° C), polysulfone (PSF: 190 ° C), cycloolefin copolymer (COC: compound of JP 2001-150584: 162 ° C), Polyimide (for example, Mitsubishi Gas Chemical Co., Ltd. neoprem: 260 ° C), fluorene ring-modified polycarbonate (BCF-PC: compound of JP-A-2000-227603: 225 ° C), alicyclic modified polycarbonate ( IP-PC: The compound of Unexamined-Japanese-Patent No. 2000-227603: 205 degreeC), and the acryloyl compound (The compound of Unexamined-Japanese-Patent No. 2002-80616: 300 degreeC or more) are mentioned (The parenthesis shows Tg). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

When using the display element substrate of this invention in combination with a polarizing plate, it is preferable to make the barrier laminated body of a display element substrate face an inner side of a cell, and to arrange | position it innermost (adjacent to an element). At this time, since the display element substrate is arranged inside the cell rather than the polarizing plate, the retardation value of the display element substrate becomes important. The use form of the board | substrate for display elements in such an aspect is a board | substrate for display elements and a circularly polarizing plate using the base film whose retardation value is 10 nm or less (1/4 wavelength plate + (1/2 wavelength plate) + linear polarizing plate) It is preferable to laminate | stack and use, or to use a linear polarizing plate in combination with the board | substrate for display elements using the base film whose retardation value is 100 nm-180 nm which can be used as a quarter wavelength plate.

Examples of the base film having a retardation value of 10 nm or less include cellulose triacetate (Fuji Film Co., Ltd .: Fuji-Tac), polycarbonate (Teijin Chemical Co., Ltd .: Pure Ace, Kaneka: Elmek Co., Ltd.), cycloolefin polymer (JSR Co., Ltd .: Aton, Nippon Xeon Co., Ltd .: Zeonoa), Cycloolefin copolymer (Mitsui Chemical Co., Ltd .: Apel (pellet), Polyplastic Co., Ltd: Topas (pellet)) Polyarylate (Uni Tica Co., Ltd .: U100 (pellet)), a transparent polyimide (Mitsubishi Gas Chemical Co., Ltd .: neoprem), etc. are mentioned.

Moreover, as a quarter wave plate, the film adjusted to the desired retardation value can be used by extending | stretching said film suitably.

Since the substrate for display elements of the present invention is used as a device such as an organic EL element, the plastic film is transparent, that is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more. to be. The light transmittance can be calculated by subtracting the diffuse transmittance from the total light transmittance by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, an integrated sphere light transmittance measuring apparatus.

Even when using the display element substrate of this invention for a display use, transparency is not necessarily required when it is not installed in an observation side. Therefore, in such a case, an opaque material can also be used as a plastic film. As an opaque material, polyimide, polyacrylonitrile, a well-known liquid crystal polymer, etc. are mentioned, for example.

Although the thickness of the plastic film used for the display element substrate of this invention is suitably selected according to a use, there is no restriction | limiting in particular, Typically, it is 1-800 micrometers, Preferably it is 10-200 micrometers. These plastic films may have functional layers, such as a transparent conductive layer and a primer layer. About a functional layer, Paragraph No. 0036 of Unexamined-Japanese-Patent No. 2006-289627-0038 are described in detail. Examples of functional layers other than these include a mat agent layer, a protective layer, an antistatic layer, a smoothing layer, an adhesion improving layer, a light shielding layer, an antireflection layer, a hard coat layer, a stress relaxation layer, an antifogging layer, an antifouling layer, a printed layer, and an adhesive layer. Easy layer etc. are mentioned.

(Inorganic layer)

An inorganic layer is a layer of the thin film which consists of a metal compound normally. Any method can be used as a method of forming an inorganic layer as long as it can form a desired thin film. For example, a coating method, a sputtering method, a vacuum vapor deposition method, an ion plating method, a plasma CVD method, etc. are suitable, Specifically, Unexamined-Japanese-Patent No. 3400324, Unexamined-Japanese-Patent No. 2002-322561, Unexamined-Japanese-Patent No. 2002-361774. The formation method as described in each each publication can be employ | adopted.

The component contained in the inorganic layer is not particularly limited as long as it satisfies the above performance, but for example, contains at least one metal selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta and the like. Oxides, nitrides, carbides, oxynitrides, oxidized carbides, nitrides, oxynitrides and the like can be used. Among these, oxides, nitrides or oxynitrides of metals selected from Si, Al, In, Sn, Zn and Ti are preferable, and metal oxides, nitrides or oxynitrides of Si or Al are particularly preferable. These may contain another element as a secondary component.

Although it does not specifically limit about the thickness of the said inorganic layer, It is preferable to exist in the range of 5 nm-500 nm, More preferably, it is 10 nm-200 nm. Moreover, you may laminate | stack two or more inorganic layers. In this case, each layer may be the same composition or a different composition. In addition, as described above, the interface with the organic layer is not clear as disclosed in US Patent Publication No. 2004-46497, and the layer may be a composition whose composition changes continuously in the film thickness direction.

(Organic layer)

The organic layer is usually a layer of a polymer. Specifically, polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluorine resin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate , Polyurethane, polyether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound It is a layer of thermoplastic resins, such as these, or polysiloxane, and other organosilicon compounds. The organic layer may consist of a single material or may consist of a mixture. You may laminate | stack two or more organic layers. In this case, each layer may be the same composition or a different composition. In addition, as described above, the interface with the inorganic layer is not clear as disclosed in U.S. Patent Publication No. 2004-46497, and the layer may be a composition whose composition changes continuously in the film thickness direction.

It is preferable that an organic layer is smooth and its film hardness is high. The smoothness of the organic layer is preferably 10 nm or less, more preferably 2 nm or less, as an average roughness (Ra value) of 10 μm in length and width. It is preferable that the film hardness of the organic layer has a hardness of HB or higher as the pencil hardness, and more preferably has a hardness of H or higher.

Although there is no restriction | limiting in particular about the film thickness of an organic layer, When too thin, it becomes difficult to obtain uniformity of a film thickness, When too thick, a crack will generate | occur | produce by external force and a barrier performance will fall. From this viewpoint, 10 nm-2000 nm are preferable and, as for the thickness of an organic layer, 100 nm-1000 nm are more preferable.

As a formation method of an organic layer, the conventional solution coating method, the vacuum film-forming method, etc. are mentioned. As the solution coating method, for example, the dip coating method, the air knife coating method, the curtain coating method, the roller coating method, the wire bar coating method, the gravure coating method, the slide coating method, or the hopper described in the specification of US Pat. It can apply | coat by the extrusion coat method which uses. Although there is no restriction | limiting in particular as a vacuum film-forming method, The film-forming methods, such as vapor deposition and plasma CVD, are preferable. In this invention, a polymer may be apply | coated solution and the hybrid coating method containing the inorganic substance as disclosed by Unexamined-Japanese-Patent No. 2000-323273 and 2004-25732 may be used. Moreover, you may form a polymer layer by polymerizing after depositing a precursor (for example, a monomer) of a polymer. As a preferable monomer which can be used for this invention, an acrylate and a methacrylate are mentioned. Preferred examples of acrylates and methacrylates include, for example, the compounds described in US Pat. No. 6083628, US Pat. No. 6,214,422. Some of these are illustrated below.

In the present invention, it is preferably an organic layer composed of a polymer of a cationic polymerizable compound having a radical polymerizable compound / or ether group as a functional group.

(Polymerizable compound)

The polymeric compound used by this invention is a compound which has an ethylenically unsaturated bond in a terminal or a side chain, and / or a compound which has an epoxy or oxetane in a terminal or a side chain. Among these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred. As an example of the compound which has an ethylenically unsaturated bond in a terminal or a side chain, (meth) acrylate type compound (together acrylate and methacrylate are represented as (meth) acrylate), an acrylamide type compound, a styrene type compound, Maleic anhydride etc. are mentioned.

As a (meth) acrylate type compound, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, etc. are preferable.

As a styrene type compound, styrene, (alpha) -methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxy styrene, 4-carboxy styrene, etc. are preferable.

Although the specific example of a (meth) acrylate type compound is shown below, this invention is not limited to these.

The monomer polymerization method is not particularly limited, but heat polymerization, light (ultraviolet light, visible light) polymerization, electron beam polymerization, plasma polymerization or a combination thereof is preferably used. In the case of carrying out heat polymerization, the base film serving as the base material needs to have a corresponding heat resistance. In this case, it is necessary that the glass transition temperature (Tg) of a base film is higher than at least heating temperature.

In the case of performing photopolymerization, a photoinitiator is used together. Examples of the photopolymerization initiator include Irgacure series (e.g. Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure), which are commercially available from Chiba Specialty Chemicals. 907, Irgacure 369, Irgacure 379, Irgacure 819, etc.Darocure series (e.g., Tarocure TPO, Tarocure 1173, etc.), Quantacure PDO, Satomer ( Ezacure series (for example, Ezacure TZM, Ezacure TZT etc.) marketed by Sartomer), etc. are mentioned.

The light to irradiate is ultraviolet-ray by a high pressure mercury lamp or a low pressure mercury lamp normally. 0.5J / cm <2> or more is preferable and 2J / cm <2> or more of irradiation energy is more preferable. Since acrylate and methacrylate are inhibited from polymerization by oxygen in the air, it is preferable to lower the oxygen concentration or oxygen partial pressure at the time of polymerization. When the oxygen concentration at the time of polymerization is reduced by the nitrogen substitution method, 2% or less is preferable and, as for oxygen concentration, 0.5% or less is more preferable. When the oxygen partial pressure at the time of polymerization is reduced by the decompression method, it is preferable that the total pressure is 1000 kPa or less, and it is more preferable that it is 100 kPa or less. Moreover, it is especially preferable to perform ultraviolet-polymerization by irradiating an energy of 2J / cm <2> or more under the pressure reduction conditions of 100 Pa or less.

At this time, it is preferable that the polymerization rate of a monomer is 80% or more, It is more preferable that it is 85% or more, It is still more preferable that it is 90% or more. The polymerization rate here means the ratio of the polymerizable group which reacted among all the polymerizable groups (acryloyl group and methacryloyl group) in a monomer mixture.

<< display element >>

The display element in this invention means a circularly polarizing plate, a liquid crystal display element, a touch panel, organic electroluminescent element, etc.

<Circular polarizer>

The circular polarizing plate can be manufactured by laminating a (lambda) / 4 plate and a polarizing plate using the board | substrate for display elements in this invention as a board | substrate. In this case, lamination | stacking is carried out so that the slow axis of (lambda) / 4 plate and the absorption axis of a polarizing plate may be 45 degrees. It is preferable to use what is extended in the direction of 45 degrees with respect to the longitudinal direction MD, and such a polarizing plate can use the thing of Unexamined-Japanese-Patent No. 2002-865554 preferably, for example.

<Liquid crystal display element>

The reflective liquid crystal display device has a structure consisting of a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The display element substrate in this invention can be used as the said transparent electrode substrate and an upper substrate. In the case of color display, it is preferable to further form a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

The transmissive liquid crystal display device has a structure consisting of a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment layer, a liquid crystal layer, an upper alignment layer, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. Have Among them, the substrate of the present invention can be used as the upper transparent electrode and the upper substrate. In the case of color display, it is preferable to further form a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the upper transparent electrode.

Although the kind of liquid crystal cell is not specifically limited, More preferably, it is TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, HAN (Hybrid Aligned Nematic) type, VA (Vertically Alignment) type, ECB (Electrically Controlled Birefringence) type It is preferable that the type, OCB (Optically Compensated Bend) type, CPA (Continuous Pinwheel Alignment) type, IPS (In Plane Switching) type.

<Touch panel>

The touch panel can be applied to those described in JP-A-5-127822, JP-A-2002-48913 and the like.

<Organic EL element>

An organic electroluminescent element means an organic electroluminescent element. The display element substrate in this invention can be used as a board | substrate of organic electroluminescent element. The organic EL device has a cathode and an anode on a substrate, and an organic compound layer including a light emitting layer between both electrodes. At least one of the anode and the cathode is transparent in view of the nature of the light emitting element.

As a laminated aspect of the organic compound layer in this invention, the aspect laminated | stacked in order of a positive hole transport layer, a light emitting layer, and an electron carrying layer from an anode side is preferable. In addition, a charge block layer or the like may be provided between the hole transporting layer and the light emitting layer, or between the light emitting layer and the electron transporting layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. In addition, only one layer may be sufficient as a light emitting layer, and a light emitting layer may be divided into a 1st light emitting layer, a 2nd light emitting layer, and a 3rd light emitting layer. In addition, each layer may be divided into a plurality of secondary layers.

Although the thickness of the board | substrate used by this invention is not specifically defined, 30 micrometers-700 micrometers are preferable, More preferably, they are 40 micrometers-200 micrometers, More preferably, they are 50 micrometers-150 micrometers. In any case, the haze is preferably 3% or less, more preferably 2% or less, still more preferably 1% or less, and the total light transmittance is preferably 70% or more, more preferably 80% or more, even more preferably Is 90% or more.

(anode)

The anode usually has a function as an electrode for supplying holes to the organic compound layer, and the shape, structure, size, and the like thereof are not particularly limited, and may be appropriately selected from known electrode materials according to the use and purpose of the light emitting device. . As described above, the anode is usually formed as a transparent anode. The transparent anode has detailed description in Sadada Yutaka Supervision "New Development of Transparent Electrode Film" CMC Publication (1999). When using a plastic base material with low heat resistance as a board | substrate, the transparent anode formed into a film at low temperature below 150 degreeC using ITO or IZO is preferable.

(cathode)

The cathode may have a function as an electrode which injects electrons into an organic compound layer normally, and there is no restriction | limiting in particular about the shape, structure, size, etc., According to the use and the objective of a light emitting element, it can select suitably from well-known electrode materials. .

As a material which comprises a cathode, a metal, an alloy, a metal oxide, an electrically conductive compound, a mixture thereof, etc. are mentioned, for example. As a specific example, rare earth metals, such as a group 2 metal (for example, Mg, Ca etc.), gold, silver, lead, aluminum, a lithium-aluminum alloy, magnesium-silver alloy, indium, ytterbium, etc. are mentioned. Although these may be used individually by 1 type, 2 or more types can be used together suitably from a viewpoint of making stability and electron injection property compatible.

Among these, as a material which comprises a cathode, the material which mainly uses aluminum is preferable.

The material mainly composed of aluminum refers to aluminum alone, or an alloy of aluminum and 0.01 to 10% by mass of an alkali metal or a group 2 metal (for example, a lithium-aluminum alloy, a magnesium-aluminum alloy, etc.). In addition, the material of a cathode is described in detail in Unexamined-Japanese-Patent No. 2-15595 and Unexamined-Japanese-Patent No. 5-121172. A dielectric layer made of a fluoride, an oxide, or the like of an alkali metal or a group 2 metal may be inserted between the cathode and the organic compound layer in a thickness of 0.1 to 5 nm. This dielectric layer may be regarded as a kind of electron injection layer.

Although the thickness of a negative electrode can be suitably selected with the material which comprises a negative electrode, Although it cannot define collectively, it is about 10 nm-about 5 micrometers normally, and 50 nm-1 micrometer is preferable.

In addition, the cathode may be transparent or opaque. The transparent cathode can be formed by thinly forming a material of the cathode with a thickness of 1 to 10 nm and further laminating transparent conductive materials such as ITO and IZO.

(Organic compound layer)

The organic EL device has at least one organic compound layer including a light emitting layer, and as another organic compound layer other than the organic light emitting layer, as described above, a hole transport layer, an electron transport layer, a charge block layer, a hole injection layer, an electron injection layer Each layer, such as these, is mentioned.

((Organic Light Emitting Layer))

The organic light emitting layer has a function of receiving holes from an anode, a hole injection layer, or a hole transport layer upon application of an electric field, receiving electrons from a cathode, an electron injection layer or an electron transport layer, and providing a field for recombination of holes and electrons to emit light. to be. The light emitting layer may be comprised only with a luminescent material, and the structure made into the mixed layer of a host material and a luminescent material may be sufficient. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and one type or two or more types of dopants may be used. The host material is preferably a charge transport material. The host material may be one type or two or more types, and the structure which mixed the electron-transport host material and the hole-transport host material is mentioned, for example. Moreover, the light emitting layer may contain a material which does not have charge transportability and which does not emit light. In addition, one layer or two or more layers may be sufficient as a light emitting layer, and each layer may light-emit in a different light emission color.

Examples of the fluorescent light emitting material include benzoxazole derivatives, benzoimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide Derivatives, coumarin derivatives, condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyrazine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives , Various metal complexes represented by metal complexes of thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidine compounds, 8-quinolinol derivatives or metal complexes of pyrromethene derivatives Polymer compounds, such as polythiophene, polyphenylene, polyphenylene vinylene, an organosilane derivative, etc. And compounds of the like.

As said phosphorescence emitting material, the complex containing a transition metal atom or a lanthanoid atom is mentioned, for example. Although it does not specifically limit as said transition metal atom, Preferably, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum are mentioned, More preferably, they are rhenium, iridium, and platinum.

Examples of the lanthanoid atoms include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and ruthenium. Among these lanthanoid atoms, neodymium, europium and gadolinium are preferable.

As the ligand of the complex, for example, G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, Inc., published in 1987, H. Yersin, `` Photochemistry and Photophysics of Coordination Compounds '' published in 1987 by Springer-Verlag, Akio Yamamoto And the ligands described in, for example, "Organic Metal Chemistry-Basics and Applications-" issued by Shokabo Corporation in 1982.

As the host material contained in the light emitting layer, for example, one having a carbazole skeleton, one having a diarylamine skeleton, one having a pyridine skeleton, one having a pyrazine skeleton, one having a triazine skeleton and aryl The thing which has a silane skeleton, and the material illustrated by the term of the below-mentioned hole injection layer, a hole transport layer, an electron injection layer, and an electron carrying layer is mentioned.

(Hole injection layer, hole transport layer)

The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, Arylamine derivatives, amino substituted calcon derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidine compounds, porphyrins It is preferable that it is a layer containing a compound, an organosilane derivative, carbon, and the like.

((Electron injection layer, electron transport layer))

The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or cathode side and transporting them to the anode side. The electron injection layer and the electron transport layer are specifically triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives and thiopyran dioxide Metal complexes of aromatic ring tetracarboxylic anhydrides, phthalocyanine derivatives and 8-quinolinol derivatives such as derivatives, carbodiimide derivatives, fluorenylidene methane derivatives, distyrylpyrazine derivatives, naphthalene and perylene, metal phthalocyanine and benzoxazole Or a layer containing various metal complexes, organosilane derivatives and the like represented by metal complexes having benzothiazole as a ligand.

((Hole block layer))

The hole block layer is a layer having a function of preventing the holes transported from the anode side to the light emitting layer from escaping to the cathode side. In the present invention, a hole block layer can be formed as an organic compound layer adjacent to the light emitting layer and the cathode side. In addition, the electron transport layer and the electron injection layer may also function as the hole block layer.

As an example of the organic compound which comprises a hole block layer, aluminum complexes, such as BAlq, a triazole derivative, phenanthroline derivatives, such as BCP, etc. are mentioned.

Further, a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from escaping to the anode side may be formed at a position adjacent to the light emitting layer and the anode side. The hole transport layer and the hole injection layer may also function as this function.

<TFT display element>

The display element substrate in this invention can be used as a board | substrate for thin film transistor (TFT) image display elements. As a manufacturing method of a TFT array, the method etc. which are described in Unexamined-Japanese-Patent No. 10-512104 are mentioned. The substrate may also have a color filter for color display. The color filter may be manufactured using any method, but it is preferable to use a photolithography method.

<Solar cell>

The gas barrier layer of this invention can be used also as the sealing film of a solar cell element. Here, it is preferable to seal the gas barrier layer of this invention so that an adhesive layer may become a side closer to a solar cell element. Although there is no restriction | limiting in particular as a solar cell element in which the gas barrier layer of this invention is used preferably, For example, amorphous silicon system comprised from a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, a tandem structure type, etc. III-V compound semiconductor solar cell elements such as solar cell elements, gallium arsenide (GaAs) or indium phosphorus (InP), II-VI compound semiconductor solar cell elements such as cadmium tellurium (CdTe), copper / indium / selenium I-III-VI compound semiconductor solar cells such as (so-called CIS system), copper / indium / gallium / selenium (so-called CIGS system), copper / indium / gallium / selenide / sulfur system (so-called CIGSS system) An element, a dye-sensitized solar cell element, an organic solar cell element, etc. are mentioned. Especially, in this invention, the said solar cell element is copper / indium / selenium system (so-called CIS system), copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur It is preferable that it is a group I-III-VI compound semiconductor solar cell element, such as a system (so-called CIGSS system).

<< Example >>

An Example is given to the following and this invention is demonstrated to it further more concretely. The materials, usage amounts, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific example shown below.

(Example 1)

Preparation of Gas Barrier Films

Gas barrier films (Sample Nos. 101 to 103) in which an inorganic layer and an organic layer were formed on a base film were manufactured according to the following procedures. The details of each gas barrier film structure are as described in Table 1. Polyethylene naphthalate (PEN, thickness 100 micrometers, Teijin Dupont Co., Ltd. product, Q65A) film was used for the base film.

[1] formation of inorganic layer (X)

An inorganic layer of aluminum oxide was formed using a reactive sputtering apparatus. Specific film forming conditions are shown below.

The vacuum chamber of the reactive sputtering apparatus was depressurized to 5 × 10 ^-4 kPa by an oil rotary pump and a turbo molecular pump. Next, argon was introduced as a plasma gas, and electric power 2000W was applied from the plasma power supply. Oxygen gas of high purity was introduced into the chamber, the film forming pressure was adjusted to 0.3 kPa, and the film was formed for a certain time to form an inorganic layer of aluminum oxide. The obtained aluminum oxide film was 40 nm in film thickness, and was 3.01 g / cm <3> in film density.

[2] formation of organic layers (Y, Z)

The organic layer was carried out using two types of film formation method (organic layer Y) by solvent coating under normal pressure and film formation method (organic layer Z) by flash deposition method under reduced pressure. Specific film forming contents are shown below.

Film formation of organic layer (Y)

As a photopolymerizable acrylate, 9 g of tripropylene glycol diacrylate (TPGDA, manufactured by Daicel Cytec) and 0.1 g of a photopolymerization initiator (Ciba Specialty Chemicals, Irgacure 907) are dissolved in 190 g of methyl ethyl ketone. It was set as the coating liquid. The coating liquid was applied onto the base film using a wire bar, and the illuminance was 350 Pa / cm 2, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm under a nitrogen purge having an oxygen concentration of 0.1% or less. Ultraviolet rays with an irradiation amount of 500 mJ / cm 2 were irradiated to form the organic layer Y. The film thickness was about 500 nm.

Film Formation of Organic Layer (Z)

As the photopolymerizable acrylate, 9.7 g of butylethylpropanediol diacrylate (BEPGA, manufactured by Kyocisha Chemical Co., Ltd.) and 0.3 g of a photopolymerization initiator (Lamberti spa, EZACURE-TZT) were mixed to obtain a vapor deposition liquid. This deposition liquid was deposited on a substrate by flash deposition under the condition that the internal pressure of the vacuum chamber was 3 kPa. Subsequently, ultraviolet rays having an irradiation amount of 2 J / cm 2 were irradiated under the same vacuum degree to form an organic layer Z. The film thickness was about 1200 nm. Formation of the organic layer Z was performed using the organic-inorganic laminated film-forming apparatus Guardian 200 (made by Vitex Systems).

[3] production of gas barrier films

The gas barrier film was manufactured by sequentially forming the said inorganic layer and organic layer in the base film according to the structure of each sample of Table 1. In addition, the manufacturing method was implemented in the following two types.

[3-1] Method of repeating organic layer formation by solvent coating and inorganic layer formation under reduced pressure (lamination A)

The organic layer and the inorganic layer were alternately laminated on the substrate. When laminating an inorganic layer on an organic layer, after forming an organic layer by solvent coating, it put into a vacuum chamber, and pressure-reduced, and hold | maintained for a fixed time in the state whose vacuum degree is ^10-3 Pa or less, and formed the inorganic layer. In addition, when laminating an organic layer on an inorganic layer, the organic layer was formed by solvent coating immediately after forming an inorganic layer.

[3-2] A method for consistently forming an organic layer and an inorganic layer under reduced pressure (lamination B)

The organic layer and the inorganic layer were laminated | stacked using the organic inorganic laminated film-forming apparatus Guardian 200 mentioned above. In this apparatus, both the organic layer and the inorganic layer form a film under a reduced pressure environment, and since the film formation chambers of the organic layer and the inorganic layer are connected, the film can be continuously formed under a reduced pressure environment. Therefore, it is not opened to the atmosphere until the barrier layer is completed.

[4] production of organic EL devices

The gas barrier film prepared above was introduced into a vacuum chamber, and a transparent electrode made of an ITO thin film having a thickness of 0.2 μm was formed by DC magnetron sputtering using an ITO target. The substrate was etched with an aqueous solution of oxalic acid (pKa = 1.04), a gas barrier film having an ITO film was placed in a washing container, ultrasonically cleaned in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. The following organic compound layers were sequentially deposited on the obtained substrate (anode) by vacuum deposition.

(1st hole transport layer)

Copper phthalocyanine: film thickness 10 nm

(2nd hole transport layer)

N, N'-diphenyl-N, N'- dinaphthylbenzidine: film thickness 40 nm

(Light emitting layer and electron transport layer)

Tris (8-hydroxyquinolinato) aluminum: film thickness 60nm

Finally, 1 nm of lithium fluoride and 100 nm of metallic aluminum were sequentially deposited to form a cathode, and a 3 µm thick silicon nitride film was deposited thereon by a parallel plate CVD method to produce an organic EL device.

[5] pretreatment of gas barrier films for sealing

The gas barrier film (what did not form an electrode) manufactured above was pretreated by the following processes.

[5-1] washing process

The gas barrier film is a medium adhesive sheet (EC-315, manufactured by Smiron, adhesive strength 1.3N / 20 mm twin glass sheet) or a weakly adhesive sheet (EC-310, manufactured by Smiron, adhesive strength 0.8 N / 20 mm twin glass sheet). ) And peeled off. Subsequently, the gas barrier film was put into a vacuum chamber, oxygen gas was introduced to adjust the vacuum degree to about 6 kPa, and treated for 2 minutes with an RF plasma apparatus (RFX-500, manufactured by Advanced Energy) having an RF power of 20W.

[5-2] drying process

The washed gas barrier film was dried at 80 ° C. for 1 hour, and then maintained at 10 ⁻² Pa or less for 10 hours.

[6] installation of gas barrier layers on organic EL elements

The gas barrier film and the organic EL element substrate which were subjected to the above cleaning and drying treatment using a thermosetting adhesive (Epotec 310, Daizo Nichimori Co., Ltd.) were used as the organic barrier element. It adhere | attached so that it might become a side, and it heated at 65 degreeC for 3 hours, and hardened the adhesive agent. Thus sealed organic EL elements (Sample Nos. 201 to 203) were manufactured for each of 20 elements. This element was flexible because both the substrate and the sealing film were made mainly of resin.

[7] Evaluation of Shape of Organic EL Device Light Emitting Surface

The organic EL elements (Sample Nos. 201 to 203) immediately after the manufacture were made to emit light by applying a voltage of 7 V using a source major unit (SMU2400 type, manufactured by Keithley). As a result of observing the light emitting surface shape using a microscope, it was confirmed that uniform light emission without dark spots was provided in any device.

Next, after leaving each element in the dark room of 60 degreeC and 90% of a relative humidity for 24 hours, the shape of the light emitting surface was observed. The ratio of the element where the dark spot larger than 300 micrometers in diameter was observed was defined as the failure rate, and the failure rate of each element is shown in Table 2.

(Comparative Example 1)

An organic EL device (Sample Nos. 301 to 303) was prepared in the same manner as in Example 1, except that the etching solution in Example 1 was used in place of an aqueous solution of oxalic acid, instead of using an aqueous hydrochloric acid solution (pKa = -6). Evaluation was performed. As a result, in relation to the occurrence of dark spots, a large number of dark spots were observed throughout the light emitting surface. In addition, it showed in Table 2 about the failure rate.

From the above result, it was confirmed that the organic electroluminescent element using the board | substrate manufactured using the patterning method of this invention has high performance.

Claims (12)

A method of patterning a substrate for a display element having a gas barrier layer composed of at least one organic region and at least one inorganic region, The patterning method of the board | substrate for display elements characterized by carrying out wet etching using the etching liquid of weak acid or weak base. The method of claim 1, The pKa of the weak acid or weak base contained in the said etching liquid exists in the range of 0.5-10, The patterning method of the board | substrate for display elements characterized by the above-mentioned. The method of claim 1, The etching solution is selected from an oxalic acid solution, an acetic acid solution, a carbonic acid solution and a phosphoric acid solution, and a mixture of two or more thereof. The method of claim 1, The etching liquid is an oxalic acid aqueous solution, The patterning method of the substrate for display elements characterized by the above-mentioned. The method according to any one of claims 1 to 4, The said display element substrate has a transparent electrode, and the transparent electrode is patterned, The patterning method of the display element substrate. The method according to any one of claims 1 to 4, The display element substrate has an anode thin film layer, and the anode thin film layer is patterned, The patterning method of the display element substrate. The method according to any one of claims 1 to 4, The display element substrate has an ITO thin film layer, and the ITO thin film layer is patterned, The patterning method of the display element substrate. The method according to any one of claims 1 to 4, The gas barrier layer has a structure in which at least one organic layer and at least one inorganic layer are laminated. The method of claim 8, The at least one organic layer and the at least one inorganic layer are alternately laminated, The patterning method of the substrate for display elements characterized by the above-mentioned. It patterned using the patterning method of the board | substrate for display elements in any one of Claims 1-9, The display element substrate characterized by the above-mentioned. The manufacturing method of the display element which includes patterning a board | substrate using the patterning method of the board | substrate for display elements in any one of Claims 1-9. It was manufactured by the manufacturing method of the display element of Claim 11, The display element characterized by the above-mentioned.