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WO2011028037A2 - Etchant for thin film transistor-liquid crystal display - Google Patents

Etchant for thin film transistor-liquid crystal display Download PDF

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Publication number
WO2011028037A2
WO2011028037A2 PCT/KR2010/005960 KR2010005960W WO2011028037A2 WO 2011028037 A2 WO2011028037 A2 WO 2011028037A2 KR 2010005960 W KR2010005960 W KR 2010005960W WO 2011028037 A2 WO2011028037 A2 WO 2011028037A2
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WO
WIPO (PCT)
Prior art keywords
etchant
group
film
total weight
content
Prior art date
Application number
PCT/KR2010/005960
Other languages
French (fr)
Other versions
WO2011028037A3 (en
Inventor
Yong Sung Song
Tai Hyung Rhee
Original Assignee
Techno Semichem Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Techno Semichem Co., Ltd. filed Critical Techno Semichem Co., Ltd.
Publication of WO2011028037A2 publication Critical patent/WO2011028037A2/en
Publication of WO2011028037A3 publication Critical patent/WO2011028037A3/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
    • 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
    • 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
    • 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
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/6729—Thin-film transistors [TFT] characterised by the electrodes
    • H10D30/6737—Thin-film transistors [TFT] characterised by the electrodes characterised by the electrode materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/6729—Thin-film transistors [TFT] characterised by the electrodes
    • H10D30/6737—Thin-film transistors [TFT] characterised by the electrodes characterised by the electrode materials
    • H10D30/6739—Conductor-insulator-semiconductor electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/674—Thin-film transistors [TFT] characterised by the active materials
    • H10D30/6741—Group IV materials, e.g. germanium or silicon carbide
    • H10D30/6743—Silicon

Definitions

  • the following disclosure relates to an etchant of a metal film and in particular, to a single layer selected from a copper film, a titanium film, a molybdenum film and an alloy film thereof or a multi-layer that the single layers are independently multi layered as many as more than two layers.
  • An embodiment of the present invention is directed to providing an etchant that performs bulk etching of a single layer selected from a copper film, a titanium film and a molybdenumfilm and an alloy film for forming a metal wiring; or a multi-layer that the single layers are independently multilayered as many as more than two layers, and that effectively adjust its etch rate, etching amount and taper angle.
  • an etchant of a metal film includes an organic chelating agent with an amino group and a carboxyl group; peroxides; oxidants fluorine compounds glycols; additives and deionized water.
  • the metal film is a single layer selected from a copper film, a titanium film, a molybdenum film and alloy films thereof; or a multilayer that the single layers are independently multilayered as many as more than two layers.
  • the present invention has advantages that bulk etching of a multi-layer that two or more layers are multilayered as well as a single layeris possible and another etching is also possible. Its process can be performed even in low temperature compared to other etching compositions.
  • the present invention relates to an etchant of metal films including 0.1 ⁇ 5wt of an organic chelating agent with an amino group and a carboxyl group; 5 - 25 wt%of peroxides; 0.5 ⁇ 5wt% of oxidants 0.1 ⁇ lwt% of fluorine compounds 1 ⁇ 10 wt% of glycols; and 0.1 ⁇ 5wt% of additives and deionized water contained to make the total weight of 100 wt .
  • the etchant according to the present invention has advantages that non-uniform etching occurring by high viscosity of the phosphorous etchant can be prevented and the safety problem can be solved when they are respectively mixed in the above-mentioned range, compared to the peroxide etchant.
  • the organic chelating agent may be one or more selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, nitrilotriacetic acid and diethylene trinitrilo pentaacetic acid (DTPA), and the organic chelating agent may be 0.1 to 5wt% based on the total amount of the etchant.
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylene trinitrilo pentaacetic acid
  • the organic chelating agent has a function thatprevents degradation of etching ability due to increased metal ions when the number of processed sheets of a metal film to be etched is increased.
  • the organic chelating agent exceeds 5 wt%, its effect is not increased as much as the amount of the increased chelating agents, which means inefficient. Also, there is a possibility to be precipitated since its solubility drops. And when the organic chelating agent is contained below 0.1 wt , it is not possible to prevent degradation of etching ability according to increase of the number of processed sheets of the metal film to be etched.
  • the peroxides are one or more selected from ammonium persulfate, sodium persulfate and patassium persulfate and its content may be 5 to 25wt% based on the total amount of the etchant.
  • the peroxides play a role of oxidizing the metal of the metal film. Specifically, the peroxides play a role of forming a copper oxide by oxidizing copper.
  • the peroxides are containedbelow 5wt%, the etching of the metal may be non-uniform, and when the peroxides are contained over 25wt%, there is a disadvantage that it maybe precipitated.
  • the oxidants according to the present invention are one or more selected from
  • the oxidant according to the present invention makes metal oxides generated by peroxides have solubility in water through substitution so that it can be dissolved in the etchant. More specifically, when the metal is copper, the copper oxide generated by peroxides is substituted by copper nitrate (Cu(N0 3 ) 2 )or copper sulfate, and the generated compound is dissolved in the etchant.
  • the content of the oxidant may be 0.5 ⁇ 5wt% of the entire compositions, and when it is below 0.5wt%, the etching of the metal film is not properly achieved. When the content of the oxidant exceeds 5wt%, it causesdamage of a substrate by enhancing activity of fluorine ions of fluorine compounds contained in the etchant.
  • the fluorine compound may be one or more selected from ammonium hydrogen fluoride (NH 4 F2), hexafluorosilicic acid (H 2 SiF 6 ) and potassium bifluoride (KHF 2 ), and its content may be 0.1 to lwt% based on the total amount of the etchant.
  • the fluorine compound is used for etching a metal film. When the fluorine compound exceeds 1 wt%, the substrate or silicone film maybe excessively etched. When the fluorine compound is contained below 0.1 wt , it remarkably degrades the etch rate of the metal film to cause generation of residues and tails and difficulty in a post-process. It is desirable that the fluorine compounds are included in a range that the substrate or silicone film is not etched.
  • a general substrate may be used without limitation, and more specifically, a glass substrate may be used.
  • the glycols may be one or more selected from ethylene glycol, polyethylene glycol and glycolic acid, and its content is 1 to 10wt% based on the total amount of the etchant.
  • the present invention can overcome a weak point in time change by using glycols, and it plays a role of a boiling point adjuster of the etchant. It is possible to overcome the weak point in time change when it is included in the range.
  • Examples of the additives may include azole compounds, and more preferably, one or more selected from 5-aminotetrazole, 1,2,3-benzotrazole, methylbenzotriazole and imidazole, and its content may be 0.1 to 5wt%based on the total amount of the etchant.
  • Critical Dimension CD which is a loss by etching, may become large.
  • the additives are contained more than5 wt%, the etch rate of the metal film may be retarded and a taper angle may be non-uniform. Accordingly, the preferred content according to the composition of the present invention should be included.
  • the residual amount of the entire compositions may be mixed with deionied water, and plays a role of diluting the etchant.
  • the loss due to etching is less than l.O/ffli, and the taper angle is 20°or more. Accordingly, the effective etching can be executed.
  • the metal film may be a single layer selected from a copper film, a titanium film, a molybdenum film and alloy films thereof: or a multi-layer thatthe single layers are independently multilayered as many as more than two layers.
  • the etchant according to the present invention is used for patterning of the metal film, which is a wiring material of a gate electrode and source/drain forming a Thin Film Transistor-Liquid Crystal Display (TFT-LCD).
  • TFT-LCD Thin Film Transistor-Liquid Crystal Display
  • the etchant according to the present invention forms uniform etching and has
  • the etchant has a uniform etching property by solving a spot problem due to high viscosity of a high composition of the phosphorous etchant.
  • the etchant has an advantage that bulk etching of the single layer as well as multi-layers is possible.
  • FIG. 1 is a picture showing a profile of a titanium film/copper film observed by
  • SEM Scanning Electron Microscope
  • FIG. 2 is a picture showing a glass substrate observed by the SEM after performing the method suggested in Test Example 1 with the etchant of Example 1 and performing strip of a photo resist of the titanium film/copper film.
  • FIG. 3 is a picture showing a profile of the titanium film/copper film oserved by the SEM after performing an etching process with the etchant of Comparative Example 1 according to the method suggested in Test Example 1.
  • FIG. 4 is a picture showing a glass substrate observed by the SEM after performing the method suggested in Test Example lwith the etchant of Comparative Example 1 and performing strip of the photo resist of the titanium film/copper film.
  • Table 2 showed a result obtained by measuring an etching loss and an i angle after performing an etching process with the etchant of Examples 1 Comparative Examples 1 to 4 according to the method described above.
  • 1 etching loss was 0.5pm 0.2pm or less and the inclination angle was 30 or 1 result of the properties evaluation was "excellent”.
  • the etching loss 0.3 m or less and the inclination angle was 20 or higher, the result of the evaluation was "good”.
  • the etching loss was obtained by observii the etched titanium film/copper film through Scanning Electron Microsa 4700 by Hitach Company) and measuring a distance between an end of tl and an end of the copper film.
  • the inclination angle was obtained b profile of the etched titanium film/copper film through Scanning Electroi (SEM, S-4700 by Hitach Company) and measuring a value of an inclinat an etched side.
  • FIG. 1 is a picture showing a profile of the titanium film/copper film ot SEM after performing an etching process with the etchant of Example la according to the method suggested in Test Example 1.
  • FIG. 4 is a picture showing a glass substrate observed by the SEM after performing the method suggested in Test Example 1 with the etchant of Comparative Example land performing strip of the photo resist of the titanium film/copper film. In FIG. 4, there are no tail and residues.

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Abstract

Provided is an etchant of a metal film including an organic chelating agent with an amino group and a carboxyl group; peroxides; oxidants fluorine compounds; glycols; additives and deionized water. Provided is a composition of an etchant for patterning of a copper film which is a wiring material of a gate electrode and source/drain forming a Thin Film Transistor-Liquid Crystal Display (TFT-LCD). The etchant generates uniform etching and has excellent stability, so it improvesnon-uniform etching generated by high viscosity, which is a disadvantage of the phosphorous etchant, as well as stability of the peroxide etchant. The etchant has a uniform etching property by solving a spot problem due to high viscosity of a high composition of the phosphorous etchant. Bulk etching of a single layer as well as a multi-layer is possible.

Description

Description
Title of Invention: ETCHANT FOR THIN FILM TRANSISTOR- LIQUID CRYSTAL DISPLAY
Technical Field
[1] The following disclosure relates to an etchant of a metal film and in particular, to a single layer selected from a copper film, a titanium film, a molybdenum film and an alloy film thereof or a multi-layer that the single layers are independently multi layered as many as more than two layers.
Background Art
[2] ur by non-uniform etching due to high viscosity. In addition, when metal ions being generated by etching of metals arrive at a concentration of a certain value or higher, a peroxide system ' s etchant is very quickly decomposed into water and oxygen by promoting decomposition of peroxide. Accordingly, heat generation and rapid composition change may occur to cause a problem in an aspect of safety. It is necessary that a unit area of wiring is increased to make low resistance wiring, and a thickness or a width can be increased in order to increase the unit area of wiring. When the thickness of wiring is increased, another wiring formed on one wiring may be disconnected by a step due to the wiring thickness. When the width of wiring is increased, there is a problem that an aperture ratio is decreased.
Disclosure of Invention
Technical Problem
[3] An embodiment of the present invention is directed to providing an etchant that performs bulk etching of a single layer selected from a copper film, a titanium film and a molybdenumfilm and an alloy film for forming a metal wiring; or a multi-layer that the single layers are independently multilayered as many as more than two layers, and that effectively adjust its etch rate, etching amount and taper angle.
Solution to Problem
[4] In one general aspect, an etchant of a metal film includes an organic chelating agent with an amino group and a carboxyl group; peroxides; oxidants fluorine compounds glycols; additives and deionized water. The metal film is a single layer selected from a copper film, a titanium film, a molybdenum film and alloy films thereof; or a multilayer that the single layers are independently multilayered as many as more than two layers.
[5] The present invention has advantages that bulk etching of a multi-layer that two or more layers are multilayered as well as a single layeris possible and another etching is also possible. Its process can be performed even in low temperature compared to other etching compositions.
[6] Hereafter, the present invention is explained more specifically.
[7] The present invention relates to an etchant of metal films including 0.1~5wt of an organic chelating agent with an amino group and a carboxyl group; 5 - 25 wt%of peroxides; 0.5 ~ 5wt% of oxidants 0.1 ~ lwt% of fluorine compounds 1 ~ 10 wt% of glycols; and 0.1 ~ 5wt% of additives and deionized water contained to make the total weight of 100 wt . The etchant according to the present invention has advantages that non-uniform etching occurring by high viscosity of the phosphorous etchant can be prevented and the safety problem can be solved when they are respectively mixed in the above-mentioned range, compared to the peroxide etchant.
[8] The organic chelating agent may be one or more selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, nitrilotriacetic acid and diethylene trinitrilo pentaacetic acid (DTPA), and the organic chelating agent may be 0.1 to 5wt% based on the total amount of the etchant.
[9] The organic chelating agent has a function thatprevents degradation of etching ability due to increased metal ions when the number of processed sheets of a metal film to be etched is increased. When the organic chelating agent exceeds 5 wt%, its effect is not increased as much as the amount of the increased chelating agents, which means inefficient. Also, there is a possibility to be precipitated since its solubility drops. And when the organic chelating agent is contained below 0.1 wt , it is not possible to prevent degradation of etching ability according to increase of the number of processed sheets of the metal film to be etched.
[10] In the present invention, the peroxides are one or more selected from ammonium persulfate, sodium persulfate and patassium persulfate and its content may be 5 to 25wt% based on the total amount of the etchant. The peroxides play a role of oxidizing the metal of the metal film. Specifically, the peroxides play a role of forming a copper oxide by oxidizing copper. When the peroxides are containedbelow 5wt%, the etching of the metal may be non-uniform, and when the peroxides are contained over 25wt%, there is a disadvantage that it maybe precipitated.
[11] The oxidants according to the present invention are one or more selected from
potassium hydrogen sulfate, sodium nitrate, ammonium sulfate and sodium sulfate and sodium hydrogen sulfate, and its content is 0.5 to 5wt% based on the total amount of the etchant. The oxidant according to the present invention makes metal oxides generated by peroxides have solubility in water through substitution so that it can be dissolved in the etchant. More specifically, when the metal is copper, the copper oxide generated by peroxides is substituted by copper nitrate (Cu(N03)2)or copper sulfate, and the generated compound is dissolved in the etchant.
[12] The content of the oxidant may be 0.5 ~ 5wt% of the entire compositions, and when it is below 0.5wt%, the etching of the metal film is not properly achieved. When the content of the oxidant exceeds 5wt%, it causesdamage of a substrate by enhancing activity of fluorine ions of fluorine compounds contained in the etchant.
[13] The fluorine compound may be one or more selected from ammonium hydrogen fluoride (NH4F2), hexafluorosilicic acid (H2SiF6) and potassium bifluoride (KHF2), and its content may be 0.1 to lwt% based on the total amount of the etchant. The fluorine compound is used for etching a metal film. When the fluorine compound exceeds 1 wt%, the substrate or silicone film maybe excessively etched. When the fluorine compound is contained below 0.1 wt , it remarkably degrades the etch rate of the metal film to cause generation of residues and tails and difficulty in a post-process. It is desirable that the fluorine compounds are included in a range that the substrate or silicone film is not etched. A general substrate may be used without limitation, and more specifically, a glass substrate may be used.
[14] The glycols may be one or more selected from ethylene glycol, polyethylene glycol and glycolic acid, and its content is 1 to 10wt% based on the total amount of the etchant. The present invention can overcome a weak point in time change by using glycols, and it plays a role of a boiling point adjuster of the etchant. It is possible to overcome the weak point in time change when it is included in the range.
[15] Examples of the additives may include azole compounds, and more preferably, one or more selected from 5-aminotetrazole, 1,2,3-benzotrazole, methylbenzotriazole and imidazole, and its content may be 0.1 to 5wt%based on the total amount of the etchant. When the additives are contained below 0.1 wt , Critical Dimension (CD), which is a loss by etching, may become large. When the additives are contained more than5 wt%, the etch rate of the metal film may be retarded and a taper angle may be non-uniform. Accordingly, the preferred content according to the composition of the present invention should be included.
[16] The residual amount of the entire compositions may be mixed with deionied water, and plays a role of diluting the etchant.
[17] When an etching process is carried out with the etchant according to the present invention, the loss due to etching is less than l.O/ffli, and the taper angle is 20°or more. Accordingly, the effective etching can be executed.
[18] The metal film may be a single layer selected from a copper film, a titanium film, a molybdenum film and alloy films thereof: or a multi-layer thatthe single layers are independently multilayered as many as more than two layers. The etchant according to the present invention is used for patterning of the metal film, which is a wiring material of a gate electrode and source/drain forming a Thin Film Transistor-Liquid Crystal Display (TFT-LCD).
[19] Other features and aspects will be apparent from the following detailed description, the drawings, and the claims.
Advantageous Effects of Invention
[20] The etchant according to the present invention forms uniform etching and has
excellent stability, so it can improve non-uniform etching generated by high viscosity, which is a disadvantage of the phosphorous etchant, as well as stability of the peroxide etchant. More specifically, the etchant has a uniform etching property by solving a spot problem due to high viscosity of a high composition of the phosphorous etchant. In addition, the etchant has an advantage that bulk etching of the single layer as well as multi-layers is possible.
Brief Description of Drawings
[21] FIG. 1 is a picture showing a profile of a titanium film/copper film observed by
Scanning Electron Microscope (SEM) after performing an etching process with an etchant of Example 1 according to a method suggested in Test Example 1.
[22] FIG. 2 is a picture showing a glass substrate observed by the SEM after performing the method suggested in Test Example 1 with the etchant of Example 1 and performing strip of a photo resist of the titanium film/copper film.
[23] FIG. 3 is a picture showing a profile of the titanium film/copper film oserved by the SEM after performing an etching process with the etchant of Comparative Example 1 according to the method suggested in Test Example 1.
[24] FIG. 4 is a picture showing a glass substrate observed by the SEM after performing the method suggested in Test Example lwith the etchant of Comparative Example 1 and performing strip of the photo resist of the titanium film/copper film.
Best Mode for Carrying out the Invention
[25] Although preferred examples of the present invention are described in detail above, it will be apparent that the scope of the present inventionis not limited thereto and diverse modifications and improved formats by a person having an ordinary skill in the art are also included in the scope of the present invention.
[26] [Example 1]
[27] An etchant was prepared by combining ammonium persulfate (5g), potassium
hydrogen sulfate (3g), ammonium hydrogen fluoride (0.5g), EDTA (0.5g), ethylene glycol (5g) and 5-aminotetrazole (0.5g) and further combining deionized water of such an amount that a weight of the entire composition could be lOOg.
[28] Table 1 below showed constituent elements and a content of the etchant.
[29] [Examples 2 to 4 and Comparative Examples 1 to 4]
[30] Examples 2 to 4 and Comparative Examples 1 to 4 were performed in the same
manner as that of the Example 1 except the content.
[31] Table 1 below showed constituent elements and content of the etchant. [32] [Test Example 1]
[33] Etching process
[34] An etching process was performed on a multi-layer obtained by multila titanium film and a copper film at 28°C using the etchant prepared accorc Examples 1 to 4 and Comparative Examples 1 to 4. The multi-layerwas∑ photo resist film was formed through patterning. The titanium film had a 100 A and the copper film had a thickness of 1200 A The etching process performed by spraying the etchanton the film through a uniform spraying
[35] In the etching process, properties evaluation was performed after 100% End Point Detect (EPD), which was a time that glass of a glass substrate The overetching exceeding by 100% should be performed to sufficiently and residues of other metal films since etch rates of other metal films wei paratively slower than that of the copper film.
[36] Properties Evaluation
[37] Table 2 showed a result obtained by measuring an etching loss and an i angle after performing an etching process with the etchant of Examples 1 Comparative Examples 1 to 4 according to the method described above. 1 etching loss was 0.5pm 0.2pm or less and the inclination angle was 30 or 1 result of the properties evaluation was "excellent". When the etching loss 0.3 m or less and the inclination angle was 20 or higher, the result of the evaluation was "good".
[38] In measuring the etching loss, the etching loss was obtained by observii the etched titanium film/copper film through Scanning Electron Microsa 4700 by Hitach Company) and measuring a distance between an end of tl and an end of the copper film.
[39] In measuring the inclination angle, the inclination angle was obtained b profile of the etched titanium film/copper film through Scanning Electroi (SEM, S-4700 by Hitach Company) and measuring a value of an inclinat an etched side.
[40] FIG. 1 is a picture showing a profile of the titanium film/copper film ot SEM after performing an etching process with the etchant of Example la according to the method suggested in Test Example 1.
[43] FIG. 4 is a picture showing a glass substrate observed by the SEM after performing the method suggested in Test Example 1 with the etchant of Comparative Example land performing strip of the photo resist of the titanium film/copper film. In FIG. 4, there are no tail and residues.
[44] Table 1
[45]
Figure imgf000007_0002
[46] Table 2
Figure imgf000007_0001

Claims

Claims
[Claim 1] An etchant of a metal film, comprising:
an organic chelating agent with an amino group and a carboxyl group; peroxides; oxidants fluorine compounds; glycols; additives and deionized water.
[Claim 2] The etchantof claim 1, wherein the organic chelating agent is one or more selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, nitrilotriacetic acid and diethylene trinitrilo pentaacetic acid (DTP A).
[Claim 3] The etchant of claim 2, wherein the organic chelating agent is 0.1 to
5wt% based on a total weight of the etchant
[Claim 4] The etchant of claim 1 , wherein the peroxides are one or more selected from the group consisting of ammonium persulfate, sodium persulfate and patassium persulfate and a content of the peroxide is 5 ~ 25wt% based on the total weight of the etchant.
[Claim 5] The etchant of claim 1, wherein the oxidants are one or more selected from the group consisting of potassium hydrogen sulfate, sodium nitrate, ammonium sulfate, sodium sulfate and sodium hydrogen sulfate and a content of the oxidant is 0.5 ~ 5wt% based on the total weight of the etchant.
[Claim 6] The etchant of claim 1, wherein the fluorine compounds are one or more selected fromthe group consisting of ammonium hydrogen fluoride (NH4F2), hexafluorosilicic acid (H2SiF6) and potassium bi- fluoride (KHF2) and a content of the fluorine compound is 0.1 ~ lwt%based on the total weight of the etchant.
[Claim 7] The etchant of claim 1, wherein the glycols are one or more selected from the group consisting of ethylene glycol, polyethylene glycol and glycolic acid and a content of the glycols is 1 ~ 10wt% based on the total weight of the etchant.
[Claim 8] The etchant of claim 1, wherein the additives are one or more selected from the group consisting of 5-aminotetrazole, 1 ,2,3-benzotrazole, methylbenzotriazole and imidazole and a content of the additives is 0.1 ~ 5wt% based on the total weight of the etchant.
[Claim 9] The etchant of claim 1, which comprises 0.1 to 5wt% of the organic chelating agent with the amino group and the carboxyl group 5 - 25wt% of the peroxides 0.5 - 5wt% of the oxidant 0.1 ~ lwt% of the fluorine compounds 1 ~ 10wt% of the glycols 0,1 ~ 5wt% of the additives and deionized water of an amount that forms the total weight of 100wt .
[Claim 10] The etchant of any one selected from claims 1 to 9, wherein the metal film is a single layer selected from a copper film, a titanium film, a molybdenum film and an alloy film thereof or a multi-layer that the single layers are independently multilayered as many as more than two layers.
PCT/KR2010/005960 2009-09-07 2010-09-02 Etchant for thin film transistor-liquid crystal display WO2011028037A2 (en)

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KR101922625B1 (en) 2012-07-03 2018-11-28 삼성디스플레이 주식회사 Etchant for metal wire and method for manufacturing metal wire using the same
KR20140013310A (en) 2012-07-23 2014-02-05 삼성디스플레이 주식회사 Etchant and manufacturing method of metal wiring and thin film transistor array panel using the same
KR102331036B1 (en) 2014-10-10 2021-11-26 삼영순화(주) Etching solution composition and etching method using the same
KR102487940B1 (en) 2018-03-19 2023-01-16 삼성디스플레이 주식회사 Etchant composition, and method for manufacturing metal pattern and array substrate using the same
KR102648664B1 (en) 2018-12-04 2024-03-19 삼성디스플레이 주식회사 Etchant composition, and method for manufacturing metal pattern and array substrate using the same
US12312695B2 (en) 2020-12-30 2025-05-27 Samsung Display Co., Ltd. Etchant composition, and method for manufacturing metal pattern and thin film transistor substrate using the same

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JP4668533B2 (en) * 2001-07-06 2011-04-13 サムスン エレクトロニクス カンパニー リミテッド Etching solution for wiring, manufacturing method of wiring using the same, and manufacturing method of thin film transistor substrate including the same
KR101174767B1 (en) * 2005-03-10 2012-08-17 솔브레인 주식회사 Method for fabricating liquid crystal display device using etchant for metal layers
JP2008547202A (en) * 2005-06-13 2008-12-25 アドバンスド テクノロジー マテリアルズ，インコーポレイテッド Compositions and methods for selective removal of metals or metal alloys after formation of metal silicides
KR101310310B1 (en) * 2007-03-15 2013-09-23 주식회사 동진쎄미켐 Etchant for thin film transistor-liquid crystal displays
KR100883960B1 (en) * 2007-10-01 2009-02-17 (주)이그잭스 Etchants of Copper or Copper Alloy Films
KR101346976B1 (en) * 2008-02-12 2014-01-03 동우 화인켐 주식회사 Fabrication method of thin film transistor, etching solution composition used the method

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WO2011028037A3 (en) 2011-07-07
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KR101146099B1 (en) 2012-05-16
TWI473910B (en) 2015-02-21

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