TW200826298A - Active matrix substrate and process for producing the substrate - Google Patents

Abstract

An active matrix substrate comprising a thin film transistor (4) having an amorphous silicone film on the surface thereof, wherein the transistor is formed on a substrate (1) and the surface of the amorphous silicone film is silylized and an organic protective film (9) is formed on the surface (8) of the silylized amorphous silicone film. Process for preparing an active matrix substrate comprising following step: a step of silylizing a surface of amorphous silicone film of a thin film transistor formed on a substrate by bringing the surface into contact with a silylizing agent, a step of forming a resin film with a radiation sensitive resin composition on the silylized surface of amorphous silicone film and a step of patterning by irradiating the resin film with an active radiation to form a latent pattern in the resin film and subsequently developing a resin pattern by bringing the resin film having the latent pattern into contact with a developing solution. The active matrix substrate can be produced by a simple process as disclosed and has a high reliability.

Description

200826298 IX. Description of the invention: [Technical field to which the invention pertains] = There is an active matrix substrate and a method of manufacturing the same. More in detail = The invention relates to an active matrix substrate which can be manufactured by a simple process, and which is also secretive, and a method of manufacturing the same. [Prior Art] The three active matrix substrate refers to a pixel electrode (m) disposed in the vicinity of the intersection of a plurality of gate signal lines and a source signal line which are orthogonally arranged on the substrate. . The substrate is used in an active matrix type flat display device. It is said that π is placed in the active matrix type flat display device, and since the system (switching element) individually controls each display image t', it is more difficult to generate X strings than the active (four) financial display device. Cross (crosstalk), suitable for high definition and large capacity. Fig. 7 is a diagram showing an example of a circuit on a conventional active matrix substrate. The TFn 4 as a switching element is disposed in the vicinity of the intersection of the gate signal line 12 and the source signal line 13 which are arranged on the substrate. According to the voltage applied to the gate electrode 15, the amount of current flowing from the source electrode 16 to the drain electrode 17 is changed, and the change is transmitted to the pixel electrode 18 via the contact hole. Conventional active matrix substrates are mostly used. The following configuration is formed by a method of a sputtering method or a CVD (Chemical Vapor Deposition) method on a surface of an array substrate on which a TFT is formed, which is formed of a nitride alloy 2219-9105-PF 6 200826298^. The purified film (8) is provided by adding (1) and planarizing the surface by an interlayer insulating film, and is disposed on the interlayer insulating film on the pixel electrode which is connected to the drain electrode of the TFT in the contact hole. For example 'in the patent literature! The intermediate system discloses an active matrix substrate having a protective layer of 4 layers (passivation film) and a planarization layer composed of benzene ring-tauene == insulating film. In the active matrix type process, the above-mentioned purification film must be formed in a vacuum, which is disadvantageous in that it is expensive and cumbersome to operate. On the other hand, Patent Document 2 discloses a configuration in which an oxygen-cut resin directly covering a source electrode, a source wiring, a gate electrode, and a back channel is formed between a pixel electrode and a spacer. An interlayer insulating film and a second insulating film made of an acrylic resin, and an underlying organic interlayer insulating film directly connected to the tft. In the manufacturing process of the cardiac substrate, there are two steps in the process of the second π-cut insulating film, and it is expected that the manufacturing is further simplified. [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 307,778, the entire disclosure of the present invention is to provide a simple process. Active material substrate having high reliability and its manufacture The present inventors have continuously "researched and solved the above-mentioned problems. Now, in the TFT which will be formed on the substrate, the non-b accessing The surface of the active matrix substrate formed by the formation of an organic protective film on the surface of the decane 2219-9105-PF 7 200826298 has a small leakage current, and the voltage of the gate electrode is increased with respect to the gate electrode. The current between the electrode electrodes rises linearly, and even if it is placed in a high-temperature and high-humidity environment for a long period of time, the relevant characteristic or the threshold voltage required for the flow current hardly changes, and the present invention has been completed based on the findings. The invention provides: (1) A method for manufacturing an active matrix substrate, comprising: (a) forming a surface of an amorphous germanium film of a thin film transistor formed on a substrate with a ceramsite burning agent a step of contacting the surface to burn the surface; (b) a step of forming a resin film on the surface of the fragmented amorphous film by the radiation-sensitive resin composition; and (c) a resin film obtained a step of irradiating active radiation to form a latent image pattern in a resin film, and then bringing it into contact with a developing liquid phase, thereby causing the latent image pattern to appear and patterning the resin film. (2) An active matrix substrate, The invention comprises a thin film transistor having an amorphous germanium film formed on a substrate, characterized in that the surface of the amorphous germanium film is sintered and organically protected on the surface of the stront-burned amorphous germanium film. (3) The active matrix substrate according to the above (2), wherein the decane-forming is a trimethyl decyl group. (4) The active matrix substrate according to (2) or (3) above, wherein The organic protective film is a film formed of a crosslinked alicyclic olefin polymer having a polar group. (5) The method for producing an active matrix substrate according to the above (1), wherein 2219-9105- PF 8 200826298 Shi Xi Burning Agent is hexamethyl dicetaxel (6) The method for producing an active matrix substrate according to the above, wherein the radiation sensitive resin composition contains a polar group-containing alicyclic olefin polymer and a crosslinking agent. (7) A planar display device comprising: the active matrix substrate according to any one of (2) to (4) above. According to the manufacturing method of the active matrix substrate of the present invention, the active matrix substrate having high reliability can be manufactured by using the simple operation of the present invention. [Embodiment] The active matrix substrate of the present invention is formed on a substrate. The surface of the amorphous austenite film of tft is burned on the stone and has an organic protective film thereon. Fig. 1(a) is a schematic plan view of a pixel unit of one aspect of the active matrix substrate of the present invention, and Fig. 1(b) is a partial cross-sectional view of the TFT. In the present example, the gate signal line 2 and the source signal line 3 are arranged orthogonally on the surface of the substrate ,, and a TFT 〇 TFT 4 is disposed near the intersection thereof, and has a gate electrode 5 and a source electrode 6. The electrode electrode 7, the semiconductor layer 19, and the interlayer insulating film 20 are provided. The surface of the amorphous ruthenium film of the TFT 4 formed on the substrate is decanolated, and the decane-forming portion 8 is formed. In the figure, the decane-forming portion is thickened, but the thickness of the decane-forming portion is at most a 〇-Si-c-Η interatomic distance, which is a thickness which cannot be called a decane-based layer. An organic protective film 9 made of an organic polymer is provided on the stone-sintering portion 8, and is passed through a contact hole 1 of the organic protective film 9, and the drain electrode 7 and the image 2219-9105-PF 9 200826298 connection. In this aspect, the TFT system has one unit per pixel unit, but two or more units may be formed as desired. The constituent elements of the active matrix substrate of the present invention, that is, the substrate, the gate signal line, the source signal line, the TFT, and the pixel electrode are, for example, the conventional actives described in the above Patent Documents 1 and 2. The matrix substrate is the same and is formed using the materials described in these well-known documents. In the active matrix substrate of the present invention, the sintering may occur at least on the surface of the amorphous germanium film of Τρτ. The surface of the amorphous germanium film of the TFT refers to the surface of the amorphous film of the channel portion of the TFT. The Shiki base to be used in the calcination is not particularly limited, and examples thereof include dimethyl decyl group, trimethyl oxalate, triethyl decyl group, triisopropyl decyl group, and tert-butyl group. Dimethyldecyl, tert-butyldiphenylalkyl, triphenylsulfanyl and the like. Among the 4, it is suitable to use trimethyl sulphide (i.e., trimethyl sulphide). Here, the term "decane" means that a proton present on the surface of a substrate or the like is replaced by a sulphuric acid group. When the surface of the amorphous ruthenium film of the TFT is decanolated, the surface of the amorphous ruthenium film becomes hydrophobic, and moisture can be prevented from immersing between the surface of the amorphous ruthenium film and the organic protective film, and excellent heat and humidity resistance can be obtained. Active active matrix substrate. In the active matrix substrate of the present invention, the organic protective film is generally formed on the entire surface of the substrate by directly contacting the surface of the amorphous germanium film of the germane-substituted TFT. In the present invention, as the material for forming the organic protective film, for example, polyalkylene such as polyethylene, polypropylene, polybutene, etc.; alicyclic thin smoke polymer; acrylic resin; Amine resin; polyoxyalkylene resin; polyether 2219-9105-PF 10 200826298 and the like. Among these, the frequency dependence of the dielectric constant is small, and the == is extremely small. The thickness of the organic protective film is generally " In the invention, it is preferable, and 0.5 to 30//ηι is more preferable. .50 "The so-called alicyclic oxime polymer of Shishan refers to the polymerization of a ring structure and an alicyclic hydrocarbon monomer containing 2 anaerobic bonds. It is a structure of a single 亓 取 取 ^ ^ 54 early body early structure, qr & In terms of a ring structure, the system is rotated like a ring structure f. In addition, the ring structure may be a single ring, or may be a multi-day occupant, a parent conjugate ring, or a combination of the 成 夕 _ w _ The number of carbon atoms in the % of h is not particularly limited, and is generally preferably from 4 to 30 t to 20, more preferably from 5 to 15. The monomeric tobacco polymer may have an alicyclic ring. Hydrocarbon monomer building unit other than the dilute hydrocarbon monomer. In the alicyclic flue-cured polymer, the alicyclic formula can be appropriately selected as desired, generally 3. = 5 〇 to 1 〇°% by weight is better, from 7. to 1. The weight is “more”. The obtained organic protective film at this time has good moist heat resistance. good. In the case of the bis-cycloalkane olefin polymer, the proportion of the polar group in the "polar group" is not particularly limited =: the total molar number of the constituents of the ring-type smoky polymer is organic From the point of view of the good resistance to heat and humidity of the protective film, a r. " ear %, with ... 〇 耳 % is a good heart «The body is better to form a monomer unit. It exists in each composition early body π The type or the number of the polar groups is not particularly limited. In the above-mentioned polar group, the series is as follows: one or more selected from the group consisting of

2219-9105-PF 11 200826298 carbonyl), alkoxycarbonyl, dicarboxylic anhydride group (carbonyloxycarbonyl), hydroxy (carboxy), nitro, epoxy, oxetanyl and quinone imine The basis of the group (hereinafter referred to as "specific polar group"). Examples of the specific polar group as a radical include, for example, a substituent containing a phenolic hydroxyl group such as a hydroxyphenyl group or a hydroxyphenylalkyl group; and a hydroxyalkyl group, a hydroxyalkoxy group, or a hydroxyalkoxycarbonyl group. The substituent of the alcoholic hydroxyl group is preferably a hydroxymethoxy group or a hydroxyethoxy group. In the case where the specific polar group is a quinone imine group, a series of N-phenyldicarboxy quinone imine groups and the like are mentioned. The alicyclic olefin polymer may have only one type of the above-mentioned specific polar group, or may have two or more types, and it is preferable to have two or more types. Among them, it is more preferable to have both a carboxyl group and a quinone imine group. The alicyclic olefin polymer having the above specific polar group is exemplified by a repeating structural unit represented by the following formula (I).

[In the formula (I), R1 to R4 are each independently a hydrogen atom or -Xn-R, (χ is a divalent group such as a methylene group or a carbonyl group, and 11 is fluorene or 1> R, which is a group which may have a substituent. a radical of 1 to 7 carbon atoms such as a benzyl group or a carboxyl group, an aromatic group or a 2219-9105-PF 12 200826298 specific polar group, and a specific polar group -Χη-R', m It is an integer of 2 to 。. An alicyclic olefin polymer having a specific polar group is an alicyclic olefin monomer having a specific polar group or an alicyclic olefin monomer having a specific polar group and the alicyclic ring by a known method The other monomer of the olefin monomer polymerization is polymerized and obtained by hydrogenation as desired. The specific polar group may be present in the other monomers described above in addition to the alicyclic olefin monomer. Further, when a specific polar group is present in other monomers, a specific polar group may not be present in the alicyclic olefin monomer. In the case of an alicyclic olefin monomer having a specific polar group, the series is as follows: 5- 5-carbylbicyclo[2·2·1]hept-2-indole, 5-methyl-5-pyridyl Bicyclo[2.2.1]hept-2-ene, 5-carboxyindolyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, 8-methyl-8-hydroxycarbonyltetracyclo[4 ·4·0·12'5·17'1()] Twelve-3-indole, 8-carboxymethyl-8-hydroxycarbonyltetracyclo[4·4.0·12'5·17'1()]10 An alicyclic olefinic monomer having one carboxy group such as di-3-indole; a 5-cyclic exo-6-ring-di-diylbicyclo[2.2.1]hept-2-ene, 8-ring Exo-9-cyclo-dihydroxycarbonyltetracyclo[4.4.0·12,5. I7,1. 11-3 - dilute, bicyclo[2.2.1]hept-2-indole-5,6- bis-anhydride, tetracyclo[4·4·0·125·171°]dodec-3-ene 8,9-dicarboxylic anhydride, hexacyclo[6·6.1 I.3'6·11()'1 3 0 2'7·09'14]heptade-4-ene-11,12-dicarboxylic anhydride An alicyclic olefin monomer having 2 carboxyl groups; 5-(4-hydroxyphenyl)bicyclo[2·2·1]hept-2-ene, 5-mercapto-5-(4-hydroxyphenyl) Bicyclo[2·2·1]hept-2-ene, 5-carboxyindolyl-5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene, 8-methyl-8 -(4-hydroxyphenyl)tetracyclo[4. 4. 0. I2,5. 17,1G]12-3- 2219-9105-PF 13 200826298 Alkene, 8-carboxymethyl-8-(4- Hydroxyphenyl)tetracyclo[4·4·0·l2'5· pu] an alicyclic olefin monomer having one hydroxyphenyl group such as dodeca-3-ene; phenyl)-(5-norbornylalkenyl) An alicyclic olefin monomer containing an N-substituted quinone imine group, such as a 2,3-dicarboxy sulfoximine group. These monomers may be used singly or in combination of two or more. For other monomers which can be polymerized with the above alicyclic olefin monomer, the series are as follows: ethylene, propylene, 1-butene, pentene, 1-hexene, 3-methyl-1, and 3, -methyl-1 -pentane, 3-ethyl-1-pentane, 4-methyl-pentene, 4-methyl-p-hexene, 4,4-dimethyl-buhexene, 4, 4-dimethyl y-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, octene, dioxins, 1-dodecene, 1-tetradecene, A-olefin having 2 to 20 carbon atoms such as hexadecene, octadecene and hexadecene; 1,4-hexadiene, 4-methyl-1-hexene-ene, 5-methyl- A non-conjugated diene such as 1,4-hexadiene or 1>7-octadiene, or a substituent of the monomers substituted with a specific polar group. These monomers may be used alone or in combination of two or more. The alicyclic olefin polymer used in the present invention is converted into polystyrene by gel permeation chromatography (JGPC, Gel Permeation Chr〇mat〇graphy) using tetrahydrofuran (THF, Tetrahydrofuran) as a solvent. The weight average molecular weight (Mw) is preferably from 1 to 1, 〇〇〇, 〇〇〇, preferably from 5, _ to 500,000, more preferably from 1 〇〇〇〇 to 2,500,000. If the weight of the alicyclic olefin polymer is an average of eight tens of enthalpy (嶋U00 to "_, 〇〇〇", it can form a moisture-repellent property: an organic protective film that maintains a balance between properties and surface smoothness. The molecular weight distribution of the material, the ratio of the weight average molecular weight (Mw) to the number average (旬η) measured by the gel permeation 2219-9105-PF 14 200826298 by thf as a solvent (MW//Mn) Preferably, it is 5 or less, and 4 is more preferably 3 or less. Preferably, the organic protective film of the present invention is composed of an alicyclic olefin group / > The alicyclic olefin polymer is preferably formed, and is excellent in processability after formation with an organic protective film, and the organic protective film is a crosslinked aliphatic alicyclic ring. The active matrix substrate of the present invention can be produced by a known method described in, for example, the above-mentioned Patent Documents 1 and 2, but it is preferable to have the following method based on the simple operation and the efficiency. That is, (a) the TF formed on the substrate a step of contacting the surface of the amorphous ruthenium film of T with a decylating agent to form a surface of the amorphous ruthenium film; (b) forming a surface of the fluorinated amorphous ruthenium film by a radiation sensitive linear resin composition a step of forming a resin film; and (c) irradiating the obtained resin film with active radiation to form a latent image pattern in the resin film, and then bringing it into contact with the developing liquid phase, thereby causing the latent image pattern to appear and patterning the resin film The step of decylating the surface of the TFT formed on the substrate in the step (a) of the method of the present invention is, for example, methyl perylene oxide. , dimethyl dichlorodecane, trimethylchlorodecane, N-dimethyl decyl decylamine, N, fluorene-bis(trimethyldecyl) acetamide, N-methyl-N-trimethyl Base alkyl acetamide, N-methyl-N-trimethyl decyl difluoroacetamide, N-trimethyl decyl dimethylamine, N-trimethyl decyl 2, 2219-9105-PF 15 200826298 Ethylamine, N,0-bis(trimethyldecyl)trifluoroacetamide, n-trimethyltinylimidazole, tetramethyldiamine, Tributyldimethyl chlorohydrazine, N-fluorenyl-N-(t-butyldimethylsulfonyl)trifluoroacetamide, dimethylmethyltetramethyldiamine, gas methyl Dimethyl gas decane, bromomethyl decyl chlorodecane, octadecyl trioxane, N, N,-bis (tridecyl decyl) urea, N-trimethyl decyl-N, N' -diphenylurea, N,0-bis(trimethyldecyl)carbamate, N,0-bis(trimethyldecyl)amine pyrogate, trimethyldecyltrifluoromethane Sulfonic acid, etc. Among these, the effect of preventing moisture from entering the surface of the amorphous tantalum film and the organic protective film and the effect of improving the adhesion between the two interfaces are excellent, so that hexamethyl group can be particularly suitably used. Amidoxime. These decylating agents may be used singly or in combination of two or more. In the method of the present invention, a method of contacting the surface of the amorphous germanium film of the TFT formed on the substrate with the decylating agent to tar the surface is not particularly limited. For example, in one method, the formed array substrate (the object on which the TFT is formed on the substrate) is separated from the heating plate (h〇t P1 ate ) and carried into the heat treatment chamber provided with the heating plate, and the processing chamber is disposed. The vapor of the decylating agent is introduced under reduced pressure, the heating plate is heated, and the array substrate is brought close to the heating plate, and the vapor of the decylating agent is uniformly diffused at 50 ° C or lower to stop the introduction and evacuation of the vapor of the decylating agent, and After the array substrate is in contact with the heating plate and after the decaneization reaction is carried out at a temperature of 80 to 9 (the temperature of rc), the vaporization of the sulphuric acid burning agent is replaced by nitrogen gas to stop the decaneization reaction. The sinter burning is performed on the array substrate and the oximation The vapor of the agent is carried out during the contact. At this time, the concentration of the alkylating agent is preferably from 0. lvol% to 5 voU. 2219-9105-PF 16 200826298 The surface of the amorphous germanium film of the TFT may be included by the above method. The entire surface of the array substrate is decanolated. The contact is usually carried out for more than 丨min. In addition to the above method, the array substrate can be exemplified by a film of a burnt agent at a normal temperature or a normal pressure. Sealed in a closed container, thereby decidating the surface of the amorphous germanium film of the TFT on the array substrate. By this method, only the surface of the amorphous austenite film of the TFT can be substantially Next, in the step (1), a resin film (organic protective film) is formed on the surface of the amorphous germanium film of the germane-crystallized TFT by the radiation sensitive linear resin composition. It is not particularly limited, and is generally suitable for use of an alicyclic olefin polymer having a polar group, a crosslinking agent, a radiation sensitive compound, and a solvent. Preferred examples of the alicyclic dilute hydrocarbon polymer having a polar group In the series, for example, an alicyclic dilute hydrocarbon polymer having a polar group. As a preferred example of the crosslinking agent, the series includes two or more epoxy groups (having a ring having three or more rings). Oxygen is preferred) bisphenol A epoxy resin, bisphenol F epoxy resin, silk (four) varnish epoxy resin, W secret varnish epoxy resin, multi-type epoxy resin, cyclic aliphatic ring Oxygen resin, aliphatic glycidyl ether, propylene glycol vinegar polymerization A polyfunctional epoxy compound, such as a radiation-sensitive compound (which can absorb a radiation such as ultraviolet rays or an electron beam to initiate a chemical reaction & a compound) < a preferred example], a series of & : i 2- Cai brewed diazide -5-sulfonyl chloride, L2 - naphthoquinonediazide_4_sulfonate, hydrazine, benzoquinonediazide-5-sulfonyl chloride and the like quinonediazide sulfonium halide, and 2219- 9105-PF 17 200826298 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropene, 4'4 —[I-[4-[1-[4 A photoacid generator such as an ester compound of a compound having a phenolic hydroxyl group such as phenyl]-1-methylethyl]phenyl]ethylidene] bisphenol. In the composition, in addition to other components commonly used for the known radiation-sensitive resin composition, the inorganic fine particles may contain, for example, colloidal cerium oxide. Further, examples of the solvent include a monoalkylene glycol solvent, a polyglycol diol solvent, a monoalkylene glycol alkyl ester solvent, a polyalkylene glycol alkyl ester solvent, and a monoalkylene glycol diester solvent. A polyalkylene glycol diester solvent or the like. The above sensed radiation linear resin composition is a positive type, and may also be a negative type. This composition can be produced by a known method. In addition, the solid content concentration of the radiation sensitive resin composition used in the method of the present invention can be appropriately selected in consideration of the desired thickness of the resin film, the coating method, and the like, and is preferably 5 to 4% by weight. The prepared radiation-sensitive resin composition is preferably coated after removing foreign matter or the like using a filter having a pore diameter of 0·1 to 5/m or the like. The method of forming the resin film is not particularly limited, and examples thereof include a coating method, a film lamination, and the like. By forming a resin film on the P train substrate by the method of (4), a desired resin film can be formed on the surface of the amorphous germanium film of the germane-crystallized TFT. The resin film is preferably formed on the entire surface of the array substrate. The coating method is a method in which a radiation-sensitive resin composition is applied onto an array substrate and then dried by heating to remove a solvent. Examples of the method of applying the radiation-sensitive resin composition on the array substrate include a spray coating method, a spin coating method, a roll coating method, and a die coating method ((1: (; 〇 slave 11^)) , doctor blade coating method, spin coating method, rod 2219-9105-PF 18 200826298 coating method, screen printing method, etc. The heating and drying temperature can be appropriately selected according to the type of each component and the mixing ratio. Generally, it is 3 to 15 (rc. The heat drying time can be appropriately selected according to the type of each component and the blending ratio, but generally 0.5 to 90 minutes. The film stacking method is to apply the radiation sensitive resin composition to After the resin film or the metal film or the like is removed, the solvent is removed by heating and drying to obtain a B pm film, followed by a method of laminating the B-stage film on the array substrate. The heating and drying conditions may be in accordance with the types of the respective components. And the mixing ratio is appropriately selected, the heating temperature is generally from 3 Torr to 15 Torr, and the heating time is generally from 0.5 to 90 minutes. The film lamination can be performed by a press laminator (Uminator), a press (press), a vacuum. Laminating machine In the step (C), the obtained resin film is irradiated with actinic radiation to form a latent image pattern in the resin film, and then brought into contact with the developing liquid solution, thereby making When the latent image pattern is formed, the resin film is patterned. The actinic radiation is not particularly limited as long as it changes the alkali solubility of the radiation sensitive resin composition, and examples thereof include ultraviolet rays. Single-wavelength ultraviolet light such as g-line or i-line, KrF excimer laser, ArF excimer laser light, etc.; particle beam such as electron beam, etc., which are formed by selectively irradiating the active radiation into a pattern. For the method of the latent image pattern, light rays such as ultraviolet rays, g-line, i-line, KrF excimer laser light, and ArF excimer laser light are transmitted through the mask pattern by reducing the projection exposure device or the like.讣pattern) a method of illuminating, and by particle lines such as electron beams

2219-9105-PF 19 200826298 Line drawing, method of sputum, etc. After the irradiation of the active radiation, the resin film 纟 60 may be desired as desired (heating treatment at rc! to 2 minutes of heat treatment) for developing the latent image pattern formed by irradiation with active radiation For the developer, an aqueous solution of the test compound can be used. For the test compound, an inorganic compound such as sodium oxyhydroxide or chlorine oxidizing, tetramethylamine hydroxide or tetraethylammonium oxide can also be used. Any of the compounds: an aqueous medium of an aqueous alkaline solution may be a water-soluble organic solvent such as water methanol or ethanol, or an aqueous solution may be added with an appropriate amount of a surfactant. The method of bringing the developer into contact with the resin film having the latent image pattern is, for example, a paddle methQd, a spray method, a dipping method, etc. The development temperature is generally 5 to a step, and the development time is generally different. After the resin film patterned as described above is formed on the array substrate, the development residue of the substrate back surface and the substrate end portion is removed on the substrate as desired, The array substrate may be rinsed with a rinse liquid such as ultrapure water. Further, in order to deactivate the radiation sensitive compound as desired, the entire surface of the array substrate having the patterned resin film may be irradiated with active radiation, ' Or ^ at the same time or after irradiation 'heating the resin film. Heating: method and § ' series of methods such as heating the array substrate in a heating plate or oven. Heating temperature is generally 1 〇〇 to 3 〇〇 t .

In the method of the present invention, it is preferable to carry out a crosslinking reaction of the resin after the patterned resin film is formed on the array substrate. The method of crosslinking the crucible formed on the substrate of the array 2219-9105-PF 20 200826298 can be appropriately selected depending on the kind of the agent, and the heating of the one used can be carried out by heating. The twisting system uses, for example, a heating plate, an oven, etc., and is 25 (TC is preferred, the heating time is turned on # and the slave is 180 to be appropriately selected by a machine, etc., for example, J 4 degrees, 60 shovel A# 』 When using a heating plate, it is generally 5 to 60 / knives. When using an oven heating system, it can be used as desired, but in a minute. It is carried out under an inert gas atmosphere. a, 氪 according to the above step (c), A+ Fortunately, the deciduous membrane is formed as a contact hole on the protective film of the hole formed by the IT two hunting by, for example, the organic mining method, in the presence of mu UmTinGxide, indium tin oxidation and the TFT... Ai is patterned through Contact hole of the resin film = the electrode of the TFT is connected to the pixel electrode. At this time, a Ray ★ W "" opening/forming electrode pattern is simultaneously formed by I τ ο constituting the pixel electrode. Thereafter, the matrix substrate is rubbed (bbi) by forming an alignment film. g) Processing of the aligning process, and obtaining the flat display device of the present invention is characterized by including the active matrix of the present invention: a substrate. Since the flat display device of the present invention uses the base: it is an excellent device which has a long service life, low power consumption, and high contrast. In a specific example of the device, the series includes an active matrix liquid crystal display device, an active matrix organic electroluminescence (display device, etc.) The so-called active matrix liquid crystal display device refers to a liquid crystal material S film-like liquid crystal. A pair of substrates 2219-9105-PF 21 200826298 which are disposed opposite to each other, wherein one of the pair of substrates is a flat display device comprising the active matrix substrate of the present invention. The substrate to be disposed on the active matrix substrate (hereinafter referred to as "opposing substrate") is a color filter substrate, a microlens (a core (10) substrate, etc. In a modification of the liquid crystal display device including the substrate and the color filter substrate, a series of color filter material layers are directly disposed on the pixel electrodes in the active matrix substrate, and no color is provided on the opposite substrate. a liquid crystal display device in the form of a filter, or a pixel electrode of an active matrix substrate formed by a color filter material having an electric current, on the opposite substrate A color filter, a light sheet, a liquid crystal display device, etc. are provided. Fig. 2 is a plan view showing an aspect of an active matrix liquid crystal display device which can be fabricated using the active matrix substrate of the present invention, in the third The figure shows a cross-sectional view of the χ-γ line. In this aspect, the active matrix substrate 1?1 having the pixel electrode 202 and the color filter substrate 102 having the counter electrode 2?6 are sandwiched with a liquid crystal layer. In the opposite direction, a pixel is formed in an opposing portion of each of the pixel electrode 202 and the counter electrode 206. The sealing material 1〇3 is provided on the outer periphery of the display region composed of the pixels, and is displayed on the display region and the sealing material. An electrode pattern exists in a region between 1 and 3. In the color filter substrate 102, a counter electrode 206 is disposed on the color filter layer 207 having the black matrix 2〇8, and an alignment is provided thereon. Membrane m. On the active matrix substrate 1 〇1, a gate signal line 2〇3 for supplying a gate signal for driving the TFT 201 as a switching element, and a source signal for 2219-9105-PF 22 200826298 are supplied to Source signal line of TF Τ 2 01 2 0 4 The diode is disposed on the substrate. The TFT2〇1 is disposed in the vicinity of the intersection of the two signal lines, and the organic protective film 104 is interposed therebetween, and the pixel electrode 202 is disposed in such a manner that a part of the signal lines overlap with the two signal lines. In the contact hole (not shown) of the organic protective film 1〇4, the pixel electrode 202 is connected to the drain electrode of the TFT 201. Further, the alignment film 1 is disposed on the organic protective film 1 〇4. 1 1. On the other hand, the gate signal line 203 and the source signal line 2〇4 extend beyond the frame region to form a signal voltage for driving the TFT 201 to extend through the input terminal 108 passing through the terminal region provided outside the gate signal line 〇4. Input to the gate signal line 2G3, and the signal voltage of the displayed data can be input to the source signal line 2〇4. The electrode pattern t 1 () 5 is formed in the outer peripheral region of the organic protective film (10), and is even extended to the terminal region' and input with a hole from the driving circuit. The liquid crystal display device described above is manufactured in accordance with the method described in Japanese Laid-Open Patent Publication No. 2003-00521-5.所谓. The so-called active matrix type organic electroluminescent (EL) display device 2 is arranged in a matrix to form each pixel on the active matrix substrate of the present invention = at least one organic EL element; and At least 2 TFTs of organic a piece. The electric EL element is not particularly limited, and the series is as follows: a hole is formed between the electrode as the anode and the electron injecting electrode as the cathode, and the hole is formed from the hole. Injecting the electric ^ t SH_A structure, or forming a structure of the luminescent material layer and the layer f and the electron ^ (SH - B structure) between the electron η sub-injection electrodes, or in the hole injection electrode

The hole transport layer and the luminescent material layer are formed between the input electrodes and the structure (DH structure) of the electron transport layer of 2219-9105-PF 23 200826298. In the case of a structure, the organic EL element utilizes a hole injected from a hole injection electrode (anode) and an electron injected from an electron injection electrode (cathode) in a luminescent material layer and a hole (or electron) transport layer. The interface and the luminescent material layer are combined to emit light and operate. Fig. 4 shows a typical configuration example of an organic EL element in the organic EL display device of the present invention. The organic EL device shown in Fig. 4 is composed of an active matrix substrate (including a pixel electrode as a lower electrode layer (anode)), a light-emitting material layer 302, and an upper electrode layer (cathode) 3〇3. Further, the start and seal film 304 are set as the outermost layer. It is composed of one of the elements of the organic EL display device [generally for at least! For the organic EL element, at least two TFTs for driving the EL element, that is, a driving transistor and a writing transistor, are required. However, in the configuration example of FIG. 4, two transistors are omitted. A crystal system is present in the active matrix substrate of the present invention. In the active matrix substrate of the present invention, a pixel electrode as an anode is connected to a gate electrode of a TFT. An example of a circuit on the active matrix substrate of the present invention is shown in FIG. 5, but in the circuit, the TFT 402 is written by a sequential yoke applied to the voltage of the scan electrode 4A connected to the horizontal drive circuit. The transistor is in an on state, and an amount of charge corresponding to a display signal from the data electrode 4〇3 connected to the vertical drive circuit is accumulated in the capacitor 404. The TFT 405 (drive transistor) is operated by the amount of charge accumulated in the capacitor 404, and current is supplied to the organic member 406 to turn on the organic EL element. This lighting state is maintained while the voltage is applied to the scan electrode 401. The method described in the above-mentioned organic EL display device 2219-9105-PF 24 200826298 is manufactured by the method described in Japanese Laid-Open Patent Publication No. 2002-333846 (Embodiment). The following examples are given to illustrate that the description is not limited to The invention will be described as an embodiment of the present invention. Manufacture of alicyclic olefin polymer) Production Example 8 - Mercaptotetracyclo [44 5 parts, N-phenyl-(卜冰冰κ) eleven-3-ene 60 heavy 1 /alkenyl-2,3 - dimethyl quinone imine) 4 〇 parts by weight, two: dilute "parts by weight ... '... tolyl) -, - hexyl phosphine) sub-nodal quinone dihydrate 〇〇 5 parts by weight in ethyl f_4GG parts by weight In a glass reactor in which a person is replaced by nitrogen, a polymerization reaction solution containing η C is subjected to polymerization for 2 hours, and a polymerization reaction solution of polymer 4 is obtained. Conversion rate = 9 : upper. The polymerization weight average molecular weight is 3, _, thousands of:: the sub-quantity is u., the molecular weight distribution is 168. Then adding bis(tricyclohexyl phenyl) B to the polymerization reaction solution 1 part by weight of oxymethylene sulphide dichloride as a hydrogenation catalyst, and chlorine is allowed to be stored for 5 hours under the force of -:, after the hydrogenation reaction, 1 part by weight of the active stone inverse powder is added and placed (4) The device (aut〇clave) was given a face, and the surface was dissolved with hydrogen at 4 MPa (iv) for 3 hours. Then, the solution was taken out and the filter was made with a pore size 〇·2” fluororesin (fm... The activated carbon was separated to obtain 476 parts by weight of a hydrogenation reaction solution containing hydrogen of 2219-9105-PF 25 200826298 1B of the ring-opening metathesis polymer 1A. The filtration system was carried out without blocking. 1Bi aerated reaction solution (4) The solid content concentration is 20.6 wt%, and the yield of hydride 1B is 98 1 wt. The obtained hydride 1B has a weight average molecular weight of 4, 43 Å, a number average molecular weight of 2,570, and a molecular weight of 2,570. The distribution is 丨·72, and the hydrogenation rate is 99 9%. The hydrogenation reaction solution of the obtained hydride 1B is concentrated by a rotary evaporator to adjust the solid content concentration to % by weight to obtain a hydride 1C (having A solution of a carboxyl group as a polar group of an alicyclic olefin polymer. The weight average molecular weight, number average molecular weight, and molecular weight distribution of the hydride before and after concentration are not changed. (Example 1) In Production Example 1 The obtained alicyclic olefin polymer solution containing hydride lc (solid content: 35 wt%) 100 parts by weight of a polyfunctional epoxide having an alicyclic structure as a crosslinking agent [Japan Daicel Chemical Industry Co., Ltd. K (shares) (Daicel Chemical Industries, Ltd.), EHPE3150

(product name), a molecular weight of about 2,700, an epoxy group number of 15] 25 parts by weight, and 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3 as a radiation sensitive compound 25 parts by weight of condensate of phenylpropane (1 mol) and 丨'2-naphthoquinonediazide-5-sulfonium (2.5 mol), anti-aging agent (丨, 2, 2, 6, 5 parts by weight of 6-pentamethyl-4-piperidinyl/tridecyl)butane tetracarboxylate, 5 parts by weight of glycidoxypropyltrimethoxydecane as a secondary auxiliary agent, and polyfluorene oxide The surfactant (Shin-Etsu Chemical Industry Co., Ltd., KP341 (product name)) 〇.05 parts by weight is mixed, and then added diethyl 222119105-PF 200826298 alcohol ethyl methyl hydrazine 92 parts by weight and N_A The base_2_π is mixed with 8 parts by weight of the Luo phase and then mixed. The mixture formed a homogenous solution within 5 minutes. This solution was filtered using a polytetrafluoroethylene filter having a pore size V to modulate the radiation sensitive resin composition 1 D. On a glass substrate [corning inc〇rp〇rated, Kang F H37 (product name)], a thick chrome film was formed using a paste (10), and patterned by lithography. Electrode, closed-circuit signal line and gate terminal. Next, the gate electrode and the gate wiring are covered by a CVD apparatus, and a tantalum nitride film as a gate insulating film having a thickness of 45 〇 nm and a layer of a semiconductor layer having a thickness of 25 〇 nm are continuously formed. The 5 〇m thickness is used as the n + Si layer of the ohmic contact layer, and the n + Si layer and the a -& layer are patterned into islands. Further, a 20 〇nm thick chromium film is formed on the gate insulating film and the n + Si layer by a sputtering device, and the source electrode, the source signal line, the drain electrode, and the data terminal portion are formed by lithography. An unnecessary n + Si layer between the source electrode and the drain electrode is removed to form a hd channel, and an array substrate in which a TFT is formed on the glass substrate is obtained. The array substrate is placed in a heat treatment chamber equipped with a heating plate, and the inside of the processing chamber is degassed, and then hexamethyldioxane is introduced as a decylating agent, and hexamethyldiamine is burned at 50C. After the vapor was uniformly diffused in the treatment chamber, the array substrate was heated to 85 Torr by a hot plate and calcined for 1 minute. Next, the hexamethyldioxane in the treatment chamber was replaced with nitrogen, and the mixture was cooled to room temperature to obtain an array substrate comprising the surface of the amorphous ruthenium film of the TFT and the surface of which was monodecanolated (trimethyl decane). The above-mentioned sensitizing radiation resin composition 1J) was spin-coated on the obtained surface 2219-9105-PF 27 200826298 after the decylated array substrate, and pre-bake was performed by using a hot plate at 9 (rc for 2 minutes). A resin film having a film thickness hm was formed, and the resin film was irradiated with ultraviolet light having a light intensity of 5 mW/cm 2 at 365 nm for 4 sec through a mask of a hole pattern of lOemxl/zm. Then, 〇. 4 was used. A 40% by weight aqueous solution of tetramethic acid hydroxide was subjected to development treatment for 25 seconds at 25 Torr, and then washed with ultrapure water for 3 sec to form a pattern of contact holes, and a residual film ratio of 90% or more was obtained. Good pattern. After using the oven, post-bake (cross-linking treatment) was heated for 2 minutes at 2301. The array substrate on which the organic protective film was formed was transferred to a vacuum chamber using argon/oxygen. The 5 gas (volume ratio 1 〇〇: 4 ) is used as a sputtering gas, the pressure is 〇.3Pa, and the DC output is 40 (10). This sputtering is performed through the mask, thereby forming a film in contact with the drain. Thick 2〇〇nmi In — Sn — bismuth-based amorphous transparent conductive layer (pixel power) The active matrix substrate is obtained. A voltage of 20V is applied between the source electrode and the drain electrode of the active matrix substrate, so that the voltage applied to the gate electrode is between 〜2〇 and 3〇v. For the change, a manual probe (manual pr〇ber) and a semiconductor parameter analyzer (Agilent, 4156c) were used to measure the current between the source electrode and the drain electrode. The result is shown in the fourth. Fig. The leakage current is lxl〇-i3A/cm2, and the threshold voltage is 4v. After the active matrix substrate is placed in a 5 (rc, 80% RH environment for 100 hours, the same measurement is performed. The leakage current is lxl "3A". /cm2, the limit value of electric waste is 4V, no change. 2219-9105-PF 28 200826298 (Example 2) In addition to the acrylic resin solution [JSR (strand), OPTIMER] replaced the radiation sensitive resin composition 1D spin coating An active matrix substrate was produced and evaluated in the same manner as in Example 1 except that the surface of the substrate obtained in Example 1 was burned on the same day as in Example 1. The leakage current after the production was 3×10 −13 A/cm 2 and the threshold voltage was 3 V. Place 1〇 in an environment of 50°C and 80% RH The leakage current after 〇 hours is lxl (T12A/cm2, and the threshold voltage is 2V. (Example 3) In addition to replacing the radiation sensitive resin with a polyimide resin solution [Toray (Photo), Photoneece] An active matrix substrate was prepared and evaluated in the same manner as in Example 1 except that the composition id was spin-coated on the surface-derived array substrate obtained in Example 1. The leakage current after the instant is 7xlO_13A/cm2, the threshold voltage is 3V °, and the leakage current is 3x10 12A/cm2 after being placed in an environment of 50 °C and 80% RH for 1 hour. The threshold voltage is 1 5V. (Comparative Example 1) The array substrate on which the TFT was formed on the glass substrate obtained in Example 1 was the same as the Example 以外 except that the step of spin-coating the radiation sensitive resin composition was not carried out without performing decaneization. The active matrix substrate was fabricated and evaluated. The leakage current after the instant is 2X1 〇 11A / cm2, and the threshold voltage is 2219-9105-PF 29 200826298 2V. The leakage current after placing loo hours in an environment of 50 ° C and 80% RH was 3 x 10 1 QA/cm 2 , and the threshold voltage was 0 V. (Comparative Example 2) The array substrate on which the TFT was formed on the glass substrate obtained in Example 1 was changed to the step of spin coating the acrylic resin solution [jsr (strand), 0PTIMER] except that the decylation treatment was not carried out. An active matrix substrate was produced in the same manner as in Example 2, and evaluation was performed in the same manner as in Example 。. The leakage current after the instant is 2xl0-6A/cm2, and the active matrix substrate does not operate. (Comparative Example 3) The array substrate on which the TFT was formed on the glass substrate obtained in Example 1 showed a yoke-free crystallization treatment, and the polyimine resin solution was changed to [T〇ray] In the same manner as in Example 3, the same procedure as in Example 3 was carried out, and the active matrix substrate was used and evaluated in the same manner as in Example 1. The leakage current after the instant is made to the board and 5 is not operated. Examples 1 to 3 and ratios 5xl〇5A/cm2 are shown in the first table in the active matrix based on the results of Comparative Examples 1 to 3.

2219-9105-PF 30 200826298 Table 1 Initial value 50 °C, 80% RH, 100 hours after treatment of leakage current (A/cm2) Threshold voltage (V) Leakage current (A/cm2) Threshold voltage ( V) Example 1 decaneated + alicyclic olefin polymer ΙχΗΓ 13 ◎ 4 ◎ lxlO'13 ® 4 ◎ Example 2 decylation + acrylic resin 3x10-13 ◎ 3〇lxlO-12 Δ 2 Δ Example 3 decaneization + Polyimine resin 7x1013 〇3〇3x1012 Δ 1.5 Δ Comparative Example 1 alicyclic olefin polymer 2x10"11 Δ 2 Δ 3x10'10 Δ 0 Δ Comparative Example 2 Acrylic resin 2x10'6 X — — — Comparative Example 3 Yttrium imine resin 5x10-5 X — — — ◎ ～ ～ X is a symbol indicating the relative evaluation results of the respective examples and comparative examples. [◎: excellent, 〇: good, △: OK, X: not] Among them, one means that it cannot be measured. As is apparent from Tables 1 and 4, an example in which the surface of the array substrate on which the TFT is formed on the glass substrate is decidated and the organic protective film is formed by using the crosslinked polar group-containing alicyclic olefin polymer The active matrix substrate of 1 and the active matrix substrate of Examples 2 and 3 in which the organic protective film is an acrylic resin and a polyimide resin have good practicability even when placed in a high temperature and humidity environment for a long time. Performance. On the other hand, compared with the active matrix substrate of Example 1 in which the surface of the array substrate is dealkylated, the surface of the array substrate is not subjected to decaneization to form an organic compound by using a crosslinked polar alicyclic olefin polymer. The active matrix substrate of Comparative Example 1 of the protective film was inferior in performance. Further, it can be seen that the active matrix substrates of Comparative Examples 2 to 3 in which the surface of the array substrate is not subjected to decaneization and the organic protective film is formed of an acrylic resin and a polyimide resin have a large leakage current, and in the case of an active matrix substrate No operation 2219-9105-PF 31 200826298 产业 (Industrial Applicability) According to the active matrix substrate of the present invention, the leakage current is small, and the phase: the voltage at the gate electrode is increased, the source electrode The current between the /electrode electrodes rises linearly, and even if it is placed in a high temperature and high humidity environment for a long time, the relevant characteristics or threshold voltage are hardly changed, so that the service life is long, the power consumption is low, and the contrast is high. Excellent active matrix type flat display device. Further, according to the manufacturing method of the active matrix substrate of the present invention, an active matrix substrate having excellent characteristics can be efficiently manufactured by a simple operation. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1(a) is a plan top view of an i-pixel unit of one aspect of the active matrix substrate of the present invention, and Fig. Ub) is a partial cross-sectional view of the TFT portion. Fig. 2 is a plan view showing an aspect of an active matrix type liquid crystal display device which can be fabricated using the active matrix substrate of the present invention. Fig. 3 is a cross-sectional view (partial) taken along the line X-Y of the active matrix type liquid crystal display device of Fig. 2. Fig. 4 is a view showing a typical configuration of an organic eL element in the organic EL display device of the present invention. Fig. 5 is an explanatory diagram showing an example of a circuit on an active matrix substrate of the present invention used in an active matrix type organic electroluminescence display device. 2219-9105-PF 32 200826298 Fig. 6 is a graph showing the relationship between the voltage of the gate electrode of the active matrix substrate of Example 1 and the current between the source electrode and the drain electrode. Fig. 7 is an explanatory view showing an example of a circuit on a conventional active matrix substrate. [Description of main component symbols] 1 Substrate 2 Gate signal line 3 Source signal line 4 Thin film transistor (TFT) 5 Gate electrode 6 Source electrode 7 Dip electrode 8 Decaneization part 9 Organic protective film 10 Contact hole 11 Pixel electrode 12 gate signal line 13 source signal line 14 thin film transistor (TFT) 15 gate electrode 16 source electrode 17 drain electrode 2219-9105-PF 33 200826298 18 pixel electrode 19 semiconductor layer 20 gate insulating film 101 Active matrix substrate 102 color filter, light substrate 103 sealing material 104 organic protective film 105 electrode pattern 108 input terminal 110 liquid crystal layer 111 alignment film 201 thin film transistor (TFT) 202 pixel electrode 203 gate signal line 204 source signal line 206 Counter electrode 207 Color filter layer 208 Black matrix 301 Active matrix substrate 302 Luminescent material layer 303 Upper electrode layer (cathode) 304 Sealing film 401 Scanning electrode 402 Thin film transistor (TFT) 2219-9105-PF 34 200826298 403 404 405 406 data electrode capacitor thin film transistor (TFT) organic EL element 2219-9105-PF 35

Claims (1)

200826298 X. Patent application scope: 1. A method for manufacturing an active matrix substrate, which is characterized in that:) a surface of an amorphous germanium film of a thin film transistor formed on a substrate is brought into contact with a stone burning agent, and a step of forming the surface (4); (b) a step of forming a tree (4) on the surface of the decanolated amorphous ruthenium film by the radiation-sensitive resin composition; and (c) illuminating the known resin film A step of forming a pattern in the resin film by radiation and then bringing it into contact with the developing liquid, thereby causing the latent image to appear, and patterning the resin film. 2. An active matrix substrate comprising a thin film transistor having an amorphous smectic film formed on a substrate, characterized in that: the surface of the amorphous ruthenium film is decanolated and is decanolated The amorphous ruthenium film has an organic protective film on its surface. 3. The active matrix substrate according to the second aspect of the invention, wherein the stone-burning system is trimethylsulfonated. 4. The active matrix substrate according to the second or third aspect of the invention, wherein the organic protective film is a film formed of a crosslinked polar alicyclic olefin polymer. 5. The method of producing an active matrix substrate according to claim 1, wherein the decylating agent is hexamethyldioxane. The method for producing an active matrix substrate according to claim 1 or 5, wherein the radiation sensitive resin composition contains an alicyclic olefin polymer having a polarity of 2219-9105-PF 36 200826298, A crosslinker, a radiation sensitive compound, and a solvent. A planar display device, comprising: the active matrix substrate according to any one of claims 2 to 4. 2219-9105-PF 37