Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
  • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
  • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
  • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
  • H01L27/1259—Multistep manufacturing methods
  • H01L27/1288—Multistep manufacturing methods employing particular masking sequences or specially adapted masks, e.g. half-tone mask
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
  • G03F7/422—Stripping or agents therefor using liquids only
  • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
  • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
  • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
  • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
  • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
  • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
  • H01L29/66007—Multistep manufacturing processes
  • H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
  • H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
  • H01L29/66409—Unipolar field-effect transistors
  • H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
  • H01L29/66742—Thin film unipolar transistors
  • H01L29/6675—Amorphous silicon or polysilicon transistors
  • H01L29/66765—Lateral single gate single channel transistors with inverted structure, i.e. the channel layer is formed after the gate

Definitions

• Stripping composition manufacturing method of TFT substrate, and recycling method of stripping composition
• the present invention relates to a stripping composition, a method for producing a TFT substrate, and a recycling method for the stripping composition.
• LCD liquid crystal display device
• PDP plasma display panel device
• organic EL display devices are widely used for reasons such as display performance and energy saving.
• display devices such as mobile phones, personal digital assistants (PDAs), laptop computers, laptop computers, and televisions have become the mainstream.
• PDAs personal digital assistants
• laptop computers laptop computers
• televisions have become the mainstream.
• TFT substrate is generally used.
• a display material such as liquid crystal is filled between a TFT substrate and a counter substrate.
• the liquid crystal display device selectively applies a voltage to the display material for each pixel.
• the TFT substrate refers to a substrate on which a thin TFT (thin film transistor) having a force such as a semiconductor thin film (also referred to as a semiconductor film) is disposed.
• a TFT substrate is also called a “TFT array substrate” because TFTs are arranged in an array.
• a TFT substrate used in a liquid crystal display device or the like has a set of TFT and one pixel of a screen of the liquid crystal display device (referred to as one unit) arranged vertically and horizontally on a glass substrate. .
• gate wirings are arranged at regular intervals in the vertical direction on a glass substrate, and source wirings or drain wirings are arranged at regular intervals in the horizontal direction.
• the gate electrode, the source electrode, and the drain electrode force are provided in each of the units constituting each pixel.
• Patent Document 1 describes a manufacturing method of a thin film transistor substrate and a stripping composition technique.
• the stripping composition is reused by heating and dissolving the conductive film present in the stripping composition in the storage tank during storage.
• a thiol compound such as thiobenzoic acid or thiolic acid is mixed in the stripping composition to dissolve the conductive film.
• the stripping composition containing the thiol compound dissolves the conductive film together with the resist. For this reason, the first time ⁇ the second time between the first time required to peel off the unnecessary conductive film from the substrate and the second time when the required pixel electrode is completely dissolved. Is necessary.
• Patent Document 1 Japanese Unexamined Patent Publication No. 2006-74039
• Patent Document 1 includes a stripping composition force, a stripping additive for a conductive film, and, for example, indium oxide and zinc oxide (IZO) must also be used.
• IZO indium oxide and zinc oxide
• the conductive film is dissolved. For this reason, when stripping an unnecessary conductive film, the necessary conductive film such as a pixel electrode is dissolved in a small amount. For this reason, there was a problem of including an element that reduces the manufacturing yield.
• the conductive film also has strength such as crystallized indium oxide 'tin oxide (ITO), the rate of dissolution in the stripping composition (weak acid) is slow, and the actual production line is practically slow. There was a problem that application was difficult. In addition, it was difficult to ensure that the conductive film was completely dissolved, and there was a problem that it contained elements that lowered the manufacturing yield.
• ITO crystallized indium oxide 'tin oxide
• the thiol compound also dissolves the conductive film during the first time and damages the pixel electrode. Therefore, there is a problem that the viewpoint power for improving the manufacturing yield and reliability is not preferable.
• sulfur-containing compounds such as thioglycolic acid degrade the working environment, which often produces malodors. For this reason, the load on the surrounding environment is large, and it is very risky to use industrially.
• the present invention has been made in view of such problems, and can improve the quality and productivity, and can improve the working environment, a stripping composition, a method for manufacturing a TFT substrate, and It aims at providing the recycling method of a stripping composition.
• the stripping composition of the present invention is used in the manufacture of a semiconductor device, and dissolves the resist to strip the conductor film laminated on the resist. It is a thing.
• the stripping composition comprises 20 to 79.5% by weight of an amine compound, 20 to 79.5% by weight of an aprotic polar compound, and 0.5 to 5% by weight of a carboxylic compound. Including.
• the conductor film is hardly dissolved when the resist is dissolved as compared with the case where a thiol compound is included.
• a carboxylic compound is included.
• the amine compound power monoethanolamine, monoisopropanolamine, methylmethanolamine, ethylethanolamine, dimethanolamine, aminoethoxyethanolamine, diethanolamine, and these It is good to include at least one selected compound as well as the group power.
• the aprotic polar compound power N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylimidazole, dimethyl sulfoxide, and the combination power thereof Group power Contains at least one selected compound.
• the stripping composition of the present invention is used in the manufacture of a semiconductor device, dissolves the resist, and peels off the conductor film laminated on the resist. Stripping composition.
• the stripping composition contains an ethylene strength carbonate and 0.5 to 5% by weight of a carboxylic compound.
• ethylene carbonate may be used in place of the amine compound and the aprotic polar compound. In this way, the manufacturing yield and reliability can be improved, and the working environment can be improved.
• the stripping composition of the present invention is used for manufacturing a semiconductor device, dissolves a resist, and peels off a conductor film laminated on the resist. Stripping composition.
• the stripping composition contains an alkoxy acrylamide compound and 0.5 to 5% by weight of a carboxylic compound.
• an alkoxyacrylamide compound may be used in place of the amine compound and the aprotic polar compound. In this way, the manufacturing yield and reliability can be improved, and the working environment can be improved.
• the alkoxyacrylamide compound may include at least one compound selected from the compound represented by the following general formula 1 and a group force that combines these compounds.
• R 1 O—CH 2 CH 2 —C—NR 2 R 3 (—general formula 1)
• R 1, R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms.
• the carboxylic compound power may include at least one compound selected from the carboxylic acids represented by the following general formulas 2 and 3 and the group power that can be combined.
• R is an alkyl group having 1 to 10 carbon atoms or an aryl group.
• R is an alkyl group having 1 to 10 carbon atoms or an aryl group.
• the pKa (acid dissociation constant) of the carboxylic compound is 4.0 or more and 5.2 or less. Yes.
• a manufacturing method of a TFT substrate of the present invention includes a step of forming a thin film transistor on a substrate, a step of laminating a protective insulating film on the substrate and the thin film transistor, A step of laminating a resist on the protective insulating film; a step of forming the resist in a predetermined shape; and forming an undercut portion at a lower peripheral edge of the resist; and a conductive material on the protective insulating film and the resist And a step of forming a pixel electrode and a conductive film on the resist separated from each other by the undercut portion, and on the substrate, according to any one of claims 1 to 8.
• the manufacturing process can be reduced and productivity can be improved.
• the conductive film is hardly dissolved when the resist is dissolved, as compared with the case of including a thiol compound, so that the necessary conductive film such as a pixel electrode is damaged. There is nothing. As a result, the manufacturing yield and reliability can be improved. In addition, the working environment can be improved without ever stinking.
• the used stripping composition containing the conductive film on the resist peeled off from the substrate cover is collected. Furthermore, it is preferable to have a recycling step of dissolving the conductive film on the resist in the used stripping composition and reusing the used stripping composition.
• the temperature of the stripping composition supplied to the substrate is 30 ° C or more and less than 60 ° C
• the temperature of the collected used stripping composition is 60 ° C or more and less than 100 ° C. Let's do it. In this way, the manufacturing yield and reliability can be improved, and the used stripping composition can be reused efficiently.
• the conductive film force on the pixel electrode and the resist indium oxide zinc oxide (IZO), indium oxide 'tin oxide' zinc oxide (ITZO), tin oxide 'zinc oxide (ZTO), and
• the TFT substrate manufacturing method of the present invention includes a step of forming a thin film transistor on a substrate, a step of laminating a protective insulating film on the substrate and the thin film transistor, A step of laminating a resist on the protective insulating film; a step of forming the resist in a predetermined shape; and forming an undercut portion at a lower peripheral edge of the resist; and a conductive material on the protective insulating film and the resist And forming a pixel electrode and a conductive film on the resist separated from each other by the undercut portion, and supplying a stripping composition on the substrate to conduct the conductive on the resist.
• the number of masks can be reduced.
• productivity can be improved.
• the used stripping composition force can be almost completely separated from the conductive film on the resist peeled from the substrate. This allows the spent stripping composition to be reused without reducing yield.
• the TFT substrate manufacturing method of the present invention includes a step of forming a thin film transistor on the substrate, and a step of stacking a protective insulating film on the substrate and the thin film transistor. Laminating a resist on the protective insulating film;
• a patterned pixel electrode and a conductive film on the resist A stripping step of supplying a stripping composition onto the substrate and stripping off the substrate film of the conductive film on the resist, wherein the stripping composition force 20 It is a method comprising -80% by weight of an amin compound and 20-80% by weight of an aprotic polar compound.
• Such rubbing dissolves only the resist and does not damage the pixel electrode. As a result, yield and reliability can be improved.
• the stripping composition should be added with a solvent that suppresses foaming during the supply and a diluent for reducing the viscosity within a range that does not adversely affect the performance of the stripping composition.
• the amine compound power monoethanolamine, monoisopropanolamine, methylmethanolamine, ethylethanolamine, dimethanolamine, aminoethoxyethanolamine, diethanolamine, and these It is good to include at least one selected compound as well as the group power.
• the aprotic polar compound power N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylimidazole, dimethyl sulfoxide, and a combination power thereof
• Group power Contains at least one selected compound.
• the TFT substrate manufacturing method of the present invention includes a step of forming a thin film transistor on the substrate, and a step of stacking a protective insulating film on the substrate and the thin film transistor. Laminating a resist on the protective insulating film;
• TFT substrate having a step of forming a patterned pixel electrode and a conductive film on the resist, and a stripping step of supplying a stripping composition onto the substrate and peeling the conductive film on the resist to the substrate force
• the stripping composition comprises an alkoxyacrylamide compound represented by the following general formula 1.
• R 1 O—CH 2 CH 2 —C—NR 2 R 3 (—general formula 1)
• R 1, R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms. Such rubbing dissolves only the resist and does not damage the pixel electrode. As a result, yield and reliability can be improved. Further, the alkoxyacrylamide compound has water solubility, and can provide a safe stripping composition that is not flammable.
• the TFT substrate manufacturing method of the present invention includes a step of forming a thin film transistor on the substrate, and a step of stacking a protective insulating film on the substrate and the thin film transistor. Laminating a resist on the protective insulating film;
• TFT substrate having a step of forming a patterned pixel electrode and a conductive film on the resist, and a stripping step of supplying a stripping composition onto the substrate and peeling the conductive film on the resist to the substrate force
• the stripping composition strength is a method including ethylene carbonate.
• Such rubbing dissolves only the resist and does not damage the pixel electrode. As a result, yield and reliability can be improved.
• the conductive film on the resist is separated from the used stripping composition containing the conductive film on the resist peeled off from the substrate, and the used stripping composition is separated. It is good to have a recycling process that reuses.
• the conductor film on the resist is separated from the used stripping composition by sedimentation-type separation, centrifugal separation, and Z or filtration-type separation. In this way, the conductor film on the resist can be separated easily and reliably.
• the conductor film is made of indium oxide / zinc oxide (IZO), indium oxide 'tin oxide (ITO), amorphous indium oxide' tin oxide (a-ITO), titanium oxide 'oxidized. Niobium, tin oxide 'zinc oxide, tin oxide' antimony oxide, fluorine-doped oxide oxide, and the combined force of these may contain at least one selected material.
• the stripping composition may be supplied onto the substrate by the stripping composition force spray method during the stripping step.
• the stripping yarn and the composition can easily enter the undercut portion, so that the conductive film on the resist can also be effectively peeled off.
• productivity can be improved.
• the lower layer portion of the resist is more soluble in the developer than the upper layer portion of the resist.
• the recycling method of the stripping composition of the present invention includes a step of forming a thin film transistor on a substrate, and a step of laminating a protective insulating film on the substrate and the thin film transistor.
• Evaporate A step of forming a pixel electrode and a conductive film on the resist separated into a ridge, and supplying the stripping composition according to any one of claims 1 to 8 on the substrate; A stripping process for peeling the conductive film on the resist from the substrate, and a used stripping composition including the conductive film on the resist peeled from the substrate is collected, and the conductive film on the resist is recovered. Membrane the used strip And a recycling step of reusing the used stripping composition.
• a method for recycling the stripping composition of the present invention includes a step of forming a thin film transistor on a substrate, a step of laminating a protective insulating film on the substrate and the thin film transistor, A step of laminating a resist on the protective insulating film; a step of forming the resist in a predetermined shape; and forming an undercut portion at a lower peripheral edge of the resist; and a conductive layer on the protective insulating film and the resist.
• FIG. 1 shows a structural formula for explaining examples of amine compounds contained in a stripping composition in a stripping yarn and composition that is useful in the first embodiment of the present invention. Yes.
• FIG. 2 shows a structural formula for explaining an example of an amine-based compound contained in the stripping composition in the stripping composition according to the first embodiment of the present invention.
• FIG. 3 shows a structural formula for explaining examples of aprotic polar compounds contained in the stripping composition in the stripping composition useful for the first embodiment of the present invention. is doing.
• FIG. 4 is a schematic flowchart for explaining a method for manufacturing a TFT substrate according to the first embodiment of the present invention.
• FIG. 5 is a schematic view for explaining a method of manufacturing a TFT substrate according to the first embodiment of the present invention.
• FIG. 5 (a) shows a gate wiring and a gate electrode formed, and a gate A plan view in which insulating films are stacked is shown, and (b) shows an AA enlarged sectional view.
• FIG. 6 is a schematic view for explaining a method of manufacturing a TFT substrate according to the first embodiment of the present invention.
• FIG. 6 (a) shows a thin film transistor formed and a protective insulating film. A laminated plan view is shown, and (b) shows an enlarged cross-sectional view of BB.
• FIG. 7 is a schematic view for explaining a manufacturing method of a TFT substrate according to the first embodiment of the present invention.
• (A) shows a case where a resist on a protective insulating film is a predetermined one.
• a plan view formed in a shape is shown, and
• (b) shows an enlarged CC cross-sectional view.
• FIG. 8 is a schematic view for explaining a method of manufacturing a TFT substrate according to the first embodiment of the present invention.
• A is an enlarged cross-sectional view in which contact holes are formed.
• B is an enlarged cross-sectional view in which the resist is re-formed and an undercut portion is formed, and
• c is a detailed view of the D portion.
• FIG. 9 shows a schematic view with a conductor film formed for explaining a method of manufacturing a TFT substrate according to the first embodiment of the present invention, and (a) is an enlarged cross-sectional view.
• Figure (b) shows a detailed view of part E.
• FIG. 10 shows a stripping process for stripping the conductive film on the resist and a used stripping composition in the TFT substrate manufacturing method according to the first embodiment of the present invention.
• the schematic sectional drawing for demonstrating the recycling process to reuse is shown.
• FIG. 11 is a schematic view for explaining a method for manufacturing a TFT substrate according to the first embodiment of the present invention.
• FIG. 11 (a) is a plan view in which pixel electrodes are formed.
• (B) shows an enlarged FF sectional view.
• FIG. 12 shows a photograph of the conductor film on the resist that remains undissolved in the stripping compositions of Examples 1 to 3.
• FIG. 13 is a schematic flowchart for explaining a method of manufacturing a TFT substrate according to the second embodiment of the present invention.
• FIG. 14 is a schematic view for explaining a method of manufacturing a TFT substrate according to the second embodiment of the present invention.
• (A) shows a gate wiring and a gate electrode formed.
• a plan view in which a gate insulating film is stacked is shown, and
• (b) shows an enlarged cross-sectional view.
• FIG. 15 is a schematic view for explaining a method of manufacturing a TFT substrate according to the second embodiment of the present invention.
• A shows a protective insulating film in which a thin film transistor is formed.
• B shows an enlarged cross-sectional view.
• FIG. 16 is a schematic view for explaining a method of manufacturing a TFT substrate according to the second embodiment of the present invention.
• A shows a case where a resist on a protective insulating film is predetermined.
• B is an enlarged cross-sectional view.
• FIG. 17 is a schematic view for explaining a method of manufacturing a TFT substrate according to the second embodiment of the present invention.
• A is an enlarged sectional view in which contact holes are formed.
• B is an enlarged cross-sectional view in which the resist is re-formed and an undercut portion is formed, and
• c is a detailed view of the ⁇ portion.
• FIG. 18 shows a schematic view in which a conductor film is formed for explaining a method of manufacturing a TFT substrate according to the second embodiment of the present invention, and (a) is an enlarged view. A cross-sectional view is shown, and (b) is a detailed view of the part.
• FIG. 19 shows a stripping process for stripping a conductive film on a resist and a used stripping composition in a TFT substrate manufacturing method according to the second embodiment of the present invention.
• the schematic sectional drawing for demonstrating the recycling process to reuse is shown.
• FIG. 20 shows a structural formula for explaining an example of an amine compound contained in the stripping composition in the TFT substrate manufacturing method according to the second embodiment of the present invention.
• FIG. 21 shows a structural formula for explaining an example of an amine compound contained in the stripping composition in the TFT substrate manufacturing method according to the second embodiment of the present invention.
• FIG. 22 is a structural formula for explaining an example of an aprotic polar compound contained in a stripping composition in the TFT substrate manufacturing method according to the second embodiment of the present invention. Is shown.
• FIG. 23 is a schematic view for explaining a method for manufacturing a TFT substrate according to the second embodiment of the present invention.
• FIG. 23 (a) is a plan view in which pixel electrodes are formed.
• (B) shows an enlarged cross-sectional view of F ′.
• FIG. 24 shows a photograph of the conductor film on the resist that remained undissolved in the stripping composition of Example 4.
• the stripping composition of the present invention is a stripping composition used for manufacturing a semiconductor device.
• This stripping yarn composition is used for a resist in which an undercut portion described later is formed and a conductor film laminated on the resist. Further, this stripping composition dissolves the resist to peel off unnecessary conductor films from the substrate. In this manner, the unnecessary conductor film is also peeled off from the substrate force, whereby a necessary conductor film having a predetermined shape (for example, a pixel electrode in the TFT substrate) is formed on the substrate.
• the semiconductor device means a device including a substrate such as a wafer or a glass plate, an electric element using a semiconductor such as a transistor or a light receiving element, and a Z or optical element.
• the stripping composition of the present embodiment comprises 20 to 79.5% by weight of an amin compound, 20 to 79.5% by weight of an aprotic polar compound, and 0.5 to 5% by weight of carvone. System compounds.
• the amine compound and the aprotic polar compound function as a resist stripping agent for dissolving the resist. Further, the carboxylic compound functions as a dissolving additive for the conductor film for dissolving the conductor film.
• Examples of amine compounds include monoethanolamine, monoisopropanolamine, methylmethanolamine, ethylethanolamine, dimethanolamine, aminoethoxyethanolamine, diethanolamine, and the like. (See Figures 1 and 2). Each of the above amine compounds may be used alone or in combination of two or more.
• aprotic polar compounds examples include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylimidazole, dimethyl Examples thereof include sulfoxide (see FIG. 3). Further, the aprotic polar compound may be used alone or in combination of two or more.
• the resist stripping agent contains about 20 to 79.5% by weight of an amine-based compound, and about 20 to 79.5% by weight of an aprotic polar compound. %.
• the [0039] stripping composition approximately the amine compound 20 to 79.5 reasons to include weight 0/0, the content of ⁇ amine-based compound is less than about 20 wt%, within a short time to resist This is because it cannot be dissolved sufficiently. Also, if the content of the amine compound exceeds about 79.5% by weight, the required conductor film is rapidly corroded while the resist is dissolved, causing damage. Also, if the amine compound exceeds about 79.5% by weight, the volatilization amount of the stripping composition increases, and there is a concern that the component ratio of the stripping composition may change. Therefore, in the stripping composition of the present invention, the content of the amine compound is preferably about 20 to 79.5% by weight, more preferably 30 to 70% by weight.
• the stripping composition contains about 20 to 79.5% by weight of the aprotic polar compound is that the content of the aprotic polar compound is less than about 20% by weight. If so, the resist stripping time may increase, or the liquid life when reused may be shortened. In addition, if the content of the aprotic polar compound exceeds about 79.5% by weight, there is a concern that the required conductor film may be corroded when stripping the resist. Accordingly, the content of the aprotic polar compound in the stripping composition of the present invention is preferably about 20 to 79.5% by weight, more preferably about 30 to 70% by weight. In addition, the stripping composition should be added with a solvent that suppresses foaming during supply and a diluent for reducing the viscosity within a range that does not adversely affect the performance of the stripping composition.
• the carboxylic compound may include at least one compound selected from the group consisting of carboxylic acids represented by the following general formulas 2 and 3 and combinations thereof.
• R-COOH (General formula 2)
• R is an alkyl group having 1 to 10 carbon atoms or an aryl group.
• R is an alkyl group having 1 to 10 carbon atoms or an aryl group.
• each said carboxylic acid individually or in combination of 2 or more.
• the stripping composition contains about 0.5 to 5% by weight of a carboxylic compound. In this way, in the stripping step, only the resist is dissolved, the necessary conductor film is not dissolved, and the conductor film is not damaged. As a result, yield and reliability can be improved. Further, in the recycling process, the conductive film is dissolved in the used stripping composition, and the used stripping composition can be reused.
• the used stripping composition refers to a stripping composition containing a conductive film on a resist peeled from a substrate.
• the reason why the stripping composition contains about 0.5 to 5% by weight of the carboxylic compound is that the content of the carboxylic compound is less than about 0.5% by weight in the recycling process. This is because the time required for dissolving the conductor film in the stripping composition may increase, and the liquid life when reused may be shortened. Also, if the content of the carboxylic compound exceeds about 5% by weight, there is a concern that the required conductor film may be corroded when stripping the resist. Therefore, the content of the carboxylic compound in the stripping composition of the present invention is preferably about 0.5 to 5% by weight, more preferably about 2 to 4% by weight.
• the pKa (acid dissociation constant) of the carboxylic compound is 4.0 or more and 5.2 or less.
• the necessary conductor film is not damaged in the stripping step.
• the used stripping composition can be dissolved efficiently.
• the carboxylic acid shows a larger value than thioglycolic acid, and the carboxylic acid is weaker than thioglycolic acid.
• the reason why the pKa is about 4.0 or more and about 5.2 or less is that if the pKa is less than 4.0, there is a high possibility that the necessary conductor film is dissolved and the quality is adversely affected. It is the power to become. Further, if p Ka exceeds 5.2, the time required for dissolving the peeled unnecessary conductor film becomes long, and the efficiency is lowered.
• the stripping composition that is effective in the present embodiment includes a carboxylic compound, and therefore, when the resist is dissolved, compared with the case where the thiol compound of the conventional example is included, the conductor film is almost completely removed. Since it is not dissolved, the necessary conductor film such as the pixel electrode is not damaged. As a result, manufacturing yield and reliability can be improved. Moreover, it is possible to improve the working environment where a bad smell is emitted.
• the stripping composition of this embodiment is configured to include ethylene carbonate and 0.5 to 5% by weight of a carboxylic compound. That is, as compared with the first embodiment, the difference is that ethylene carbonate is contained instead of the amine compound and the aprotic polar compound.
• the stripping composition of the present embodiment has substantially the same effect as the stripping composition of the first embodiment, and can improve the production yield and reliability.
• the stripping composition of this embodiment is configured to include an alkoxyacrylamide compound and 0.5 to 5% by weight of a carboxylic compound. That is, the first embodiment described above The difference is that, instead of the amine-based compound and the aprotic polar compound, an alkoxyatyramide compound is included instead of the amine-based compound and the aprotic polar compound.
• the alkoxyacrylamide compound may include a compound represented by the following general formula 1 and at least one compound selected as a group force that also has a combination force thereof.
• R 1 O—CH 2 CH 2 —C—NR 2 R 3 (General Formula 1)
• R 1, R 2, and R 3 are each independently an alkyl group having 1 to 10 carbon atoms.
• examples of the alkoxyacrylamide compound include N, N-dimethyl-n-butoxyacrylamide, N, N-jetyl-n-butoxyacrylamide, and the like. Moreover, you may use each said alkoxyacrylamide compound individually or in combination of 2 or more.
• the stripping composition of the present embodiment has substantially the same effect as the stripping composition of the first embodiment, and can improve the manufacturing yield and reliability.
• the alkoxyacrylamide compound has water solubility, and the stripping composition of this embodiment can be used as an aqueous solution.
• the water content is less than about 50% by weight, preferably about 10-40% by weight, more preferably about 20-30% by weight. By doing so, the stripping composition of the present embodiment is not flammable, so safety is improved.
• FIG. 4 is a schematic flowchart for explaining a manufacturing method of a TFT substrate according to the first embodiment of the present invention.
• a thin film transistor 1050 is formed on a substrate 1010 (step S 1001).
• FIG. 5 is a schematic diagram for explaining a method of manufacturing a TFT substrate according to the first embodiment of the present invention.
• FIG. 5A shows a gate insulating film formed with a gate wiring and a gate electrode.
• (B) shows an A-A enlarged cross-sectional view.
• a glass substrate 1010 is prepared, and a gate wiring 1021 and a gate electrode 1022 made of a conductive thin film such as Al (aluminum) are formed by a photolithography method. Subsequently, a gate insulating film 1023 is stacked over the exposed glass substrate 1010, the gate wiring 1021, and the gate electrode 1022.
• a gate insulating film 1023 is stacked over the exposed glass substrate 1010, the gate wiring 1021, and the gate electrode 1022.
• a first mask is used to form the gate wiring 1021 and the gate electrode 1022.
• FIG. 6 is a schematic view for explaining a method for manufacturing a TFT substrate according to the first embodiment of the present invention.
• FIG. 6A shows a thin film transistor formed and a protective insulating film laminated.
• (B) shows an enlarged cross-sectional view of BB.
• a source wiring 1031, a source electrode 1032, a channel portion 1051, and a drain electrode 1042 are formed over the gate insulating film 1023.
• the thin film transistor 1050 is formed on the glass substrate 1010 (step S1001).
• a protective insulating film 1054 is stacked over the glass substrate 1010 and the thin film transistor 1050 (step S 1002).
• a half-tone exposure technique (and a second half-tone mask (not shown)) is used when forming the source wiring 1031, the source electrode 1032, the channel portion 1051, and the drain electrode 1042.
• a half-tone exposure technique (and a second half-tone mask (not shown)) is used when forming the source wiring 1031, the source electrode 1032, the channel portion 1051, and the drain electrode 1042.
• an amorphous silicon thin film 1052, an n-type amorphous silicon thin film 1053, a conductor thin film 1033 such as molybdenum Z aluminum Z molybdenum thin film, and a resist (not shown) are sequentially formed on the gate insulating film 1023. Stack up.
• a resist is formed using a halftone exposure technique, and a source wiring 1031 is formed by first etching.
• portions to be the source electrode 1032, the channel portion 1051, and the drain electrode 1042 are formed. Subsequently, the resist is re-formed, and the conductive thin film 1033 and the n-type amorphous silicon thin film 1053 above the channel portion 1051 are etched by the second selective etching, so that the channel portion 1051, the source electrode 1032, and the drain electrode are etched. 1042 is formed. Next, source wiring 1031, thin film transistor A protective insulating film 1054 is stacked on the register 1050 and the gate insulating film 1023 (step S 1002).
• a resist 1055 is laminated on the protective insulating film 1054 (step S1003). Subsequently, using a halftone exposure technique (and a third halftone mask (not shown)), the laminated resist 1055 is formed into a predetermined shape and etched. Further, the resist 1055 is re-formed, and an undercut portion 1554 is formed at the lower peripheral edge of the re-formed resist (re-formed resist 1553) (step S 1004).
• FIG. 7 is a schematic diagram for explaining a method for manufacturing a TFT substrate, which is useful for the first embodiment of the present invention.
• FIG. 7 (a) shows that the resist on the protective insulating film has a predetermined shape. The formed plan view is shown, and (b) shows the CC enlarged cross-sectional view.
• a resist 1055 is stacked on the protective insulating film 1054 (step S1003).
• a resist 1055 is formed into a predetermined shape by a halftone exposure technique. That is, in the resist 1055, an opening 1056 for forming the contact hole 1 541 is formed above the drain electrode 1042. Furthermore, a thin halftone exposure resist 1552 is formed on the portion where the pixel electrode 1612 is formed (see FIG. 11), and a thick full exposure resist is formed on the portion where the pixel electrode 1612 is not formed. 1551 is formed.
• FIG. 8 shows a schematic diagram for explaining a method of manufacturing a TFT substrate according to the first embodiment of the present invention, and (a) shows an enlarged cross-sectional view in which contact holes are formed. (B) is an enlarged cross-sectional view in which the resist is re-formed and an undercut portion is formed, and (c) is a detailed view of the D portion.
• etching (usually dry etching) is performed on the protective insulating film 1054 using a resist 1055 formed by a halftone exposure technique. Further, a contact hole 1541 for connecting the pixel electrode 1612 and the drain electrode 1042 is formed.
• the resist 1055 is re-formed. That is, Regis G 1055 is gradually removed by oxygen plasma ashing to remove all of the halftone exposure resist 1 552.
• the all-exposure resist 1551 has a thickness for functioning as a force resist that is gradually removed from above and becomes a re-formed resist 1553 with a reduced thickness.
• the upper surface of the re-formed resist 1553 maintains a predetermined shape.
• an undercut portion 1554 is formed in the lower portion of the periphery of the predetermined shape by re-developing with a developer (step S1004).
• the re-formed resist 1553 has a two-layer structure in which an upper resist layer 155la and a lower resist layer 1551b are used.
• the upper resist 1551a and the lower resist 1551b have different solubility in the developer.
• the lower resist 1551b is set to be more easily dissolved than the upper resist 1551a. As a result, the undercut portion 1554 can be more reliably formed, and the yield can be improved.
• the components are adjusted by blending two or more resist resins.
• the photoreaction can be used to provide a difference in solubility by providing a difference in the degree of cure.
• a transparent conductive material is deposited above the glass substrate 1010 to form pixel electrodes 1612 and a conductive film 1611 on the resist that are separated from each other (step) S 1005).
• FIG. 9 shows a schematic view with a conductor film formed for explaining a manufacturing method of a TFT substrate according to the first embodiment of the present invention, and (a) is an enlarged sectional view. (B) shows a detailed view of part E.
• a transparent conductive material is vapor-deposited above the glass substrate 1010 to form a conductor film 1061 (pixel electrode 1612 separated from each other and conductor film 1611 on the resist) (step S1005).
• a conductor film 1611 on the resist is formed on the re-formed resist 1553.
• the pixel An electrode 1612 is formed on the exposed drain electrode 1042 and the protective insulating film 1054.
• the pixel electrode 1612 is separated from the conductive film 1611 on the resist by an undercut portion 1554 and is not electrically connected.
• the pixel electrode 1612 is electrically connected to the drain electrode 1042 through a contact hole 1541.
• the conductive material usually a group consisting of indium oxide / zinc oxide (IZO), indium oxide / tin oxide 'zinc oxide (ITZO), zinc oxide' tin oxide (ZTO), and combinations thereof.
• IZO indium oxide / zinc oxide
• ITZO indium oxide / tin oxide 'zinc oxide
• ZTO zinc oxide' tin oxide
• the thing containing is used. In this way, when the stripping composition is heated during the recycling process, the carboxylic compound can easily dissolve the conductor film. Thereby, productivity can be improved.
• the conductive materials are preferably those described above, but are not limited thereto.
• the stripping composition in the stripping process, the stripping composition is hardly dissolved by the stripping composition, and the stripping composition is used in the recycling process. It only needs to be dissolved in the product.
• ITO Indium oxide 'tin oxide
• amorphous indium oxide' tin oxide a—
• These conductive films selected from the group consisting of (ITO), titanium oxide 'niobium oxide, tin oxide' dumbbell oxide, tin oxide 'antimony oxide, fluorine-doped tin oxide, and combinations thereof are used in the present invention. It does not dissolve at all in such stripping compositions.
• a stripping composition is supplied to the glass substrate 1010, and the conductive film 1611 on the resist is peeled from the glass substrate 1010 (step S1006). Subsequently, the conductive film 1611 on the resist is dissolved in the used stripping composition and reused (step S 1007).
• the conductive film 1611 on the resist is peeled from the glass substrate 1010, and the conductive film 1611 on the resist is dissolved in the used stripping composition, and then the used stripping yarn and the composition are re-used.
• a method to be used will be described with reference to the drawings.
• FIG. 10 shows a stripping process for stripping a conductor film on a resist and reuses a used stripping composition in the TFT substrate manufacturing method according to the first embodiment of the present invention.
• the schematic sectional drawing for demonstrating a recycling process is shown.
• the glass substrate 1010 on which the conductor film 1061 is laminated has a re-resisting resist 1553 dissolved by a stripping device 1007 as a stripping process.
• the upper conductive film 1611 is peeled off (step S 1006).
• the stripping apparatus 1007 stores a stripping liquid 1070 containing a stripping composition, and a storage tank 1071a, 1071b, and a glass substrate 1010 spraying the stripping liquid 1070 in a spray form, spray 1072, pump 1073, suction
• the pipe 1074, the recovery tank 1075 for recovering the sprayed stripping liquid 1070, and the recovery pipe 1076 are in force.
• One end of the recovery pipe 1076 is connected to the recovery tank 1075, and the other end is connected to the storage tanks 1071a and 1071b via two branch pipes provided with electromagnetic valves 1761 and 1762, respectively. Yes.
• the stripping solution 1070 in the collection tank 1075 flows down to the storage tank 1071b.
• one end of the suction pipe 74 is connected to the pump 73, and the other end is connected to the storage tanks 1071a and 1071b via two branch pipes provided with electromagnetic valves 1711 and 1712, respectively. Therefore, for example, when the electromagnetic valve 1712 is closed and the electromagnetic valve 1711 is opened, the stripping solution 1070 in the storage tank 1071a is sucked into the pump 1073.
• the stripping apparatus 1007 uses any one of the stripping compositions of the above-described embodiments as the stripping composition. As a result, when the re-formed resist 1553 is dissolved, the pixel electrode 1612 is hardly dissolved, so that the pixel electrode 1612 is not damaged. Thereby, the manufacturing yield and reliability can be improved. Moreover, it is possible to improve the working environment where a bad smell is emitted.
• a low temperature (usually less than about 50 ° C) stripping solution 1070 is stored in the storage tank 1071a. Further, the electromagnetic valve 1711 is open, the electromagnetic valve 1761 is closed, the electromagnetic valve 1762 is open, and the electromagnetic valve 1712 is closed.
• the conductor film 1611 on the resist is completely dissolved in the stripping composition.
• the peeling liquid 1070 force in the storage tank 1071a is sucked into the pump 1073 via the electromagnetic valve 1711 and the suction pipe 1074, and is sprayed from the spray nozzle 1072 onto the glass substrate 1010.
• the stripping solution 1070 is removed from the spray nozzle 1072. It is injected in a play shape. As a result, the stripping solution 1070 enters the undercut portion 155 4 through a minute gap. As a result, the conductor film 1611 on the resist can be effectively peeled off from the glass substrate 1010 (step S1006).
• the stripping solution 1070 sprayed on the glass substrate 1010 has a problem in that the necessary pixel electrode 1612 is dissolved because the carboxylic compound of the stripping composition is a weak acid and the temperature is low. To prevent.
• FIG. 10 shows a state during stripping, and the re-formed resist 1553 and the conductor film 1611 on the resist partially remain.
• the stripping composition can dissolve the re-formed resist 1553 and separate all the conductor film 1611 on the resist formed on the upper surface of the re-formed resist 1553 from the glass substrate 1010. it can.
• the stripping composition does not dissolve the conductor film 1061. Therefore, the optimum stripping conditions (spray pressure, spraying time, etc.) can be selected. Generally, when using the stripping composition of this embodiment, the spraying time is about 0.5-5 minutes, preferably about 1-3 minutes. Further, it is preferable that the re-forming resist 1553 is dissolved in a temperature range of about 30 ° C. to less than 60 ° C. The temperature force of the stripping composition is preferably about 40 ° C. to 50 ° C. .
• the reason for setting the temperature of the stripping composition in the stripping step to about 30 ° C or more and less than 60 ° C is that when the temperature is lower than about 30 ° C, the time for dissolving the re-formed resist 1553 becomes longer. This is because production efficiency decreases. Further, when the temperature is higher than about 60 ° C., the dissolution rate of the carboxylic compound is increased, so that there is a concern that the pixel electrode 1612 is dissolved and the manufacturing yield is lowered.
• the stripping solution 1070 sprayed onto the glass substrate 1010 dissolves the reshaped resist 1553 of the glass substrate 1010, and includes the conductor film 1611 on the stripped resist, Then, it flows down to the storage tank 171b through the recovery pipe 1076 and the electromagnetic valve 1762. At this time, the conductor film 1611 on the stripped resist is mixed in the stripping solution 1070 as microscopic pieces such as particles and strings. Then, a stripping solution 1070 (referred to as a used stripping composition as appropriate) containing the conductor film 1611 on the resist is stored in the storage tank 10. When flowing into 71b, the conductive film 1611 on the resist settles in the storage tank 1071b, and the dissolution of the conductive film 1611 on the carboxylic compound force resist starts.
• the temperature of the stripping solution 1070 is increased by providing temperature control means and stirring means (not shown) in the storage tank 1071b. That is, the dissolution of the conductive film 16 11 on the resist is preferably performed in a temperature range of about 60 ° C. or more and less than 100 ° C. C or less is preferable. Generally, when the stripping composition of the above embodiment is used, the time required for dissolving the conductor film 1611 on the resist is about 10 to 30 minutes.
• the reason for setting the temperature of the stripping composition in the recycling process to be about 60 ° C or higher and lower than 100 ° C is that when the temperature is lower than about 60 ° C, the carboxylic compound is a weak acid. This is because the conductive film 1611 cannot be dissolved. In addition, when the temperature is higher than about 100 ° C, the components in the stripping composition may evaporate, and the composition may change.
• the conductor film 1611 on the resist can be dissolved in a shorter time.
• the temperature force of the stripping composition is about 70 ° C or higher, the activity of the acid in the carboxylic compound is improved and the behavior is almost equal to that of the strong acid. As a result, the conductor film 1611 on the resist is easily dissolved.
• the conductive film 1611 on the resist is completely dissolved in the storage tank 1071b, and the conductive film 1611 on the resist.
• the stripping solution 1070 that does not contain is stored in the storage tank 1071b.
• the regenerated stripping solution 1070 is sucked from the suction pipe 1074 by the pump 1073 after the electromagnetic valve 1071 is closed, the electromagnetic valve 1761 is opened, the electromagnetic valve 1762 is closed, and the electromagnetic valve 1762 is opened.
• the glass substrate 1010 is sprayed from 1072. That is, the conductive film 1611 on the resist is dissolved from the used stripping composition and reused (step S 1007).
• FIG. 11 is a schematic diagram for explaining a method for manufacturing a TFT substrate according to the first embodiment of the present invention, and (a) is a plan view in which pixel electrodes are formed. , (B) is F— F An enlarged sectional view is shown.
• the manufacturing method of the TFT substrate 1001 of the present embodiment uses three masks: a first mask, a second halftone mask, and a third halftone mask. As a result, the manufacturing method of the TFT substrate 1001 of the present embodiment is excellent in productivity because the manufacturing process is reduced.
• the number of masks can be reduced. As a result, manufacturing steps can be reduced and productivity can be improved.
• the conductor film 1061 is hardly dissolved when the resist is dissolved as compared with the case where the thiol compound is included. As a result, the manufacturing yield and reliability without damaging the pixel electrode 1612 can be improved. Moreover, it is possible to improve the working environment where a bad smell is emitted. Furthermore, quality and productivity can be improved by reliably and efficiently recycling the used stripping composition used in the stripping process.
• Example 1 Example 1
• the stripping composition useful for the first embodiment the stripping solutions a, b, c, d, e shown in Table 1 are prepared.
• a square glass substrate of about 100 mm ⁇ 100 mm ⁇ 0.7 mm was prepared, washed with a pure water shower, and then a resist was applied and formed with a spin coater.
• the resist used was a negative resist ZTN2464-27 manufactured by ZEON. Subsequently, after heating in an oven at about 80 ° C. for about 15 minutes, exposure was performed at an exposure intensity of 300 mjZcm 2 .
• a mask to be used a stripe mask in which about 20 ⁇ m lines and about 90 ⁇ m spaces were arranged in order was used.
• a thin film having a thickness of about lOOnm was formed by sputtering.
• the glass substrate obtained above is immersed in the stripping solution for 2 minutes to strip the resist and clean with pure water. After air blowing, it was dried with a dryer. As a result, a glass substrate having a thin film (width of about m) having an IZO force and a space of about 20 m was obtained.
• the contents of the used stripping solutions a, b, c, d, e were observed with an optical microscope, it was confirmed that there was a stripped coiled soot film with a width of about 20 ⁇ m (see Fig. 12). ).
• stripping solutions f and g shown in Table 2 were prepared as stripping compositions that are effective in the second embodiment.
• Example 2 After heating the stripping solutions f and g to about 40 ° C., the same glass substrate as in Example 1 was immersed in the stripping solution for 2 minutes to perform resist stripping, After washing and air blowing, it was dried with a dryer. As a result, a glass substrate having a thin film (width of about 90 / z m) having an IZO force and a space of about 20 ⁇ m was obtained.
• ITZO In O: SnO: ZnO
• the composition of IZO is about 60 to 95 wt% In O and about 5 to 40 wt% ZnO.
• InO is about 70 to 95 wt% and ZnO is about 5 to 30 wt%. Yes.
• composition of ITZO is about 20-90 wt% In O, about 5-40 wt% SnO, Zn
• O is preferably about 5 to 40 wt%. More preferably, InO is about 40-80 wt%, SnO
• the composition of ZTO is preferably about 50 to 90 wt% for ZnO and about 10 to 50 wt% for SnO.
• ZnO is about 55-80 wt% and SnO is about 20-45 wt%.
• the present invention is also effective as a method for recycling the stripping composition.
• the recycling method of the stripping composition that works in this embodiment is almost the same as the method for manufacturing the TFT substrate of the first embodiment described above.
• the thin film transistor 1050 is formed over the substrate 1010 (step S1001).
• a protective insulating film 1054 is stacked on the glass substrate 1010 and the thin film transistor 1050 (step S1002).
• a resist 1055 is stacked on the protective insulating film 1054 (step S 1003).
• the laminated resist 1055 is formed into a predetermined shape and etched, and further, the resist 1055 is re-formed.
• Reformed resist Reformed resist 1553
• An undercut portion 1554 is formed at the lower peripheral edge (step S1004).
• a transparent conductive material is deposited on the glass substrate 1010 to form pixel electrodes 1612 and a conductive film 1611 on resist that are separated from each other (step S1005).
• a stripping composition is supplied to the glass substrate 10 10 to peel off the conductive film 1611 on the resist also in the glass substrate 1010 force (step S1006), and then the used stripping composition is applied to the conductor on the resist.
• the membrane 1611 is dissolved and reused (step S1007).
• FIG. 13 is a schematic flowchart for explaining a method for manufacturing a TFT substrate according to the second embodiment of the present invention.
• a thin film transistor 2050 is formed on a substrate 2010 (step S200 j).
• FIG. 14 is a schematic view for explaining a method of manufacturing a TFT substrate according to the second embodiment of the present invention.
• FIG. 14 (a) shows a gate insulating film formed with a gate wiring and a gate electrode.
• a glass substrate 2010 is prepared, and a gate wiring 2021 and a gate electrode 2022 made of a conductive thin film such as Al (aluminum) are formed by a photolithography method, and then an exposed glass substrate 2010 is formed.
• a gate insulating film 2023 is stacked over the gate wiring 2021 and the gate electrode 2022.
• a first mask is used to form the gate wiring 2021 and the gate electrode 2022.
• FIG. 15 is a schematic view for explaining a method for manufacturing a TFT substrate according to the second embodiment of the present invention.
• FIG. 15A shows a thin film transistor formed by laminating a protective insulating film.
• (B) shows an enlarged cross-sectional view.
• the source substrate 2031, the source electrode 2032, the channel portion 2051, and the drain electrode 2042 are formed.
• a thin film transistor 2050 is formed thereon (step S2001), and then a protective insulating film 2054 is stacked on the glass substrate 2010 and the thin film transistor 2050 (step S). 2002).
• a halftone exposure technique (second halftone mask (not shown)) is used. That is, first, an amorphous silicon thin film 2052, an n-type amorphous silicon thin film 2053, a conductive thin film 2033 such as molybdenum Z aluminum Z molybdenum thin film, and a resist (not shown) are sequentially stacked on the gate insulating film 2023. .
• a resist is formed by using a halftone exposure technique, and the source wiring 2031 is formed by the first etching, and the source electrode 2032, the channel portion 2051, and the drain electrode 2042 are formed. Forming part. Subsequently, the resist is reformed, and the conductive thin film 2033 and the n-type amorphous silicon thin film 2053 above the channel portion 2051 are etched by the second selective etching, so that the channel portion 2051, the source electrode 2032, and the drain are etched. An electrode 2042 is formed. Next, a protective insulating film 2054 is stacked over the source wiring 2031, the thin film transistor 2050, and the gate insulating film 2023 (step S2002).
• a resist 2055 is laminated on the protective insulating film 2054 (step S2003), and then halftone exposure technology (third halftone mask (not shown)) is formed. ) Is used to form a laminated resist 2055 into a predetermined shape and then etched, and further, the resist 2055 is re-formed, and the undercut portion 2554 is formed at the bottom of the periphery of the re-formed resist (re-formed resist 2553). (Step S2004).
• FIG. 16 is a schematic view for explaining a method for manufacturing a TFT substrate according to the second embodiment of the present invention, and (a) shows that the resist on the protective insulating film has a predetermined shape. The formed plan view is shown, (b) shows an enlarged cross-sectional view.
• a resist 2055 is stacked on the protective insulating film 2054 (step S2003). Subsequently, a resist 2055 is formed into a predetermined shape by a halftone exposure technique. That is, the resist 2055 is formed above the drain electrode 2042, an opening 2056 for forming the contact hole 2541 is formed, and the pixel electrode 2612 is formed further. A thin halftone exposure resist 2552 is formed in the portion (see FIG. 23), and a thick full exposure resist 2551 is formed in the portion where the pixel electrode 2612 is not formed.
• FIG. 17 is a schematic view for explaining a manufacturing method of a TFT substrate according to the second embodiment of the present invention, and (a) shows an enlarged sectional view in which contact holes are formed. (B) is an enlarged cross-sectional view in which the resist is re-formed and an undercut portion is formed, and (c) is a detailed view of the ⁇ portion.
• the protective insulating film 2054 is etched (usually dry etching) using a resist 2055 formed by a halftone exposure technique, and the pixel electrode 2612 and the drain electrode 2042 are connected. A contact hole 2541 for connection is formed.
• the resist 2055 is re-formed. That is, the resist 2055 is gradually removed by oxygen plasma ashing, and all the halftone exposure resist 2552 is removed. At this time, the total exposure resist 2551 has a thickness for functioning as a force resist that is gradually removed from the upward force and becomes a re-formed resist 2553 with a reduced thickness. Further, the upper surface of the re-formed resist 2553 maintains a predetermined shape. Subsequently, by re-developing with a developer, an undercut portion 2554 is formed at the lower portion of the periphery of the predetermined shape (step S2004).
• the re-formed resist 2553 may have a two-layer structure in which an upper layer resist 2551a and a lower layer resist 2551b also have a force.
• the upper resist 2551a and the lower resist 2551b have different solubility in the developer, and are set so that the lower resist 2551b has higher solubility in the developer than the upper resist 2551a.
• the undercut portion 2554 can be more reliably formed, and the yield can be improved.
• the ingredients can be adjusted by blending two or more resist resins, or a photoreaction can be used.
• a difference in solubility by providing a difference in the degree of curing.
• a transparent conductive material is vapor-deposited above the glass substrate 2010. Then, the pixel electrode 2612 and the conductive film 2611 on the resist that are separated from each other are formed (step S2005).
• FIG. 18 shows a schematic diagram with a conductor film formed for explaining a method of manufacturing a TFT substrate according to the second embodiment of the present invention, and (a) is an enlarged sectional view. (B) is a detailed view of the part.
• a transparent conductive material is deposited above the glass substrate 2010 to form a conductive film 2061 (pixel electrodes 2612 separated from each other and a conductive film 2611 on the resist) (step S2005). That is, as a transparent conductive material is deposited above the glass substrate 2010, a conductor film 2611 on the resist is formed on the re-formed resist 2553. A pixel electrode 2612 is formed on the exposed drain electrode 2042 and protective insulating film 2054. The pixel electrode 2612 is separated from the conductor film 2611 on the resist by an undercut portion 2554 and is not electrically connected. The pixel electrode 2612 is electrically connected to the drain electrode 2042 through a contact hole 2541.
• the conductive material usually indium oxide / zinc oxide (IZO), indium oxide / tin oxide (ITO), amorphous indium oxide 'tin oxide (a-ITO), titanium oxide' niobium oxide, tin oxide “Zinc oxide, tin oxide”, antimony oxide, fluorine-doped tin oxide, and those containing the group consisting of combinations thereof are used. Since these conductor films are not dissolved at all in the stripping composition, it is possible to eliminate the concern that the required yield of the pixel electrode 2612 is dissolved in a small amount, which lowers the manufacturing yield. Furthermore, since the specific gravity of the conductive film is about 5 times or more than the specific gravity of the stripping composition, sedimentation-type separation and centrifugal separation can be performed easily and accurately.
• IZO indium oxide / zinc oxide
• ITO indium oxide / tin oxide
• a-ITO amorphous indium oxide 'tin oxide
• titanium oxide' niobium oxide titanium
• a stripping composition is supplied to the glass substrate 2010, and the conductive film 2611 on the resist is peeled off from the glass substrate 2010 (step S2006), and then used.
• the conductive film 2611 on the resist is separated from the stripping composition and reused (step S 2007).
• a method of peeling the conductive film 2611 on the resist from the glass substrate 2010, and separating the conductive film 2611 on the peeled resist from the used stripping composition, the used stripping composition A method of reusing objects will be described with reference to the drawings.
• FIG. 19 shows a stripping process for stripping a conductive film on a resist and reuses a used stripping composition in a TFT substrate manufacturing method according to the second embodiment of the present invention.
• the schematic sectional drawing for demonstrating a recycling process is shown.
• the glass substrate 2010 on which the conductor film 2061 is laminated is subjected to a stripping process in which the re-forming resist 2553 is dissolved by the stripping apparatus 2007, and the conductor film 2611 on the resist is peeled off (step S2006).
• the stripping device 2007 has a force in combination with a storage tank 2071 for storing a stripping solution 2070 containing a stripping composition, a spray nozzle 2072 for spraying the stripping solution 2070 onto a glass substrate 2010, a pump 2073 and a suction pipe 2074. ! /
• the stripping solution 2070 is sprayed from the spray nozzle 2072 in a spray form, and in this case, the stripping solution 2070 enters the undercut portion 2 554 through a minute gap.
• the upper conductive film 2611 can be effectively peeled off the glass substrate.
• FIG. 19 shows the state during stripping, and the re-formed resist 2553 and the conductive film 2611 on the resist partially remain.
• the stripping composition contained in the stripping solution 2070 is made of a photoresist stripping agent for stripping the re-formed resist 2553.
• the photoresist stripping agent contains an amine compound and an aprotic polar compound.
• amine compounds include monoethanolamine, monoisopropanolamine, methylmethanolamine, ethylethanolamine, dimethanolamine, aminoethoxyethanolamine, diethanolamine and the like (FIG. 20). , 21). Each of the above amine compounds may be used alone or in combination of two or more.
• aprotic polar compounds examples include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylimidazole, dimethyl Examples thereof include sulfoxide (see FIG. 22). Further, the aprotic polar compound may be used alone or in combination of two or more.
• the resist stripping agent about 20 to 80 weight amine compound comprises 0/0, and an aprotic polar I ⁇ product may comprise from about 20 to 80 wt%. In this way, only the re-formed resist 2553 is dissolved, and the necessary pixel electrode 2612 is not damaged, so that the yield and reliability can be improved.
• the resist stripping agent the reason to include about 20 to 80 weight 0/0 amine-based compound, the content of the amine compound is less than about 20 wt%, within a short period of time to re-form the resist 2553
• the amine compound content exceeds about 80% by weight, the conductor film forming the pixel electrode 2612 is formed while the re-forming resist 2553 is dissolved. This is because the pixel electrode 2612 is damaged due to rapid corrosion.
• the amine compound exceeds about 80% by weight, the volatilization amount of the stripping composition increases, and there is a concern that the component ratio of the stripping composition may change. Therefore, in the stripping composition of the present invention, the content of the amine compound is preferably about 20 to 80% by weight, more preferably 30 to 70% by weight.
• the content of the aprotic polar compound exceeds about 80% by weight, the pixel electrode 2612 may be corroded when the re-formed resist 2553 is stripped. Accordingly, in the stripping composition of the present invention, the content of the aprotic polar compound is preferably about 20 to 80% by weight, more preferably about 30 to 70% by weight.
• the stripping yarn is not limited to the above-mentioned yarn and includes, for example, an alkoxyacrylamide compound represented by the following general formula 1 or ethylene carbonate as a resist stripping agent. Good.
• R 1 O—CH 2 CH 2 —C—NR 2 R 3 (—general formula 1)
• R 1, R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms.
• the alkoxy atta amide compound has water solubility, is not flammable, and can provide a safe stripping composition.
• the stripping composition can dissolve the re-formed resist 2553 and separate all of the conductor film 2611 on the resist formed on the upper surface of the re-formed resist 2553 from the glass substrate 2010. it can.
• the stripping composition does not dissolve the conductor film 2061, it is possible to eliminate the worry when the pixel electrode 2612 is dissolved. That is, since the pixel electrode 2612 is not damaged by the stripping composition, an optimum stripping condition can be selected.
• the spray duration is about 0.5-5 minutes, preferably about 1-3 minutes.
• the etching of the re-formed resist 2553 and the dissolution of the conductive film are preferably performed in a temperature range of about 30 ° C. to 60 ° C. Further, about 40 to 50 ° C. is preferable.
• the conductor film 2611 on the resist separated from the glass substrate 2010 flows into the storage tank 2071 together with the stripping solution 2070.
• the conductor film 2611 on the peeled resist is mixed in the stripping solution 2070 as fine pieces such as particles and string-like bodies.
• the stripping solution 2070 containing the conductive film 2611 on the resist (referred to as a used stripping composition as appropriate) flows into the storage tank 2071, the conductive film 2611 on the resist is stored in the storage tank 2071. Settles.
• the fine pieces have a higher density. That is, the specific gravity of the fine pieces present in the used stripping composition is much larger than the specific gravity of the stripping composition, so that it can easily settle and separate in the storage tank 2071. It is possible to easily and efficiently reuse the stripping solution 2070 that does not contain any of the above.
• the guide plate 2711 that guides the used stripping composition to one end of the storage tank 2071 and the minute piece (the conductive material on the resist) on the other end where the suction pipe 74 is located. By providing a partition plate 2712 that prevents the body film 2611) from moving, the suction pipe 2074 more reliably prevents the conductor film 2611 on the resist from being sucked.
• the method for separating the conductive film 2611 on the resist contained in the used stripping composition is not limited to the above method.
• the conductive film 2611 is allowed to stand in a dedicated precipitation tank for about 10 to 30 minutes and then decane. It is good also as a method of collecting a supernatant liquid by a tasting.
• the conductive film 2611 on the resist is completely settled in the storage tank 2071, and the stripping solution 2070 that does not include the conductive film 2611 on the resist is removed from the suction pipe 2074 by the pump 2073. It is sucked and sprayed again on the glass substrate 2010 from the spray nozzle 2072. That is, the conductive film 2611 on the resist is separated from the used stripping composition and reused (step S2007).
• FIG. 23 is a schematic view for explaining a method for manufacturing a TFT substrate according to the second embodiment of the present invention.
• FIG. 23 (a) is a plan view in which a pixel electrode is formed.
• (B) shows an enlarged cross-sectional view!
• the manufacturing method of the TFT substrate 2001 of this embodiment uses three masks: a first mask, a second half-tone mask, and a third half-tone mask, which reduces the manufacturing process and increases the productivity. Is excellent.
• stripping composition about 30 wt% of an amino compound and about 70 wt% of a non-product
• a stripping solution I consisting of an oral polar solvent and a stripping solution consisting of about 70 wt% amino compound and about 30 wt% aprotic polar solvent were prepared (see Table 4).
• a glass substrate a square glass substrate of about 100 mm X 100 mm X O. 7 mm was prepared, washed with a pure water shower, and then a resist was applied and formed by a spin coater.
• the resist used was a negative resist made by Nippon Zeon: ZTN2464-27. Subsequently, after heating in an oven at about 80 ° C. for about 15 minutes, exposure was performed at an exposure intensity of 300 mjZcm 2 .
• a mask to be used a stripe mask in which about 20 ⁇ m lines and about 90 ⁇ m spaces were arranged in order was used.
• a thin film having a thickness of about lOOnm was formed by sputtering.
• the glass substrate obtained above was immersed in the stripping solution for 2 minutes to perform resist stripping, washed with pure water, and air blown. Thereafter, the glass substrate was dried in a drier to obtain a glass substrate having a thin film (width of about m) having an IZO force and a space of about 20 m.
• the above-mentioned used stripping solution I and used stripping solution II were separated into individual liquids using a centrifuge.
• the resist was peeled off from the new glass substrate using the regenerated stripping solution I and the separated stripping solution II, it was confirmed that the resist could be removed normally. Further, no coiled IZO or powdered IZO was observed on the peeled glass substrate.
• the stripping operation can be performed by using ethylene carbonate instead of the stripping solution I in the same manner.
• this used stripping solution was allowed to stand for about 10 minutes, it was confirmed that a coiled IZO thin film settled and settled to the bottom. Furthermore, no coiled IZO thin film was observed in the supernatant.
• IZO is an amorphous conductive film having an indium oxide / acid / zinc strength, and an indium oxide power having about 10% added zinc oxide.
• the amount of zinc oxide added is appropriately selected, but good results are obtained when about 5 to 40 wt% of zinc oxide is added.
• ITO indium oxide 'tin oxide
• a-ITO Tin oxide
• tin oxide zinc oxide oxide
• the conductor film in the stripper I and II is allowed to settle, and the resist can be stripped without any problem even if the stripper I or II is reused. In addition, no conductive film particles were observed on the substrate.
• indium oxide / tin oxide is indium oxide containing about 5 to 15 wt% of tin oxide.
• Amorphous indium oxide 'Tin oxide is an amorphous ITO film.
• Acid-titanium acid-niobium is a titanium oxide to which about 0.1 to 5% of niobium oxide is added.
• Tin oxide 'Zinc oxide is a complex oxide composed of tin oxide: about 60 to 95 wt%, and zinc oxide: about 5 to 40 wt%.
• Tin oxide 'antimony oxide is tin oxide containing about 0.5 to 5 wt% of antimony oxide.
• Fluorine-doped tin oxide is tin oxide added with about 0.01 to 1% of fluorine. These tin oxide-based conductive films are difficult to pattern by etching with a weak acid such as oxalic acid, and the patterning force due to lift-off is effective as in this example.
• the liquid crystal panel is completed after the subsequent alignment film application, alignment treatment, liquid crystal injection, and sealing process.
• the deposits may diffuse into the alignment film or into the liquid crystal in the subsequent process. This causes display defects and display defects.
• the present invention is also effective as a method for recycling the stripping composition.
• the recycling method of the stripping composition that works in this embodiment is almost the same method as the TFT substrate manufacturing method of the second embodiment described above.
• a thin film transistor 2050 is formed on the substrate 2010 (step S2001). Then, the protective insulating film 2054 is laminated on the glass substrate 2010 and the thin film transistor 2050 (step S2002). Next, a resist 2055 is stacked on the protective insulating film 2054 (step S2003), and then the stacked resist 2055 is formed using a halftone exposure technique (third halftone mask (not shown)). A predetermined shape is formed and etching is performed. Further, a resist 2055 is formed again, and an undercut portion 2554 is formed at the lower peripheral portion of the re-formed resist (reformed resist 2553) (step S2004).
• a transparent conductive material is deposited on the glass substrate 2010 to form pixel electrodes 2612 and a conductive film 2611 on the resist, which are separated from each other (step S 2005). Further, the stripping composition is supplied to the glass substrate 2010, and the conductive film 2611 on the resist is peeled off from the glass substrate 2010 (Step S 2006). Subsequently, the conductive material on the resist is removed from the used stripping composition. The body membrane 2611 is separated and reused (step S 2007).
• the used stripping composition force is almost completely separated from the conductive film 2611 on the resist peeled off from the glass substrate 2010.
• the used stripping composition can be reused without reducing the yield.
• stripping composition As described above, the stripping composition, the TFT substrate manufacturing method, and the stripping composition recycling method of the present invention have been described with reference to preferred embodiments.
• the stripping composition according to the present invention and the TFT substrate manufacturing It goes without saying that the method and the recycling method of the stripping composition are not limited to the above-described embodiments, and various modifications can be made within the scope of the present invention.
• a solvent that suppresses foaming when supplying the stripping composition in a range that does not adversely affect the performance of the stripping composition and a viscosity reducing agent. You can add diluents.
• the force separation method adopting the sedimentation-type separation method in which the conductive film 2611 on the peeled resist is settled and separated in the storage tank 2071 is
• the present invention is not limited to this.
• a centrifugal separation method using a centrifugal separator or a filter-type separation method using a filter may be employed.
• any one of the sedimentation separation method, the centrifugal separation method, and the filtration separation method is not limited to the method of adopting one.
• a combination of the above separation methods may be employed.

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