CN109385634B - Metal film etching liquid composition and conductive pattern forming method using the same - Google Patents

Metal film etching liquid composition and conductive pattern forming method using the same Download PDF

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CN109385634B
CN109385634B CN201810813657.8A CN201810813657A CN109385634B CN 109385634 B CN109385634 B CN 109385634B CN 201810813657 A CN201810813657 A CN 201810813657A CN 109385634 B CN109385634 B CN 109385634B
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acid
film
etching
metal film
transparent conductive
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CN109385634A (en
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田玹守
沈庆辅
尹暎晋
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/02—Local etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material
    • 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
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
    • 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
    • G02F1/136286—Wiring, e.g. gate line, drain line
    • 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
    • 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier 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
    • H01L27/124—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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier 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 with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits
    • 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
    • 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier 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 at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier 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
    • H01L27/1296—Multistep manufacturing methods adapted to increase the uniformity of device parameters
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/131—Interconnections, e.g. wiring lines or terminals

Abstract

The invention provides a metal film etching solution composition and a conductive pattern forming method using the same, wherein the metal film etching solution composition comprises an etching initiator, an inorganic acid, an organic acid, a polyalcohol profile improving agent and the balance of water, and has the pH value of less than 2. By using the metal film etching liquid composition, a fine conductive pattern with reduced etching failure can be formed.

Description

Metal film etching liquid composition and conductive pattern forming method using the same
Technical Field
The present invention relates to a metal film etchant composition and a method for forming a conductive pattern using the same. More particularly, the present invention relates to a metal film etching solution composition containing an acid component and a method for forming a conductive pattern using the same.
Background
For example, a Thin Film Transistor (TFT) is used as a part of a driver circuit of a semiconductor device or a display device. TFTs are arranged for each pixel on a substrate of an Organic Light Emitting Display (OLED) device or a Liquid Crystal Display (LCD), for example, and wirings such as a pixel electrode, a counter electrode, a source electrode, a drain electrode, a data line, and a power line may be electrically connected to the TFTs.
In order to form the electrodes or the wirings, a metal film may be formed on a display substrate, and after a photoresist is formed on the metal film, the metal film may be partially removed using an etchant composition.
In order to reduce wiring resistance, prevent signal propagation delay, and ensure chemical resistance and stability of wiring, the metal film may be formed as a multilayer film including dissimilar metals or dissimilar conductive substances having different chemical characteristics from each other.
For example, a silver (Ag) -containing film may be formed to exhibit low resistance characteristics, and a transparent conductive Oxide film such as Indium Tin Oxide (ITO) may be additionally formed to improve chemical resistance, stability and transmittance.
As disclosed in Korean patent application No. 10-0579421, the etching solution composition uses an inorganic strong acid such as phosphoric acid or sulfuric acid as a basic component. However, when the inorganic strong acid is used, defects such as uneven etching profile, over-etching (over-etching), and over-hanging (over-hanging) due to a difference in etching rate between different conductive films may be caused, and it is difficult to adjust the etching rate for forming a fine pattern.
Documents of the prior art
Patent document
Korean registered patent publication No. 10-0579421 (2006.05.08.)
Disclosure of Invention
Problems to be solved
An object of the present invention is to provide a metal film etching solution composition having improved etching uniformity and high resolution.
An object of the present invention is to provide a method for forming a conductive pattern using the metal film etchant composition.
An object of the present invention is to provide a method for manufacturing a display substrate using the metal film etchant composition.
Means for solving the problems
1. A metal film etching solution composition which comprises an etching initiator, an inorganic acid, an organic acid, a polyhydric alcohol-based profile-improving agent and the balance of water and has a pH of 2 or less.
2. The metal film etching solution composition as set forth in claim 1, wherein the etching initiator contains at least one selected from the group consisting of a peroxide sulfide, hydrogen peroxide, persulfate and a peroxynitrate.
3. The composition for etching a metal film as described in claim 2, wherein the etching initiator comprises oxone.
4. The metal film etchant composition according to claim 1, wherein the inorganic acid comprises nitric acid.
5. The metal film etchant composition according to claim 1, wherein the organic acid comprises a first organic acid and a second organic acid that is weaker in acidity than the first organic acid.
6. The metal film etchant composition according to claim 5, wherein the first organic acid comprises acetic acid,
the second organic acid includes at least one selected from the group consisting of iminodiacetic acid (IDA), ethylenediaminetetraacetic acid (EDTA), glycine (glycine), salicylic acid (salicylic acid), citric acid (citric acid), formic acid (formic acid), oxalic acid (oxalic acid), malonic acid (malonic acid), succinic acid (succinic acid), butyric acid (butyric acid), gluconic acid (gluconic acid), glycolic acid (glycolic acid), and valeric acid (valeric acid).
7. The metal film etchant composition according to claim 1, wherein the polyol-based profile improver comprises at least one selected from the group consisting of glycerol (glycerin), ethylene glycol (ethylene glycol), diethylene glycol (diethylene glycol), triethylene glycol (triethylene glycol), and polyethylene glycol (polyethylene glycol).
8. The metal film etchant composition according to claim 1, further comprising a metal salt.
9. The metal film etchant composition according to claim 8, wherein the metal salt comprises at least one selected from the group consisting of ferric nitrate (ferricnitrate), sodium nitrate (sodium nitrate) and potassium nitrate (potassium nitrate).
10. The metal film etching solution composition as described in claim 1, comprising, based on the total weight of the composition:
1 to 20 wt% of the etching initiator; 1-15 wt% of the inorganic acid; 0.1 to 20 wt% of the organic acid; 1 to 20 wt% of the polyol profile improver; and the balance water.
11. The metal film etchant composition as described in claim 10, further comprising 0.1 to 5 wt% of a metal salt.
12. The metal film etchant composition according to claim 1, which does not contain phosphoric acid or a phosphoric acid-based compound.
13. A conductive pattern forming method, comprising:
a step of forming a metal film on a substrate; and
etching the metal film using the metal film etchant composition according to any one of 1 to 12.
14. The conductive pattern forming method according to claim 13, wherein the step of forming the metal film includes a step of forming a silver-containing film.
15. The method of forming a conductive pattern according to claim 14, wherein the step of forming the metal film further comprises a step of forming a transparent conductive oxide film.
16. The method of forming a conductive pattern according to claim 15, wherein the transparent conductive oxide film includes a first transparent conductive oxide film and a second transparent conductive oxide film formed through the silver-containing film.
17. The method of forming a conductive pattern according to claim 15, wherein the transparent conductive oxide film comprises at least one selected from the group consisting of Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), Indium Tin Zinc Oxide (ITZO), Gallium Zinc Oxide (GZO), and Indium Gallium Zinc Oxide (IGZO).
18. The conductive pattern forming method of claim 13, further comprising: forming a thin film transistor on the substrate; forming a pixel electrode electrically connected to the thin film transistor; and forming a display layer on the pixel electrode, wherein the metal film is formed on the display layer.
19. The conductive pattern forming method according to claim 18, wherein the conductive pattern is provided as a common electrode, a reflective electrode, or a wiring of the image display device.
Effects of the invention
The metal film etchant composition according to the embodiment of the present invention may include an etching initiator, an inorganic acid, an organic acid, and a polyol profile improver, and have a pH of 2 or less. In the pH range, the etching rate and the etching efficiency can be improved, and the etching uniformity on the sidewall of the conductive pattern can be improved by the action of the organic acid and the polyol profile improver.
According to an exemplary embodiment, the inorganic acid includes nitric acid, and since the content of strong acid such as phosphoric acid, sulfuric acid, or the like is excluded or reduced, etching characteristic adjustment for forming a fine pattern can be achieved.
In addition, in the case where the metal film includes a silver-containing film and a transparent conductive oxide film, the etching initiator can initiate a metal oxide substitution reaction, and the silver-containing film and the transparent conductive oxide film are simultaneously and uniformly etched. In this case, the etching uniformity of the silver-containing film and the transparent conductive oxide film can be further improved.
By using the etching solution composition, for example, an electrode or wiring such as a reflective electrode of a display device, a sensing electrode of a touch sensor, a trace, a pad, or the like can be formed to have a desired aspect ratio and profile.
Drawings
Fig. 1 and 2 are sectional views of a conductive pattern forming method for illustrating an exemplary embodiment.
Fig. 3 is a sectional view for explaining a method of manufacturing a display substrate of an exemplary embodiment.
Description of the symbols
100. 200: substrate 110: lower insulating film
115: lower conductive pattern 120: metal film
120 a: conductive pattern 121: a first transparent conductive oxide film
122. 262, 272: a first transparent conductive oxide film pattern
123: silver-containing films 124, 264, 274: silver-containing pattern
125: second transparent conductive oxide film
126. 266, 276: second transparent conductive oxide film pattern
210: active layer 225: gate electrode
233: source electrode 237: drain electrode
245: pixel electrode 260: counter electrode
270: wiring harness
Detailed Description
According to an embodiment of the present invention, there is provided a metal film etching liquid composition (hereinafter, simply referred to as "etching liquid composition") including an etching initiator, an inorganic acid, an organic acid, and a polyol-based profile improver, and having a pH of 2 or less. Also provided are a method for forming a conductive pattern using the metal film etchant composition and a method for manufacturing a display substrate.
The term "metal film" used in the present application is used as a term including a metal single layer film and a laminated structure of the metal single layer film and a transparent conductive oxide film. Further, the metal film may include a plurality of metal single layer films formed of different metals.
In an exemplary embodiment, the metal film may include a silver-containing film. The silver-containing film may be a film containing silver or a silver alloy. The silver-containing film may have a multilayer structure having 2 or more layers.
For example, the silver alloy may include: neodymium (Nd), copper (Cu), palladium (Pd), niobium (Nb), nickel (Ni), molybdenum (Mo), chromium (Cr), magnesium (Mg), tungsten (W), protactinium (Pa), titanium (Ti), or an alloy of two or more thereof with silver (Ag); silver compounds containing doping elements such as nitrogen (N), silicon (Si), and carbon (C); or a combination of two or more thereof.
The transparent conductive oxide film may contain a transparent metal oxide. For example, the transparent metal oxide may include Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), Indium Tin Zinc Oxide (ITZO), Gallium Zinc Oxide (GZO), Indium Gallium Zinc Oxide (IGZO), or a combination thereof.
Hereinafter, examples of the present invention will be described in detail, and a case where the metal film includes a silver-containing film and a transparent conductive oxide film will be described as an example. However, this is a preferable example, and the spirit and scope of the present invention are not necessarily limited thereto.
< etching solution composition >
The etching initiator contained in the etching solution composition according to the embodiment of the present invention may be provided as a component capable of promoting the etching rate of silver (Ag) or the like and improving the etching uniformity. The component may be contained as a component that promotes etching by inducing or inducing a metal substitution reaction with respect to the transparent conductive oxide film having relatively low oxidation/reduction characteristics compared to silver.
In addition, the content of the inorganic acid can be relatively reduced by including the etching initiator to promote the activity of the inorganic acid described later. Therefore, overetching, etching unevenness, and the like caused when an excessive amount of the inorganic acid is contained can be suppressed.
According to an exemplary embodiment, the above-mentioned etching initiator may comprise a peroxide sulfide, hydrogen peroxide, persulfate and/or peroxynitrite, and preferably may comprise a peroxide sulfide such as oxone.
As the persulfate, potassium persulfate (K) can be used2S2O8) Sodium persulfate (Na)2S2O8) And ammonium persulfate ((NH)4)2S2O8) The peroxynitrate salt may be potassium peroxynitrate (KNO)4) Sodium peroxynitrate (NaNO)4) And ammonium Nitrate (NH)4NO4) At least one substance of (1).
In some embodiments, the etching initiator may be present in an amount of 1 to 20 wt% based on the total weight of the composition. If the content of the etching initiator is less than 1% by weight, the etching rate may be excessively decreased to cause uneven etching. In addition, wiring short-circuiting due to silver residue may occur, and the etching promoting effect of the transparent conductive oxide film may be insignificant. In the case where the content of the etching initiator exceeds 20% by weight, the oxidation action of the inorganic acid may be adversely inhibited.
In one embodiment, the content of the etching initiator may be adjusted to 3 to 10% by weight in order to minimize a difference in etching rate between the silver-containing film and the transparent conductive oxide film and to achieve excellent etching uniformity.
The inorganic acid may interact with the etching initiator to function as an oxidizing agent. For example, the inorganic acid can function as a main oxidant for a transparent conductive oxide film such as ITO. The inorganic acid acts together with the etching initiator, whereby the silver-containing film and the transparent conductive oxide film can be uniformly etched at the same time.
According to an exemplary embodiment, the inorganic acid may include nitric acid. In some embodiments, the inorganic acid may also include a nitrate. Examples of the nitrate include sodium nitrate (sodium nitrate), potassium nitrate (potassium nitrate), ammonium nitrate (ammonium nitrate), and the like. These may be used alone or in combination of two or more.
In some embodiments, the inorganic acid may be present in an amount of 1 to 15 wt% based on the total weight of the composition. When the content of the inorganic acid is less than 1% by weight, the etching rate is excessively decreased, and a short circuit of a wiring due to, for example, ITO residue or silver residue may be caused. Further, black spots (dark spots) may be generated due to the ITO residues or silver residues. If the content of the inorganic acid exceeds 15 wt%, poor etching control of the metal film such as overetching may occur.
In one embodiment, the content of the inorganic acid may be adjusted to 3 to 10% by weight in consideration of uniform etching rate and control characteristics of the silver-containing film and the transparent conductive oxide film.
The organic acid may be included, for example, in order to appropriately accelerate or adjust the etching rate of the silver-containing film, thereby reducing the critical dimension Loss (CD Loss) of the obtained conductive pattern and accelerating the formation of a fine pattern.
In some embodiments, the organic acid may include a first organic acid and a second organic acid that is weaker in acidity than the first organic acid.
For example, the first organic acid may include acetic acid and may function as a co-oxidant or a main oxidant for silver. The above-mentioned second organic acid may include iminodiacetic acid (IDA), ethylenediaminetetraacetic acid (EDTA), glycine (glycine), salicylic acid (salicylic acid), citric acid (citric acid), formic acid (formic acid), oxalic acid (oxalic acid), malonic acid (malonic acid), succinic acid (succinic acid), butyric acid (butyric acid), gluconic acid (gluconic acid), glycolic acid (glycolic acid), valeric acid (valeric acid), and the like. These may be used alone or in combination of two or more.
The second organic acid can function as an etching profile accelerator. By suppressing or controlling a part of the oxidation caused by the first organic acid by using the second organic acid, the CD loss or CD variation of the conductive pattern can be significantly reduced.
In some embodiments, the organic acid may be present in an amount of 0.1 to 20 wt% based on the total weight of the composition. In the case where the content of the above organic acid is less than 0.1 wt%, the CD loss of the conductive pattern may increase. In the case where the content of the organic acid exceeds 20% by weight, the stability of the composition with time may be lowered.
In view of the improvement of the profile characteristics of the conductive pattern, in a preferred embodiment, the organic acid may be contained in an amount of 10 to 20 wt%.
In an exemplary embodiment, the polyol profile improver may further finely control an etching profile of the conductive pattern.
For example, since the polyol profile improver contains a plurality of hydroxyl groups, the pH of the etching liquid composition can be slightly increased, and overetching and tip (tip) phenomena can be suppressed. The polyol profile improver can function as a surfactant of the etching solution composition or a surface protecting agent for a conductive pattern, thereby suppressing pattern loss.
The polyhydric alcohol-based profile-improving agent may include, for example, glycerin (glycerol), ethylene glycol (ethylene glycol), diethylene glycol (diethylene glycol), triethylene glycol (triethylene glycol), polyethylene glycol (polyethylene glycol), and the like. They may be used alone or in combination of two or more
Preferably, in order to prevent the etching performance of the composition from being excessively hindered, a diol compound may be used as the polyol profile improver.
In some embodiments, the polyol profile improver may be present in an amount of 1 to 20 wt% based on the total weight of the composition. When the content of the polyol profile improver is less than 1% by weight, sufficient surface protection and pH adjustment functions may not be achieved, and when the content exceeds 20% by weight, etching performance may be excessively inhibited or the pH of the composition may excessively increase.
In one embodiment, the content of the polyol profile improver may be adjusted to 1 to 10% by weight in order to achieve fine adjustment of etching characteristics.
In some exemplary embodiments, the etching solution composition may further include a metal salt. The metal salt may be additionally included in order to further improve the etching uniformity of the silver-containing film and the transparent conductive oxide film. For example, the metal salt can prevent the etching rate of the transparent conductive oxide film from decreasing by removing or dissociating a natural oxide film of silver formed on the surface of the transparent conductive oxide film by desorption from the silver-containing film. Further, the metal salt can improve the overall etching rate while maintaining the etching uniformity.
In some embodiments, the metal salt may further include a metal nitrate, for example, iron nitrate (ferric nitrate), sodium nitrate (sodium nitrate), potassium nitrate (potassium nitrate), or the like. Preferably, iron nitrate may be used.
In some embodiments, the metal salt may be present in an amount of 0.1 to 5 wt% based on the total weight of the composition. When the content of the metal salt is less than 0.1 wt%, silver may be re-adsorbed on the transparent conductive oxide film, and when the content exceeds 5 wt%, the etching rate of the silver-containing film is excessively increased, which may cause over-etching or a spiking phenomenon.
In view of uniform etching of the silver-containing film and the transparent conductive oxide film, the content of the metal salt is preferably 0.1 to 3% by weight.
The etching solution composition may contain water in a balance other than the above components, and may contain deionized water, for example. In the case of the above deionized water, for example, the resistivity value may be 18M Ω/cm or more.
The term "balance" used in the present application means, in the case where other additives are contained, a variable amount including an amount other than the above components and the above additives.
In some embodiments, the additive may be included within a range that does not inhibit the action of the component in order to improve etching efficiency or etching uniformity. For example, the additive may include agents widely used in the art for preventing corrosion, preventing adsorption of etching byproducts, adjusting the taper angle of an etched pattern, and the like.
In some embodiments, the etching solution composition may substantially include the etching initiator, an inorganic acid, an organic acid, a polyol profile improver, a metal salt, and water.
In some embodiments, the etchant composition may not include phosphoric acid or a phosphoric acid-based compound (e.g., a phosphate). In the case of the phosphoric acid or the phosphoric acid-based compound, there is a possibility that loss due to over-etching of the metal film, damage of a lower structure, re-adsorption of silver, and the like are caused. In the case of the phosphoric acid or the phosphoric acid-based compound, the viscosity of the etching liquid composition may be excessively increased to cause etching variations in each region of the film to be etched.
However, the etching solution composition can prevent overetching of the silver-containing film and can form a conductive pattern having a fine pattern size by excluding phosphoric acid or the phosphoric acid-based compound.
The inorganic acid contained in the etching solution composition of some exemplary embodiments is substantially composed of nitric acid, and may not contain hydrochloric acid or sulfuric acid. This enables an etching process in which the problem of environmental pollution and the problem of silver deposition are reduced.
The pH of the etching liquid composition of the exemplary embodiment may be adjusted to 2 or less. The content of the above-mentioned composition components may be adjusted within a range of pH 2 or less. For example, in the range of pH 2 or less, the pH can be finely controlled by the polyol profile improver. Since the pH is adjusted to 2 or less, defects such as non-etching, silver precipitation, and silver re-adsorption can be reduced, and the etching rate and etching uniformity can be improved by the interaction of the above components.
< method for Forming conductive Pattern >
Fig. 1 and 2 are schematic sectional views for explaining a wiring forming method of an exemplary embodiment.
Referring to fig. 1, a lower conductive pattern 115 and a lower insulating film 110 may be formed on a substrate 100.
The substrate 100 may include a glass substrate, a polymer resin or plastic substrate, an inorganic insulating substrate, and the like.
The lower conductive pattern 115 may be formed to include a transparent conductive oxide such as aluminum (Al), copper (Cu), molybdenum (Mo), tungsten (W), titanium (Ti), tantalum (Ta), ITO, or the like. The lower insulating film 110 may be formed to include an organic insulating material such as acrylic resin or polysiloxane, and/or an inorganic insulating material such as silicon oxide, silicon nitride, or silicon oxynitride.
The lower conductive pattern 115 may be provided as, for example, a conductive via or a conductive contact.
According to an exemplary embodiment, the metal film 120 including the first transparent conductive oxide film 121, the silver-containing film 123, and the second transparent conductive oxide film 125 sequentially stacked may be formed on the lower insulating film 110 and the lower conductive pattern 115.
The first and second transparent conductive oxide films 121 and 125 may be formed to include transparent metal oxides such as ITO, IZO, GZO, IGZO, and the like. The silver-containing film 123 may be formed to contain silver and/or a silver alloy as described above. The first transparent conductive oxide film 121, the silver-containing film 123, and the second transparent conductive oxide film 125 can be formed by an evaporation process such as a sputtering process.
A mask pattern 130 may be formed on the metal film 120. For example, after a photoresist film is formed on the second transparent conductive oxide film 125, the photoresist film may be partially removed through an exposure and development process to form the mask pattern 130.
Referring to fig. 2, the metal film 120 may be etched using the metal film etchant composition of the above exemplary embodiment to form a conductive pattern 120 a. The conductive pattern 120a may include, for example, a first transparent conductive oxide film pattern 122, a silver-containing pattern 124, and a first transparent conductive oxide film pattern 126, which are sequentially stacked on the lower insulating film 110.
The conductive pattern 120a may be used as a pad, an electrode, or a wiring of the image display device, for example. Since the silver-containing pattern 124 having low resistance and relatively excellent signal transmission characteristics is formed between the first and second transparent conductive oxide film patterns 122 and 126 having excellent corrosion resistance, a conductive pattern having low resistance and improved mechanical and chemical reliability can be realized.
In addition, since the etching solution composition containing the etching initiator, the inorganic acid, the organic acid, the polyol-based profile improver, the metal salt, and the like, and excluding or reducing the phosphoric acid is applied, it is possible to prevent the over-etching of the silver-containing pattern 124 and form the conductive pattern 120a having a substantially uniform and continuous sidewall profile.
In some embodiments, the thickness of the silver-containing film 123 or the silver-containing pattern 124 is about
Figure BDA0001739805290000101
Above, in one embodiment, may be about
Figure BDA0001739805290000102
The above. The first and second transparent conductive oxide film patterns 122 and 126 may have a thickness of about
Figure BDA0001739805290000103
In order to realize low resistance, the thickness of the silver-containing pattern 124 is increased, and the aspect ratio of the conductive pattern 120a is increased, which may cause poor etching due to silver residue and overetching. However, by using the etching liquid composition of the exemplary embodiment, a wet etching process in which the above etching failure is suppressed can be realized.
Fig. 3 is a sectional view for explaining a method of manufacturing a display substrate of an exemplary embodiment. For example, fig. 3 shows a display substrate including the wiring and the electrode structure formed by the above-described conductive pattern forming method.
Referring to fig. 3, a Thin Film Transistor (TFT) may be formed on a substrate 200. For example, the TFT may include an active layer 210, a gate insulating film 220, and a gate electrode 225.
According to an exemplary embodiment, the gate insulating film 220 covering the active layer 210 may be formed after the active layer 210 is formed on the substrate 200.
The active layer 210 may be formed to include polycrystalline silicon or an oxide semiconductor such as Indium Gallium Zinc Oxide (IGZO). The gate insulating film 220 may be formed to include silicon oxide, silicon nitride, and/or silicon oxynitride.
A gate electrode 225 may be formed on the gate insulating film 220 so as to overlap with the active layer 210. The gate electrode 225 may be formed to contain metal such as Al, Ti, Cu, W, Ta, Ag, or the like.
After forming the interlayer insulating film 230 covering the gate electrode 225 on the gate insulating film 220, a source electrode 233 and a drain electrode 237 which are in contact with the active layer 210 through the interlayer insulating film 230 and the gate insulating film 220 may be formed. The source electrode 233 and the drain electrode 237 may be formed to contain metal such as Al, Ti, Cu, W, Ta, Ag, or the like.
A channel (via) insulating film 240 covering the source electrode 233 and the drain electrode 237 may be formed on the interlayer insulating film 230. The tunnel insulating film 240 can be formed using an organic insulating material such as acrylic resin or silicone resin.
A pixel electrode 245 electrically connected to the drain electrode 237 may be formed on the channel insulating film 240. The pixel electrode 245 may include a channel portion (via portion) that penetrates the channel insulating film 240 and contacts the drain electrode 237. The pixel electrode 245 may be formed to contain metal such as Al, Ti, Cu, W, Ta, Ag, etc., and/or transparent conductive oxide.
A pixel defining film 250 may be formed on the channel insulating film 240, and a display layer 255 may be formed on the pixel defining film 250 exposed by the pixel defining film 250. The display layer 255 may be formed as, for example, an organic light emitting layer (EML) included in an OLED device or a liquid crystal layer included in an LCD device.
A counter electrode 260 may be formed on the pixel defining film 250 and the display layer 255. The counter electrode 260 may be provided as a common electrode, a reflective electrode, or a cathode (cathode) of the image display device.
According to an exemplary embodiment, the counter electrode 260 may be formed by patterning through a wet etching process using the above-described etchant composition after sequentially laminating the first transparent conductive oxide film, the silver-containing film, and the second transparent conductive oxide film.
Thus, the counter electrode 260 may include a first transparent conductive oxide film pattern 262, a silver-containing pattern 264, and a second transparent conductive oxide film pattern 266 sequentially stacked on the pixel defining film 250 and the display layer 255.
In some embodiments, the image display device may include a display area I and a non-display area II. The above-described TFT, pixel electrode 245, display layer 255, and counter electrode 260 may be formed on the display region I. The wiring 270 may be formed on the non-display region II. The wiring 270 may be electrically connected to the TFT or the counter electrode 260.
The wiring 270 also includes, for example, a first transparent conductive oxide film pattern 272, a silver-containing pattern 274, and a second transparent conductive oxide film pattern 276, which are sequentially stacked on the channel insulating film 240, and may be patterned using the etchant composition of the exemplary embodiment.
In one embodiment, the wiring 270 may be formed by a wet etching process substantially the same as the counter electrode 260 on the display region I.
As described above, since the counter electrode 260 and/or the wiring 270 of the image display device are formed in the laminated structure including the first transparent conductive oxide film pattern-the silver-containing pattern-the second transparent conductive oxide film pattern, it is possible to exhibit the low resistance characteristic and simultaneously improve the mechanical/chemical stability and the optical characteristic. Further, since the etching liquid composition is used, defects such as silver residue, side damage, and edge chipping can be suppressed.
In some embodiments, the gate electrode 225, the source electrode 233, the drain electrode 237, and the pixel electrode 245 may be patterned by using the etching solution composition or the conductive pattern forming method.
The etching solution composition can be used for forming various conductive patterns of a touch sensor included in an image display device using the display substrate. For example, the etching solution composition may be used to form a sensing electrode, a trace, a pad, etc. of the touch sensor.
Hereinafter, experimental examples including specific examples and comparative examples are provided to help understanding of the present invention, but the examples are only illustrative of the present invention and do not limit the scope of the appended claims, and various changes and modifications of the examples may be made within the scope and technical spirit of the present invention, which will be apparent to those skilled in the art, and such changes and modifications also fall within the scope of the appended claims.
Examples and comparative examples
The metal film etching liquid compositions of examples and comparative examples were prepared in accordance with the compositions and contents (wt%) described in table 1 below.
[ Table 1]
Figure BDA0001739805290000131
Examples of the experiments
Formed on a glass substrate
Figure BDA0001739805290000132
The three-layer film was cut into a size of 10cm × 10cm with a diamond knife to produce a sample.
The metal film etching liquid compositions of examples and comparative examples were injected into a jet etching apparatus (ETCHER, manufactured by k.c. tech). After the temperature of the metal film etching liquid composition was set to 40 ℃, the metal film etching liquid composition was sprayed to the sample to perform an etching process for 85 seconds when the temperature reached 40 ± 0.1 ℃.
After the etching step was completed, the sample was washed with deionized water, dried by a hot air dryer, and then the photoresist was removed by a photoresist stripper (PR stripper).
(1) Evaluation of etching Rate (Etch Rate: ER)
The thickness of the etched sample was measured by an electron scanning microscope (SU-8010, manufactured by hitachi corporation), and the longitudinal etching rate was measured by dividing the thickness of the etched sample by the etching execution time. Thereafter, the etching rate was evaluated according to the following criteria, and the results are shown in table 2.
< evaluation criteria >
Very good: longitudinal etching rate over
Figure BDA0001739805290000141
O: a longitudinal etching rate of
Figure BDA0001739805290000142
X: longitudinal etching rate less than
Figure BDA0001739805290000143
(2) Evaluation of undercut (Side Etch)
For the etched sample, the undercut of the formed conductive pattern and the etching distance distribution between the upper and lower portions of the substrate were measured using an electron scanning microscope (SU-8010, manufactured by hitachi).
The undercut (S/E) was calculated from the following numerical formula 1, and evaluated as follows.
[ mathematical formula 1]
Undercut (S/E) ((width of both end portions of photoresist) - (width of etched wiring))/2
Very good: excellent (less than 0.5 μm)
O: good (more than 0.5 μm and 1.0 μm or less)
X: failure (more than 1.0 μm)
(3) Critical dimension bias (CD bias) determination
The substrate was cut after the etched sample was washed and dried, and the cross section was measured by an electron scanning microscope (SEM; model: SU-8010, manufactured by Hitachi Co.). For the critical dimension variation evaluation, after the etching was completed, the upper width of the wiring in contact with the photoresist pattern was measured and evaluated. The evaluation criteria are as follows.
Very good: the width of the wiring connected with the photoresist pattern exceeds 31 μm and is less than 34 μm
O: the width of the wiring connected with the photoresist pattern exceeds 23 μm and is less than 31 μm
And (delta): the width of the wiring connected with the photoresist pattern exceeds 9 μm and is less than 23 μm
X: the width of the wiring not etched or connected with the photoresist pattern is less than 9 μm
The evaluation results of the above experimental examples are shown in table 2 below.
[ Table 2]
Distinguishing ER evaluation Side etching CD bias
Example 1 ◎ ◎ ◎
Example 2 ◎ ◎ ◎
Example 3 ◎ ◎ ◎
Example 4 ◎ ○ ○
Example 5 ○ ○ ○
Comparative example 1 X X △
Comparative example 2 X X X
Comparative example 3 X ○ △
Referring to table 2, the etching solution compositions of the examples including the pH ranges and components of the exemplary examples showed excellent etching characteristics as a whole. In particular, examples 1 to 3, which included a metal salt and a second organic acid, showed excellent etching rate and etching uniformity.
On the other hand, the etching rate of the comparative examples, in which the pH exceeded 2 or components such as the etching initiator were omitted, was decreased, and the undercut and CD variation were also deteriorated.

Claims (15)

1. A metal film etching solution composition which is an etching solution composition comprising a transparent conductive oxide film and a silver-containing film laminated film, wherein the metal film etching solution composition comprises an etching initiator, an inorganic acid, an organic acid, a polyhydric alcohol-based profile-improving agent and the balance of water, does not contain phosphoric acid or a phosphoric acid-based compound, and has a pH of 2 or less, and the inorganic acid comprises nitric acid but does not contain hydrochloric acid and sulfuric acid.
2. The metal film etching liquid composition according to claim 1, wherein the etching initiator comprises at least one selected from the group consisting of a sulfur peroxide, hydrogen peroxide, a persulfate, and a peroxynitrate.
3. The metal film etchant composition according to claim 2, wherein the etching initiator comprises oxone.
4. The metal film etchant composition according to claim 1, wherein the organic acid comprises a first organic acid and a second organic acid that is less acidic than the first organic acid.
5. The metal film etchant composition according to claim 4, wherein the first organic acid comprises acetic acid,
the second organic acid includes at least one selected from the group consisting of iminodiacetic acid (IDA), ethylenediaminetetraacetic acid (EDTA), glycine, salicylic acid, citric acid, formic acid, oxalic acid, malonic acid, succinic acid, butyric acid, gluconic acid, glycolic acid, and valeric acid.
6. The metal film etchant composition according to claim 1, wherein the polyhydric alcohol-based profile improver comprises at least one selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol.
7. The metal film etchant composition according to claim 1, further comprising a metal salt.
8. The metal film etching solution composition according to claim 7, wherein the metal salt comprises at least one selected from the group consisting of iron nitrate, sodium nitrate and potassium nitrate.
9. The metal film etching solution composition according to claim 1, comprising, based on the total weight of the composition:
1-20 wt% of the etching initiator;
1-15 wt% of the inorganic acid;
0.1-20 wt% of an organic acid;
1 to 20 wt% of the polyol profile improver; and
the balance of water.
10. The metal film etchant composition according to claim 9, further comprising 0.1 to 5% by weight of a metal salt.
11. A conductive pattern forming method, comprising:
a step of forming a laminated film including a transparent conductive oxide film and a silver-containing film on a substrate; and
a step of etching the laminated film by using the metal film etchant composition according to any one of claims 1 to 10.
12. The method according to claim 11, wherein the transparent conductive oxide film comprises a first transparent conductive oxide film and a second transparent conductive oxide film formed through the silver-containing film.
13. The conductive pattern forming method according to claim 11, the transparent conductive oxide film comprising at least one selected from the group consisting of Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), Indium Tin Zinc Oxide (ITZO), Gallium Zinc Oxide (GZO), and Indium Gallium Zinc Oxide (IGZO).
14. The conductive pattern forming method according to claim 11, further comprising:
a step of forming a thin film transistor on the substrate;
a step of forming a pixel electrode electrically connected to the thin film transistor; and
a step of forming a display layer on the pixel electrode,
the laminated film is formed on the display layer.
15. The conductive pattern forming method according to claim 14, wherein the conductive pattern is provided as a common electrode, a reflective electrode, or a wiring of an image display device.
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