CN111755461A - Method for manufacturing array substrate for liquid crystal display device and copper-based metal film etching solution composition used for same - Google Patents

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

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CN111755461A
CN111755461A CN202010231299.7A CN202010231299A CN111755461A CN 111755461 A CN111755461 A CN 111755461A CN 202010231299 A CN202010231299 A CN 202010231299A CN 111755461 A CN111755461 A CN 111755461A
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acid
copper
based metal
metal film
film
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CN111755461B (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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    • 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 solution composition used for the same, wherein the copper-based metal film etching solution composition comprises hydrogen peroxide; a fluorine-containing compound or an inorganic acid; an azole compound; an organic acid; a citrate salt; one or more of sulfate and phosphate; a polyol-type surfactant; and water, wherein the method for manufacturing the array substrate for the liquid crystal display device is capable of etching the copper-based metal film at a time without damaging the oxide semiconductor layer by forming the source/drain electrodes by etching the copper-based metal film using the etching solution composition.

Description

Method for manufacturing array substrate for liquid crystal display device and copper-based metal film etching solution composition used 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 solution composition used for the same.
Background
As the information age has formally entered, the field of displays for processing and displaying a large amount of information has been rapidly developed, and accordingly, various flat panel displays have been developed and paid attention to.
Examples of such flat Panel Display devices include Liquid crystal Display devices (LCDs), Plasma Display devices (PDPs), Field Emission Display devices (FEDs), electroluminescent Display devices (ELDs), Organic light emitting Display devices (OLEDs), and the like, and such flat Panel Display devices are used in various applications in the fields of televisions, video recorders, and the like, and in computers such as notebooks, mobile phones, and the like. In fact, these flat panel display devices are rapidly replacing the conventional Cathode Ray Tube (NIT) due to excellent performance such as reduction in thickness, weight, and power consumption.
In a liquid crystal display device, a process of forming metal wiring on a substrate generally includes steps using: a metal film formation step by sputtering or the like; a photoresist forming step in a selective area by photoresist coating, exposure and development; and an etching step, and includes a cleaning step before and after the individual unit step. Such an etching step is a step of leaving a metal film in a selective region using a photoresist as a mask, and dry etching using plasma or wet etching using an etchant composition is generally used.
In such a liquid crystal display device, attention has been paid mainly to the resistance of metal wiring in recent years. This is because resistance is a main factor inducing RC signal delay, and in a thin film transistor-liquid crystal display (TFT-LCD), it is essential to increase the panel size and realize high resolution to solve the RC signal delay problem. Therefore, in order to reduce the RC signal delay required when the TFT-LCD is increased in size, it is necessary to develop a low-resistance material.
Chromium (Cr, resistivity: 12.7 × 10) mainly used in the past-8Ω m), molybdenum (Mo, resistivity: 5 × 10-8Ω m), aluminum (Al, resistivity: 2.65 × 10-8Ω m) and their alloys have a large resistance, and thus are difficult to be used for gate wirings, data wirings, and the like used in large-sized TFT-LCDs. Therefore, copper-based metal films such as copper films and copper molybdenum films, which are low-resistance metal films, and etching solution compositions therefor have attracted attention. However, the copper-based metal film etching solution compositions known so far have not yet satisfied the performance required by users, and therefore 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 solution 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 solution composition, when an oxide semiconductor is used as a semiconductor layer, there are problems as follows: in the process, the etchant composition is concentrated by the exhaust gas, and the degree of damage of the oxide semiconductor changes, making it difficult to control the process, and thus it is difficult to maintain the performance of the liquid crystal display device.
Documents of the prior art
Patent document
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 collectively etching a copper-based metal film 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 the substrate including the gate electrode; c) forming an oxide semiconductor layer (IGZO) on the gate insulating layer; d) forming source/drain electrodes on the oxide semiconductor layer; and e) forming a pixel electrode connected to the source/drain electrode, wherein 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 containing hydrogen peroxide to form the source/drain electrode; a fluorine-containing compound or an inorganic acid; an azole compound; an organic acid; a citrate salt; one or more of sulfate and phosphate; a polyol-type surfactant; and water.
In addition, the present invention provides a copper-based metal film etching solution composition comprising (A) 5.0 to 30.0 wt% of hydrogen peroxide, based on the total weight of the composition; (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 wt% of citrate; (F) 0.01-5 wt% of one or more of sulfate and phosphate; (G) 0.001 to 5.0 wt% of a polyol-type 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 reduce the occurrence of a tip (tip) of a molybdenum film or a molybdenum alloy film including a copper-based metal film by collectively etching the copper-based metal film without damaging the oxide semiconductor layer using an etchant composition having an excellent etching profile and etching straightness, and has an effect of suppressing a change in Side etching (Side etch) by reducing a change in a Damage rate (Damage rate) of the oxide semiconductor layer due to outgassing during etching using a device, thereby facilitating control of a process.
Detailed Description
The present invention relates to compositions comprising hydrogen peroxide; a fluorine-containing compound or an inorganic acid; an azole compound; an organic acid; a citrate salt; one or more of sulfate and phosphate; a polyol-type surfactant; and an etchant composition for water, and a method for manufacturing an array substrate for a liquid crystal display device using the etchant composition, which can etch a copper-based metal film without damaging an oxide semiconductor layer at a time, have excellent etching profile and etching straightness, reduce the occurrence of a sharp edge of a molybdenum film or a molybdenum alloy film including the copper-based metal film, and suppress a change in undercut due to a low amount of change in the damage rate of the oxide semiconductor layer caused by outgassing during etching using a device, thereby providing an effect of facilitating the control of a process.
The structure 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 the substrate including the gate electrode; c) forming an oxide semiconductor layer (IGZO) on the gate insulating layer; d) forming source/drain electrodes on the oxide semiconductor layer; and e) forming a pixel electrode connected to the source/drain electrode, wherein 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 containing hydrogen peroxide to form the source/drain electrode; a fluorine-containing compound or an inorganic acid; an azole compound; an organic acid; a citrate salt; one or more of sulfate and phosphate; a polyol-type surfactant; and water.
The copper-based metal film is a metal film containing copper in a film constituent component, and specifically may contain a single-layer film composed of copper or a copper alloy, or a multilayer film such as a two-layer film and a three-layer film composed of 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, a copper film-molybdenum alloy film, a copper alloy film-molybdenum film, and a copper alloy film-molybdenum alloy film as a double layer film, and a molybdenum film-copper film-molybdenum film, a molybdenum alloy film-copper film-molybdenum alloy film, a molybdenum film-copper alloy film-molybdenum film, a molybdenum alloy film-copper alloy film-molybdenum alloy film, a molybdenum film-copper film-molybdenum alloy film, a molybdenum alloy film-copper film-molybdenum film, a molybdenum film-copper alloy film-molybdenum alloy film, and a molybdenum alloy film-copper alloy film-molybdenum film as a triple layer film.
The alloy film may be an alloy film of copper or molybdenum and one or more selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), or the like, or may be a nitride film or an oxide film of copper or molybdenum.
When the copper-based metal film is etched using the etchant composition of the present invention, the copper-based metal film can be etched at once without damaging (dam) the oxide semiconductor layer.
In one embodiment of the etching solution composition of the present invention, hydrogen peroxide; a fluorine-containing compound; an azole compound; an organic acid; a citrate salt; one or more of sulfate and phosphate; a polyol-type surfactant; and water, preferably containing hydrogen peroxide as another embodiment of the etching solution composition of the present invention; an inorganic acid; an azole compound; an organic acid; a citrate salt; one or more of sulfate and phosphate; a polyol-type surfactant; and water.
Hereinafter, the etching liquid composition of the present invention will be described in detail.
< copper-based Metal film etching solution composition >
The copper-based metal film etchant composition of the present invention may contain hydrogen peroxide; a fluorine-containing compound or an inorganic acid; an azole compound; an organic acid; a citrate salt; one or more of sulfate and phosphate; a polyol-type surfactant; and water.
In one embodiment of the etching solution composition of the present invention, hydrogen peroxide; a fluorine-containing compound; an azole compound; an organic acid; a citrate salt; one or more of sulfate and phosphate; a polyol-type surfactant; and water, preferably containing hydrogen peroxide as another embodiment of the etching solution composition of the present invention; an inorganic acid; an azole compound; an organic acid; a citrate salt; one or more of sulfate and phosphate; a polyol-type surfactant; and water.
(A) Hydrogen peroxide
The hydrogen peroxide (H) contained in the etchant composition of the present invention2O2) Can be used as a main oxidant for the copper-based metal film.
The content of the hydrogen peroxide may be 5.0 to 30.0 wt%, preferably 8.0 to 25.0 wt%, based on the total weight of the composition. When the content of the 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 is entirely increased, so that the process control is difficult.
(B-1) fluorine-containing Compound
The fluorine-containing compound contained in the etching liquid composition of the present invention is a compound that can dissociate in water to release fluorine ions. The fluorine-containing compound is a main component for etching the copper-based metal film, and plays a role of removing a residue 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 that can be dissociated into fluoride ions or polyatomic fluoride ions in a solution as a substance used in the art, and is preferably selected from ammonium fluoride (NH)4F) Sodium fluoride (sodium fluoride: NaF), potassium fluoride (potassium fluoride: KF), ammonium bifluoride (ammonium bifluoride: NH (NH)4F · HF), sodium hydrogen fluoride (sodium bifluoride: NaF · HF) and potassium hydrogen fluoride (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, preferably 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 is lowered and etching residue may be generated, and when the content is more than 1.0 wt%, there is a problem that the etching rate of the oxide semiconductor layer under the copper-based metal film becomes large.
(B-2) inorganic acid
The inorganic acid contained in the etching solution composition of the present invention can be used as an auxiliary oxidant for the copper-based metal film. When the etching solution composition does not contain the inorganic acid, there is a problem that the etching rate is decreased and the process time is increased. Further, if the etching rate of the molybdenum film or the molybdenum alloy film is decreased, a defect may be induced in a subsequent process if a tip of the molybdenum film or the molybdenum alloy film is generated on the copper-based metal film.
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% by weight, preferably 0.005 to 0.5% by weight, based on the total weight of the composition. When the content of the inorganic acid is less than 0.001 wt%, the etching rate decreases and the process time increases, and when the content is more than 1.0 wt%, the etching rate of the copper film or the copper alloy film may be 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 is located on the copper film or the copper alloy film.
(C) Azole compounds
The azole compound contained in the etchant composition of the present invention functions to adjust the etching rate and reduce the variation in etching (Etch) profile due to the number of processed sheets, thereby improving the process margin (process margin).
In one or more embodiments, the azole compound may be selected from the group consisting of pyrrole (pyrrole) based compounds; pyrazole (pyrazol) based compounds; imidazole-based compounds including imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole, 4-propylimidazole and the like; triazole (triazole) compounds including benzotriazole (benzotriazole), tolyltriazole (tolyltriazole), and methyltriazole; tetrazole-based formulations including aminotetrazole and methyltetrazoleA compound; a pentazole (pentazole) based compound;
Figure BDA0002429367310000061
azole (oxazole) compounds; different from each other
Figure BDA0002429367310000062
Azole (isoxazole) -based compounds; more than one of the group consisting of thiazole (thiazole) compounds and isothiazole (isothiazole) compounds, preferably tetrazole (tetrazole) compounds.
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 may be increased to cause an excessive CD Loss (CD Loss), and when the content is more than 2.0 wt%, the etching rate of the copper-based metal film may be too slow to generate an etching residue.
(D) Organic acids
The organic acid contained in the etchant composition of the present invention is an agent for increasing the number of processed sheets, and can function to chelate copper ions and increase the number of processed sheets 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, ethylenediaminetetraacetic 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 may be one or more selected from the group consisting of citric acid, gluconic acid, and iminodiacetic acid.
The organic acid may be contained in an amount of 1.0 to 10.0 wt%, preferably 2.0 to 7.0 wt%, based on 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 lowered and etching residue may be generated as the number of processed sheets increases, and when the content is more than 10.0 wt%, over-etching of the copper-based metal film may be caused.
(E) Citric acid salt
The citrate contained in the etching solution composition of the present invention assists the action of the organic acid to chelate copper ions to suppress the decomposition reaction of hydrogen peroxide. In addition, when the copper-based metal film is etched by using a device, the citrate may play a role of minimizing a change in etching characteristics of the etchant composition due to concentration of the etchant composition by exhaust gas. In the case where the etching liquid composition does not contain the above citrate, the change in the etching Rate (Etch Rate) increases as the exhaust time increases, and thus the Rate of change in the undercut (SideEtch) may become large.
In one embodiment, the Citrate may be one or more selected from the group consisting of Monosodium Citrate (Monosodium Citrate), Disodium Citrate (Disodium Citrate), and trisodium Citrate (trisodium Citrate), preferably trisodium Citrate, in the form of a salt of citric acid.
The content of the citrate may be 0.1 to 5.0% by weight, preferably 0.5 to 3% by weight, 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 may increase and the element characteristics may be degraded as the exhaust time increases, and when the content is more than 5.0 wt%, the etching rate of the copper film may decrease due to the increase in pH, which makes the process difficult.
When the citrate is used in the above range, the damage rate of the oxide semiconductor layer is maintained constant even if the exhaust time is increased, and thus, even if the process is performed, the characteristics of the element are not degraded, and the process is easily controlled.
(F) One or more 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 a molybdenum film or a molybdenum alloy film, and a fine pattern can be realized by adjusting the etching rate. In particular, when the copper-based metal film is configured as a multilayer film, the etching rates of the upper and lower metal films of the multilayer film can be compatible, and a fine pattern can be realized.
The sulfate is not particularly limited as long as it is selected from salts in which one or two hydrogens of sulfuric acid are replaced with ammonium, an alkali metal, or an alkaline earth metal, and for example, one or more selected from the group consisting of ammonium sulfate, ammonium persulfate, sodium sulfate, sodium persulfate, potassium sulfate, and potassium persulfate may be used, and sodium sulfate may be used preferably.
The phosphate may be, for example, one or more 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 wt%, preferably 0.01 to 1.0 wt%, based on the total weight of the etching solution 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, it is possible to prevent the copper film or the copper alloy film from being excessively etched to form a stepped tapered profile during the etching of the molybdenum film or the molybdenum alloy film. 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 is serious and the line width is narrowed, so that the resistance is increased and the advantage of the low-resistance metal is lost.
(G) Polyol-type surfactant
The polyol-type surfactant contained in the etching solution composition of the present invention reduces surface tension to improve etching uniformity. Further, the polyol-type surfactant can surround copper ions dissolved in the etching solution 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 reduced, the process can be stably performed during the use of the etching solution composition.
In one embodiment, the polyol-type surfactant may be one or more selected from the group consisting of glycerol (glycerin), diethylene glycol (diethylene glycol), triethylene glycol (triethylene glycol), tetraethylene glycol (tetraethylene glycol), and polyethylene glycol (polyethylene glycol), and more preferably, is one or more selected from the group consisting of triethylene glycol, diethylene glycol, and tetraethylene glycol.
The content of the polyol-type surfactant may be 0.001 to 5.0% by weight, preferably 0.1 to 3.0% by weight, based on the total weight of the composition. When the content of the polyol-type surfactant is less than 0.001 wt%, etching uniformity may be reduced, and decomposition of the hydrogen peroxide may be accelerated, and when the content is more than 5.0 wt%, a large amount of bubbles may be generated.
(H) Water (W)
The water contained in the copper-based metal film etching solution composition of the present invention may be deionized water for a semiconductor process, and preferably the deionized water is 18M Ω · cm or more.
The water may be contained in an amount such that the balance is 100 wt% based on the total weight of the composition. Specifically, in the present invention, "the balance" means a balance of 100% by weight based on the total weight of the composition containing the essential components of the present invention and other additional components, and the composition of the present invention does not contain any additional components in view of the "balance".
The present invention will be described in more detail below with reference to examples. However, the following examples are intended to explain the present invention more specifically, and the scope of the present invention is not limited to the following examples. The scope of the present invention is indicated by the appended 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 "part(s)" representing the content are based on mass unless otherwise mentioned.
Production of copper-based Metal film etching solution compositions of examples and comparative examples
The copper-based metal film etching solution compositions of examples and comparative examples were produced with reference to the following [ table 1 ].
[ Table 1]
(unit: wt%)
Figure BDA0002429367310000091
(A) The method comprises the following steps Hydrogen peroxide
(B-1): ammonium fluoride
(B-2): nitric acid
(C) The method comprises the following steps Methyl tetrazole
(D1) The method comprises the following steps Glycolic acid
(D2) The method comprises the following steps Citric acid
(D3) The method comprises the following steps Iminodiacetic acid
(E1) The method comprises the following steps Trisodium citrate
(E2) The method comprises the following steps Monosodium citrate
(E3) The method comprises the following steps Citric acid disodium salt
(F1) The method comprises the following steps Sodium sulfate
(F2) The method comprises the following steps Ammonium dihydrogen phosphate
(G) The method comprises the following steps Triethylene glycol
Test example 1: evaluation of etching Profile and etching straightness
A Mo — Ti film was deposited on an IGZO Active layer (Active layer) on a glass substrate (100 mm × 100 mm), a copper film was deposited on the Mo — Ti film, and then a photoresist having a predetermined pattern was formed on the substrate through a photolithography (photolithography) process. Then, the etching step was performed on the Cu/Mo — Ti bilayer film using the etching solution compositions of examples and comparative examples, respectively.
In the etching step, a spray etching system (model name: ETCHER (TFT), SEMES) was used, and the temperature of the etching solution composition was about 32 ℃ and the etching time was 150 seconds. The cross section of the copper-based metal film etched by the etching step was photographed by SEM (Hitachi product, model name S-4700), and evaluated according to the following evaluation criteria, and the results are shown in table 2 below.
< evaluation criteria of etching Profile >
O: the cone angle is more than 30 degrees and less than 65 degrees
And (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: the cone angle being less than 25 DEG or greater than 70 DEG
Untech: fail to etch
< evaluation criteria for etching straightness >
O: the pattern being formed in straight lines
And (delta): the pattern has a curve form of 20% or less
X: the curve form in the pattern is more than 20%
Untech: fail to etch
Test example 2: damage rate (Damage) of oxide semiconductor layer (IGZO) according to exhaust time Rate) change Quantity measurement
The copper-based metal film was etched by the same etching process as in test example 1, and the amount of change in the damage ratio of the oxide semiconductor layer (IGZO) immediately after 72 hours from the production of the etching liquid composition was measured, and the results are shown in table 2 below.
[ Table 2]
Figure BDA0002429367310000111
When the etching process was performed using the copper-based metal film etchant composition of the example, it was confirmed that the etching profile, the etching straightness, and the damage rate change characteristics of IGZO with time of exhaustion were all excellent.
On the other hand, when the etching process was carried out using the copper-based metal film etchant composition of comparative example, it was confirmed that the etching profile and etching straightness were poor, and the change amount of the damage rate of IGZO with change in exhaust time exceeded that of IGZO
Figure BDA0002429367310000112
sec, it is difficult to control the process, and the characteristics of the device are deteriorated.

Claims (13)

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 the 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 source/drain electrodes on the oxide semiconductor layer; and
e) a step of forming a pixel electrode connected to the source/drain electrodes,
in the step d), a copper-based metal film is formed on the oxide semiconductor layer, and the source/drain electrodes are formed by etching the copper-based metal film using an etchant composition containing hydrogen peroxide; a fluorine-containing compound or an inorganic acid; an azole compound; an organic acid; a citrate salt; one or more 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 solution composition comprises the following components by weight:
(A) 5.0 to 30.0 wt% 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 wt% of citrate;
(F) 0.01-5 wt% of one or more of sulfate and phosphate;
(G) 0.001 to 5.0 wt% of a polyol-type surfactant; and
(H) and (3) water.
5. The copper-based metal film etching solution composition according to claim 4, wherein the copper-based metal film is a single-layer film composed of copper or a copper alloy, or a multilayer film comprising the single-layer film and a molybdenum-based single-layer film composed of molybdenum or a molybdenum alloy.
6. The copper-based metal film etchant composition according to claim 4, wherein the fluorine-containing compound is selected from the group consisting of ammonium fluoride (NH)4F) Sodium fluoride (NaF), potassium fluoride (KF), ammonium hydrogen fluoride (NH)4F & HF), sodium hydrogen fluoride (NaF & HF), and potassium hydrogen fluoride (KF & HF).
7. The copper-based metal film etchant composition according to claim 4, wherein the inorganic acid is one or more selected from the group consisting of nitric acid, sulfuric acid and phosphoric acid.
8. The copper-based metal film etchant composition according to claim 4, wherein the azole compound is selected from the group consisting of an azole compound, a pyrazole compound, an imidazole compound, a triazole compound, a tetrazole compound, a pentazole compound, a hexamidine compound, a perylene,
Figure FDA0002429367300000021
Azole compound, isozyme
Figure FDA0002429367300000022
One or more compounds selected from the group consisting of azole compounds, thiazole compounds and isothiazole compounds.
9. The copper-based metal film etchant composition according to claim 4, wherein the organic acid is at least one selected from the group consisting of acetic acid, iminodiacetic acid, ethylenediaminetetraacetic 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 solution composition according to claim 4, wherein the citrate comprises one or more selected from the group consisting of monosodium citrate, disodium citrate, and trisodium citrate.
11. The copper-based metal film etchant composition according to claim 4, wherein the sulfate is one or more selected from the group consisting of ammonium sulfate, ammonium persulfate, sodium sulfate, sodium persulfate, potassium sulfate, and potassium persulfate.
12. The copper-based metal film etching solution composition according to claim 4, wherein the phosphate is one or more selected from the group consisting of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
13. The copper-based metal film etchant composition according to claim 4, wherein the polyol-type surfactant comprises one or more selected from the group consisting of glycerol, diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycol.
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