CN111755461B - Method for manufacturing array substrate for liquid crystal display device and copper-based metal film etching liquid composition for same - Google Patents

Method for manufacturing array substrate for liquid crystal display device and copper-based metal film etching liquid composition for same Download PDF

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CN111755461B
CN111755461B CN202010231299.7A CN202010231299A CN111755461B CN 111755461 B CN111755461 B CN 111755461B CN 202010231299 A CN202010231299 A CN 202010231299A CN 111755461 B CN111755461 B CN 111755461B
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acid
copper
metal film
based metal
liquid composition
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CN111755461A (en
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郑敬燮
朴镛云
梁圭亨
金相正
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Dongwoo Fine Chem Co Ltd
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Priority claimed from KR1020190037295A external-priority patent/KR102639573B1/en
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells
    • 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
    • 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
    • H01L27/127—Multistep manufacturing methods with a particular formation, treatment or patterning of the active layer specially adapted to the circuit arrangement

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Abstract

The invention provides a method for manufacturing an array substrate for a liquid crystal display device and a copper-based metal film etching liquid composition used for the same, wherein the copper-based metal film etching liquid composition comprises hydrogen peroxide; fluorine-containing compounds or inorganic acids; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water, the above-mentioned method for manufacturing array base plate for liquid crystal display device, by etching the copper-based metal film and forming the source electrode/drain electrode by using the above-mentioned etchant composition, can etch the copper-based metal film together under the condition of not damaging the oxide semiconductor layer.

Description

Method for manufacturing array substrate for liquid crystal display device and copper-based metal film etching liquid composition for same
Technical Field
The present invention relates to a method for manufacturing an array substrate for a liquid crystal display device and a copper-based metal film etching liquid composition used for the same.
Background
With the formal entry into the information age, the field of displays that process and display a large amount of information has been rapidly developed, and accordingly, various flat panel displays have been developed and attracting attention.
Examples of such flat panel display devices include Liquid crystal display devices (Liquid CRYSTAL DISPLAY DEVICE: LCD), plasma display devices (PLASMA DISPLAY PANEL DEVICE: PDP), field Emission display devices (Field Emission DISPLAY DEVICE: FED), electroluminescent display devices (Electroluminescence DISPLAY DEVICE: ELD), organic LIGHT EMITTING Diodes (OLED), and the like, and such flat panel display devices are used in various applications in the fields of home appliances such as televisions and video recorders, and in computers and mobile phones such as notebooks. In practice, these flat panel display devices are rapidly replacing the conventional Cathode Ray Tube (NIT) devices due to their excellent performances such as thickness reduction, light weight, and low power consumption.
In a liquid crystal display device, a process of forming a metal wiring on a substrate generally includes steps of: a metal film forming step using sputtering or the like; a photoresist forming step in a selective region by photoresist coating, exposure and development; and an etching step, and includes a cleaning step before and after the individual unit steps, and the like. Such etching step is a step of leaving a metal film in a selective region using a photoresist as a mask, and generally uses dry etching using plasma or the like or wet etching using an etchant composition.
In such a liquid crystal display device, in recent years, attention has been paid mainly to the resistance of the metal wiring. This is because the resistance is a major factor inducing RC signal delay, and in a thin film transistor liquid crystal display (thin film transistor-liquid CRYSTAL DISPLAY, TFT-LCD), solving the RC signal delay problem is a key to increase the panel size and achieve high resolution. Therefore, in order to reduce the RC signal delay required for the large-scale TFT-LCD, low-resistance materials have to be developed.
Chromium (Cr, resistivity: 12.7x -8 Ω m), molybdenum (Mo, resistivity: 5 x 10 -8 Ω m), aluminum (Al, resistivity: 2.65x -8 Ω m) and alloys thereof, which have been mainly used in the past, have large resistances, and thus are difficult to be used for gate lines, data lines, and the like, which are used in large-sized TFT-LCDs. Therefore, attention has been paid to copper-based metal films such as copper films and copper-molybdenum films, which are low-resistance metal films, and etching liquid compositions therefor. However, the hitherto known copper-based metal film etchant compositions still fail to satisfy the performance required by users, and thus research and development for improving the performance have been required.
In connection with this, korean laid-open patent No. 10-2015-0004971 discloses a copper-based metal film etching liquid composition comprising a polyol surfactant, citric acid, hydrogen peroxide, a fluorine-containing compound and an azole compound, but in the case of the above etching liquid composition, when an oxide semiconductor is used as a semiconductor layer, there are the following problems: when the process is performed, the etching liquid composition is concentrated by the exhaust gas, and the degree of damage of the oxide semiconductor is changed, so that it is difficult to control the process, and thus it is difficult to maintain the performance of the liquid crystal display device.
Prior art literature
Patent literature
Korean laid-open patent No. 10-2015-0004971
Disclosure of Invention
Problems to be solved
In order to solve the above-described problems of the prior art, an object of the present invention is to provide a method for manufacturing an array substrate for a liquid crystal display device, which uses an etchant composition capable of etching copper-based metal films simultaneously without damaging an oxide semiconductor layer.
Means for solving the problems
In order to achieve the above object, the present invention provides a method for manufacturing an array substrate for a liquid crystal display device, comprising: a) A step of forming a gate electrode on a substrate; b) Forming a gate insulating layer on a substrate including the gate electrode; c) A step of forming an oxide semiconductor layer (IGZO) on the gate insulating layer; d) Forming a source electrode/drain electrode on the oxide semiconductor layer; and e) forming a pixel electrode connected to the source electrode and the drain electrode, wherein in the d), a copper-based metal film is formed on the oxide semiconductor layer, and the copper-based metal film is etched by using an etchant composition, the etchant composition including hydrogen peroxide; fluorine-containing compounds or inorganic acids; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water.
The present invention also provides a copper-based metal film etching liquid composition comprising (A) 5.0 to 30.0 wt% of hydrogen peroxide, based on the total weight of the composition; 0.001 to 1.0 wt% of a fluorine-containing compound or an inorganic acid; (C) 0.01 to 2.0% by weight of an azole compound; (D) 1.0 to 10.0% by weight of an organic acid; (E) 0.1 to 5% by weight of citrate; (F) More than 0.01 to 5 weight percent of one of sulfate and phosphate; (G) 0.001 to 5.0 wt% of a polyol surfactant; and (H) water.
Effects of the invention
The method for manufacturing an array substrate for a liquid crystal display device according to the present invention can simultaneously etch a copper-based metal film without damaging an oxide semiconductor layer, and can reduce the generation of a tip (tip) of a molybdenum film or a molybdenum alloy film including the copper-based metal film by using an etching liquid composition excellent in etching profile and etching straightness, and can suppress the change of Side etching (Side etching) by reducing the change of the damage rate (DAMAGE RATE) of the oxide semiconductor layer caused by outgas during etching by using equipment, thereby providing an effect of easy control of a process.
Detailed Description
The present invention relates to a composition comprising hydrogen peroxide; fluorine-containing compounds or inorganic acids; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and an etching liquid composition of water, and a method for manufacturing an array substrate for a liquid crystal display device using the etching liquid composition, wherein the etching liquid composition can etch a copper-based metal film without damaging an oxide semiconductor layer, and the etching profile and the etching straightness are excellent, so that the generation of tips of a molybdenum film or a molybdenum alloy film containing the copper-based metal film is reduced, and the damage rate variation of the oxide semiconductor layer caused by exhaust gas is low in the etching process using equipment, so that the side etching variation is suppressed, thereby providing the effect of easy control of the process.
The constitution of the present invention will be specifically described below.
< Method for manufacturing array substrate for liquid Crystal display device >
The invention provides a method for manufacturing an array substrate for a liquid crystal display device, which is characterized by comprising the following steps: a) A step of forming a gate electrode on a substrate; b) Forming a gate insulating layer on a substrate including the gate electrode; c) A step of forming an oxide semiconductor layer (IGZO) on the gate insulating layer; d) Forming a source electrode/drain electrode on the oxide semiconductor layer; and e) forming a pixel electrode connected to the source electrode and the drain electrode, wherein in the d), a copper-based metal film is formed on the oxide semiconductor layer, and the copper-based metal film is etched by using an etchant composition, the etchant composition including hydrogen peroxide; fluorine-containing compounds or inorganic acids; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water.
The copper-based metal film is a metal film containing copper in the constituent components of the film, and specifically may be a single-layer film composed of copper or a copper alloy, or a multilayer film such as a double-layer film and a three-layer film including the single-layer film and a film composed of molybdenum or a molybdenum alloy.
For example, the copper-based metal film may include a copper film and a copper alloy film as a single layer film, may include a copper film-molybdenum film, a copper film-molybdenum alloy film, a copper alloy film-molybdenum alloy film, and a molybdenum film-copper alloy film-molybdenum alloy film, a molybdenum film-copper alloy film-molybdenum film, a molybdenum alloy film-copper alloy film-molybdenum alloy film, a molybdenum alloy film-copper alloy film-molybdenum alloy film, and the like as a three-layer film.
The alloy film may be an alloy film of copper or molybdenum and at least one selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and the like, or may be a nitride film or an oxide film of copper or molybdenum.
When the copper-based metal film is etched by using the etching liquid composition of the present invention, the copper-based metal film can be etched simultaneously without damaging (damage) the oxide semiconductor layer.
As an embodiment of the etching liquid composition of the present invention, hydrogen peroxide is preferably contained; a fluorine-containing compound; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water, as another embodiment of the etching liquid composition of the present invention, preferably contains hydrogen peroxide; an inorganic acid; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water.
The etching liquid composition of the present invention will be described in detail below.
< Copper-based Metal film etchant composition >
The copper-based metal film etching liquid composition of the present invention may contain hydrogen peroxide; fluorine-containing compounds or inorganic acids; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water.
As an embodiment of the etching liquid composition of the present invention, hydrogen peroxide is preferably contained; a fluorine-containing compound; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water, as another embodiment of the etching liquid composition of the present invention, preferably contains hydrogen peroxide; an inorganic acid; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water.
(A) Hydrogen peroxide
The hydrogen peroxide (H 2O2) contained in the etching solution composition of the present invention can be used as a main oxidizing agent for the copper-based metal film.
The content of the hydrogen peroxide may be 5.0 to 30.0 wt%, and preferably may be 8.0 to 25.0 wt%, with respect to the total weight of the composition. When the content of hydrogen peroxide is less than 5.0 wt%, the copper-based metal film may not be etched or the etching rate may be very slow, and when the content is more than 30.0 wt%, the etching rate becomes fast as a whole, and the process may not be easily controlled.
(B-1) fluorine-containing Compound
The fluorine-containing compound contained in the etching liquid composition of the present invention is a compound capable of dissociating in water to release fluorine ions. The fluorine-containing compound is a main component of etching the copper-based metal film, and serves to remove residues inevitably generated in the molybdenum film or the molybdenum alloy film.
The fluorine-containing compound is not particularly limited as long as it is a compound which is used in the art and can be dissociated into fluoride ions or polyatomic fluoride ions in a solution, and is preferably at least one selected from the group consisting of ammonium fluoride (ammonium fluoride: NH 4 F), sodium fluoride (sodium fluoride: naF), potassium fluoride (potassium fluoride: KF), ammonium bifluoride (ammonium bifluoride: NH 4 F. HF), sodium bifluoride (sodium bifluoride: naF. HF) and potassium bifluoride (potassium bifluoride: KF. HF), more preferably at least one selected from the group consisting of ammonium bifluoride and ammonium fluoride.
The content of the fluorine-containing compound may be 0.001 to 1.0% by weight, and preferably may be 0.02 to 0.20% by weight, based on the total weight of the composition. When the content of the fluorine-containing compound is less than 0.001 wt%, the etching rate of the molybdenum film or the molybdenum alloy film may be reduced, and an etching residue may be generated, and when the content is more than 1.0 wt%, the etching rate of the oxide semiconductor layer in the lower portion of the copper-based metal film may be increased.
(B-2) mineral acid
The inorganic acid contained in the etching liquid composition of the present invention can be used as a co-oxidizing agent for the copper-based metal film. When the etching liquid composition does not contain the above-mentioned inorganic acid, there is a problem that the etching rate is lowered and the process time is increased. In addition, if the tip of the molybdenum film or the molybdenum alloy film is generated on the upper portion of the copper-based metal film as the etching rate of the molybdenum film or the molybdenum alloy film decreases, defects may be induced in the subsequent steps.
In one embodiment, the inorganic acid may be one or more selected from the group consisting of nitric acid, sulfuric acid, and phosphoric acid.
The content of the inorganic acid may be 0.001 to 1.0 wt%, and preferably may be 0.005 to 0.5 wt%, with respect to the total weight of the composition. In the case where the content of the inorganic acid is less than 0.001 wt%, the etching rate is decreased and the process time is increased, and in the case where the content is more than 1.0 wt%, there is a possibility that the etching rate of the copper film or the copper alloy film is significantly faster than that of the molybdenum film or the molybdenum alloy film, thereby causing a problem that the tip of the molybdenum film or the molybdenum alloy film located on the upper portion of the copper film or the copper alloy film is located.
(C) Azole compounds
The azole compound contained in the etching solution composition of the present invention serves to adjust the etching rate and reduce the variation of the etching (Etch) profile due to the number of processed sheets, thereby improving the process margin.
In one or more embodiments, the azole compound may be selected from pyrrole (pyrrole) based compounds; pyrazole (pyrazol) compound; imidazole (imidazole) compounds including imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole, and 4-propylimidazole; triazole (triazole) compounds including benzotriazole (benzotriazole), methylbenzotriazole (tolyltriazole), and methyltriazole; tetrazole (tetrazole) compounds including aminotetrazole (aminotetrazole) and methyltetrazole; a pentazole (pentazole) compound; an azole (oxazole) compound; different species An azole (isoxazole) compound; more than one kind of thiazole (thiazole) compound and isothiazole (isothiazole) compound is preferably tetrazole (tetrazole) compound.
The azole compound may be contained in an amount of 0.01 to 2.0 wt%, preferably 0.05 to 1.0 wt%, based on the total weight of the composition. When the content of the azole compound is less than 0.01 wt%, the etching rate becomes high, and a CD Loss (CD Loss) may occur excessively, and when the content is more than 2.0 wt%, the etching rate of the copper-based metal film is too low, and an etching residue may occur.
(D) Organic acid
The organic acid contained in the etching solution composition of the present invention is a treatment number improver, and can chelate copper ions to improve the treatment number of the copper-based metal film.
In one embodiment, the organic acid may be one or more selected from the group consisting of acetic acid, iminodiacetic acid, ethylenediamine tetraacetic acid, butyric acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, valeric acid, sulfobenzoic acid, succinic acid, sulfosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, and acrylic acid, and preferably one or more selected from the group consisting of citric acid, gluconic acid, and iminodiacetic acid.
The content of the organic acid may be 1.0 to 10.0% by weight, and preferably may be 2.0 to 7.0% by weight, relative to the total weight of the composition. When the content of the organic acid is less than 1.0 wt%, the etching rate of the copper-based metal film may be reduced to generate etching residues as the number of processed sheets increases, and when the content is more than 10.0 wt%, overetching of the copper-based metal film may be caused.
(E) Citrate salt
The citrate contained in the etching solution composition of the present invention assists the action of the organic acid to chelate copper ions, thereby suppressing the decomposition reaction of the hydrogen peroxide. In addition, when the copper-based metal film is etched by using the apparatus, the citrate can serve to minimize a change in etching characteristics of the etchant composition due to concentration of the etchant composition by the exhaust gas. In the case where the etching solution composition does not contain the citrate, as the exhaust time increases, the etching Rate (Etch Rate) changes more, and thus the Rate of change of the undercut (SideEtch) may become more.
In one embodiment, the Citrate may be in the form of a salt of citric acid, and may be at least one selected from the group consisting of monosodium Citrate (Monosodium Citrate), disodium Citrate (Disodium Citrate), and trisodium Citrate (Trisodium Citrate), and preferably may be trisodium Citrate.
The citrate may be contained in an amount of 0.1 to 5.0 wt%, preferably 0.5 to 3 wt%, based on the total weight of the composition. When the content of the citrate is less than 0.1 wt%, the damage rate of the oxide semiconductor layer increases as the exhaust time increases, and the element characteristics may be lowered, and when the content is more than 5.0 wt%, the etching rate of the copper film may be lowered due to an increase in pH, which may cause difficulty in the process.
When the citrate is used in the above-described range, the damage rate of the oxide semiconductor layer is constantly maintained even if the exhaust time increases, and thus, even if the process is performed, the deterioration of the element characteristics does not occur, and the process can be easily controlled.
(F) More than one of sulfate and phosphate
The sulfate and the phosphate contained in the etching solution composition of the present invention are components for increasing the etching rate of the molybdenum film or the molybdenum alloy film, and can realize a fine pattern by adjusting the etching rate. In particular, when the copper-based metal film is formed as a multilayer film, the etching rates of the upper and lower metal films of the multilayer film can be simultaneously made to realize a fine pattern.
The sulfate is not particularly limited as long as one or two hydrogens selected from the group consisting of sulfuric acid are replaced with ammonium, alkali metal or alkaline earth metal, and may be, for example, one or more selected from the group consisting of ammonium sulfate, ammonium persulfate, sodium sulfate, sodium persulfate, potassium sulfate and potassium persulfate, and preferably may be sodium sulfate.
The phosphate may be, for example, at least one selected from the group consisting of monoammonium phosphate and diammonium phosphate.
The content of one or more of the sulfate and the phosphate is not particularly limited, and may be, for example, 0.01 to 5% by weight, preferably 0.01 to 1.0% by weight, based on the total weight of the etching liquid composition. When the content of one or more of the sulfate and the phosphate is within the above range, the etching rate of the copper-based metal film can be adjusted to realize a fine pattern. In particular, by increasing the etching rate of the molybdenum film or the molybdenum alloy film, the phenomenon that the copper film or the copper alloy film is excessively etched to form a stepped tapered profile during etching of the molybdenum film or the molybdenum alloy film can be prevented. When the content of one or more of the sulfate and the phosphate is out of the above range, the CD loss of the upper copper film or the copper alloy film becomes serious and the line width becomes narrow, so that the resistance becomes large and the advantage of the low-resistance metal is lost.
(G) Polyol type surfactant
The above-mentioned polyol type surfactant contained in the etching liquid composition of the present invention plays a role of reducing the surface tension and improving the etching uniformity. The polyol surfactant can also surround copper ions dissolved in the etchant composition after etching the copper-based metal film, thereby suppressing the activity of the copper ions and suppressing the decomposition reaction of the hydrogen peroxide. If the activity of copper ions is lowered, the process can be stably performed during the use of the etching liquid composition.
In one embodiment, the polyol-type surfactant may be one or more selected from the group consisting of glycerol (glycerol), diethylene glycol (DIETHYLENE GLYCOL), triethylene glycol (TRIETHYLENE GLYCOL), tetraethylene glycol (tetraethyleneglycol) and polyethylene glycol (polyethylene glycol), and more preferably one or more selected from the group consisting of triethylene glycol, diethylene glycol and tetraethylene glycol.
The content of the above-mentioned polyol type surfactant may be 0.001 to 5.0% by weight, preferably 0.1 to 3.0% by weight, relative to the total weight of the composition. When the content of the polyol surfactant is less than 0.001 wt%, there is a possibility that etching uniformity is lowered, and the decomposition of the hydrogen peroxide is accelerated, and when the content is more than 5.0 wt%, there is a disadvantage that a large amount of bubbles are generated.
(H) Water and its preparation method
The water contained in the copper-based metal film etching liquid composition of the present invention may be deionized water for a semiconductor process, and preferably 18mΩ·cm or more.
The water may be contained in an amount of 100% by weight based on the total weight of the composition. Specifically, in the present invention, the term "balance" means that the total weight of the composition containing the essential components of the present invention and other additional components is set to 100% by weight, and the composition of the present invention does not contain additional components in the meaning of "balance".
Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are provided to more specifically illustrate the present invention, and the scope of the present invention is not limited by the following examples. The scope of the present invention is indicated in the claims, and all changes that come within the meaning and range of equivalency of the claims are intended to be embraced therein. In the following examples and comparative examples, "%" and "parts" indicating the content are based on mass unless otherwise specified.
Production of copper-based Metal film etchant composition of examples and comparative examples
Copper-based metal film etchant compositions of examples and comparative examples were prepared with reference to the following [ table 1].
TABLE 1
(Unit: wt%)
(A) : hydrogen peroxide
(B-1): ammonium fluoride
(B-2): nitric acid
(C) : methyltetrazole
(D1) : glycolic acid
(D2) : citric acid
(D3) : iminodiacetic acid
(E1) : citric acid trisodium salt
(E2) : citric acid monosodium salt
(E3) : citric acid disodium salt
(F1) : sodium sulfate
(F2) : monoammonium phosphate
(G) : triethylene glycol
Test example 1: etch profile and etch straightness evaluation
A Mo-Ti film is deposited on an IGZO active layer (ACTIVE LAYER) on a glass substrate (100 mm x 100 mm), a copper film is deposited on the Mo-Ti film, and then a photoresist having a predetermined pattern is formed on the substrate by a photolithography (photolithography) process. Then, etching steps were performed on the Cu/mo—ti bilayer films using the etching liquid compositions of examples and comparative examples, respectively.
In the etching step, a jet etching type experimental apparatus (model name: ETCHER (TFT), SEMES) was used, and the etching time was 150 seconds at a temperature of about 32℃in the etching step. The cross section of the copper-based metal film etched by the etching step was photographed using SEM (model name S-4700 of Hitachi) and then evaluated according to the following evaluation criteria, and the results are shown in table 2 below.
< Etching Profile evaluation criterion >
O: cone angle of 30 DEG or more and less than 65 DEG
Delta: the taper angle is 25 DEG or more and less than 30 DEG or 65 DEG or more and 70 DEG or less
X: cone angle of 25 deg. or less or more than 70 deg
Unetch: failure to etch
< Evaluation criterion of etching straightness >
O: the pattern is formed in a straight line
Delta: the curve form in the pattern is below 20%
X: the curve form in the pattern is more than 20 percent
Unetch: failure to etch
Test example 2: measurement of change in damage ratio (DAMAGERATE) of oxide semiconductor layer (IGZO) with change in exhaust time
The copper-based metal film was etched in the same etching process as in test example 1, and the amount of change in the damage rate of the etching solution composition with respect to the oxide semiconductor layer (IGZO) immediately after the production was measured for 72 hours, and the results are shown in table 2 below.
TABLE 2
When the etching process was performed using the copper-based metal film etching solution composition of the example, it was confirmed that the etching profile, etching straightness, and the change amount characteristics of the IGZO rate with the change in the exhaust time were excellent.
On the other hand, when the etching step was performed using the copper-based metal film etching solution composition of the comparative example, it was confirmed that the etching profile and etching straightness were poor, and the amount of change in the damage rate of IGZO with the change in the exhaust time exceededSec, the process is not easily controlled, and the characteristics of the element are degraded.

Claims (12)

1. A method for manufacturing an array substrate for a liquid crystal display device, comprising:
a) A step of forming a gate electrode on a substrate;
b) A step of forming a gate insulating layer on a substrate including the gate electrode;
c) A step of forming an oxide semiconductor layer IGZO on the gate insulating layer;
d) A step of forming a source electrode/drain electrode on the oxide semiconductor layer; and
E) A step of forming a pixel electrode connected to the source/drain electrode,
In the step d), a copper-based metal film is formed on the oxide semiconductor layer, and the copper-based metal film is etched by an etchant composition including hydrogen peroxide to form the source/drain electrodes; fluorine-containing compounds or inorganic acids; an azole compound; an organic acid; comprises one or more citrates selected from the group consisting of monosodium citrate, disodium citrate, and trisodium citrate; more than one of sulfate and phosphate; a polyol type surfactant; and water.
2. The method of manufacturing an array substrate for a liquid crystal display device according to claim 1, wherein the copper-based metal film is a single-layer film made of copper or a copper alloy, or a multilayer film including the single-layer film and a film made of molybdenum or a molybdenum alloy.
3. The method of manufacturing an array substrate for a liquid crystal display device according to claim 1, wherein the array substrate for a liquid crystal display device is a thin film transistor TFT array substrate.
4.A copper-based metal film etching liquid composition comprising, relative to the total weight of the composition:
(A) 5.0 to 30.0 weight percent of hydrogen peroxide;
(B) 0.001 to 1.0 wt% of a fluorine-containing compound or an inorganic acid;
(C) 0.01 to 2.0 wt% of an azole compound;
(D) 1.0 to 10.0 wt% of an organic acid;
(E) 0.1 to 5% by weight of one or more citrates selected from the group consisting of monosodium citrate, disodium citrate and trisodium citrate;
(F) More than 0.01 to 5 weight percent of one of sulfate and phosphate;
(G) 0.001 to 5.0 wt% of a polyol surfactant; and
(H) And (3) water.
5. The copper-based metal film etchant composition according to claim 4, wherein the copper-based metal film is a single-layer film made of copper or copper alloy, or a multi-layer film comprising the single-layer film and a molybdenum-based single-layer film made of molybdenum or molybdenum alloy.
6. The copper-based metal film etching liquid composition according to claim 4, wherein the fluorine-containing compound is at least one selected from the group consisting of ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 F-HF), sodium bifluoride (NaF-HF) and potassium bifluoride (KF-HF).
7. The copper-based metal film etching liquid composition according to claim 4, wherein the inorganic acid is at least one selected from the group consisting of nitric acid, sulfuric acid and phosphoric acid.
8. The copper-based metal film etching liquid composition according to claim 4, wherein the azole compound is selected from the group consisting of pyrrole-based compounds, pyrazole-based compounds, imidazole-based compounds, triazole-based compounds, tetrazole-based compounds, and pentazole-based compounds,Azole compounds, iso-compoundsAt least one kind selected from the group consisting of azole compounds, thiazole compounds and isothiazole compounds.
9. The copper-based metal film etching liquid composition according to claim 4, wherein the organic acid is at least one selected from the group consisting of acetic acid, iminodiacetic acid, ethylenediamine tetraacetic acid, butyric acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, valeric acid, sulfobenzoic acid, succinic acid, sulfosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, and acrylic acid.
10. The copper-based metal film etching liquid composition according to claim 4, wherein the sulfate is at least one selected from the group consisting of ammonium sulfate, ammonium persulfate, sodium sulfate, sodium persulfate, potassium sulfate and potassium persulfate.
11. The copper-based metal film etching liquid composition according to claim 4, wherein the phosphate is at least one selected from the group consisting of monoammonium phosphate and diammonium phosphate.
12. The copper-based metal film etching liquid composition according to claim 4, wherein the polyhydric alcohol-type surfactant comprises at least one selected from the group consisting of glycerol, diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycol.
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