US20190301026A1 - Etchant compositions and method for etching - Google Patents

Etchant compositions and method for etching Download PDF

Info

Publication number
US20190301026A1
US20190301026A1 US16/316,054 US201716316054A US2019301026A1 US 20190301026 A1 US20190301026 A1 US 20190301026A1 US 201716316054 A US201716316054 A US 201716316054A US 2019301026 A1 US2019301026 A1 US 2019301026A1
Authority
US
United States
Prior art keywords
etching
etchant composition
titanium nitride
film
nitride film
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US16/316,054
Inventor
Ryou Kouno
Takuo Ohwada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kanto Chemical Co Inc
Original Assignee
Kanto Chemical Co Inc
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 Kanto Chemical Co Inc filed Critical Kanto Chemical Co Inc
Assigned to KANTO KAGAKU KABUSHIKI KAISHA reassignment KANTO KAGAKU KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KOUNO, RYOU, OHWADA, TAKUO
Publication of US20190301026A1 publication Critical patent/US20190301026A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • C23F1/26—Acidic compositions for etching refractory metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604—Chemical etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
    • 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
    • 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
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics

Definitions

  • the present invention relates to an etchant composition for batch etching treatment of tungsten film and titanium nitride film, and a method for etching using said etchant composition.
  • Tungsten and titanium nitride are both widely used for electric devices such as a semiconductor element. They are deposited as a film having film properties that are appropriate for a desired electric device, processed into a predetermined pattern, and used. As a method for processing tungsten film or titanium nitride film in a predetermined pattern, processing by etching has widely been adopted.
  • Patent References 1 and 2 disclose methods of processing a tungsten film using an etchant comprising hydrogen peroxide or ortho periodic acid.
  • Patent References 3 and 4 disclose methods of processing a titanium nitride film using an etchant comprising hydrogen peroxide.
  • an object of the present invention is to provide an etchant composition that is capable of batch etching treatment of tungsten film and titanium nitride film and a method for etching using said etchant composition. Furthermore, another object of the present invention is to provide the etchant composition that is capable of batch etching treatment of tungsten film and titanium nitride film and the method for etching using said etchant composition, while controlling the value of the quotient obtained by dividing the etching rate for the tungsten film by the etching rate for the titanium nitride film (hereinbelow, also referred to as “selection ratio”).
  • the present invention relates to the followings:
  • Etchant composition for batch etching treatment of tungsten film and titanium nitride film comprising nitric acid and water.
  • the etchant composition according to [1] further comprising at least one selected from the group consisting of sulfuric acid and aliphatic sulfonic acid.
  • an etchant composition that is capable of batch etching treatment of tungsten film and titanium nitride film and a method for etching using said etchant composition can be provided.
  • the etchant composition of the present invention by including at least one selected from the group consisting of sulfuric acid and aliphatic sulfonic acid in the etchant composition of the present invention, it becomes possible to control the selection ratio at approximately 1, which makes the aforementioned effect remarkable.
  • FIG. 1 is a graph showing the etching rate of the etchant composition (E.R.) of Working Examples 1 to 4 and Comparative Examples 1 to 3.
  • FIG. 2 is a graph showing the selection ratio of the etchant composition of Working Examples 1 to 4 and Comparative Examples 1 to 3.
  • FIG. 3 is a graph showing the change in the etching amount of the etchant composition of Working Example 4 over time.
  • the etchant composition of the present invention is used for batch etching treatment of tungsten film and titanium nitride film.
  • the etchant composition of the present invention comprises nitric acid and water. This enables a reduction in etching rates for tungsten film and titanium nitride film to appropriate level, which in turn enables providing an etchant composition for batch etching treatment of tungsten film and titanium nitride film which has never been investigated so far.
  • water is used as a solvent.
  • the content of water in the etchant composition is, though not being particularly limited, preferably between 2.0 and 80.0 wt %, more preferably between 5.0 and 70.0 wt %.
  • the content of water is made to be preferably between 8.0 and 65.0 wt % in order to suppress a change in the constitution of the etchant composition due to water evaporation. It is preferred to suppress the change in the constitution of the etchant composition because it reduces a risk of a change in the selection ratio during etching treatment due to constitution change even when the etching treatment under the temperature-rising condition requires a prolonged time. Moreover, it enables a repeated use of the etchant composition because the change in the selection ratio before and after the etching treatment is small. This is preferred from the perspective of reduction of the cost and environmental burden resulting from waste liquid processing of the etchant.
  • the etchant composition of the present invention preferably comprises at least one selected from the group consisting of sulfuric acid and aliphatic sulfonic acid.
  • the etchant composition consists of nitric acid and water
  • the water content can further be decreased by adding at least one selected from the group consisting of sulfuric acid and aliphatic sulfonic acid.
  • the content of a constituent of the etchant composition of the present invention is not particularly limited because it is adjusted as appropriate by the intended selection ratio and the film properties of the tungsten film and the titanium nitride film, though the content of at least one selected from the group consisting of sulfuric acid and aliphatic sulfonic acid is preferably between 5.0 and 95.0 wt %, more preferably between 8.0 and 40.0 wt %.
  • aliphatic sulfonic acid examples include an aliphatic sulfonic acid having 1 to 10 carbon atoms. More specific examples include such as methanesulfonic acid, ethanesulfonic acid and 1-propanesulfonic acid. As an aliphatic sulfonic acid used in the etchant composition of the present invention, methanesulfonic acid is preferred.
  • the etchant composition of the present invention preferably comprises phosphoric acid. It is preferred to include phosphoric acid in the etchant composition, because it enables adjusting of the constitution of the etchant composition in wider range.
  • the content of a constituent of the etchant composition of the present invention is not particularly limited because it is adjusted as appropriate by the intended selection ratio and the film properties of the tungsten film and the titanium nitride film, though the content of phosphoric acid is preferably between 0.1 and 90.0 wt %, more preferably between 0.5 and 80.0 wt %.
  • the etchant composition of the present invention may comprise any ingredient in addition to the above-mentioned ingredients, as long as it does not hinder the batch etching treatment of tungsten film and titanium nitride film.
  • Optional ingredients which may be used in the present invention include such as, for example, a surfactant.
  • a highly volatile ingredient when it is required to suppress the change in constitution of the etchant composition under a temperature-rising condition, it is preferred not to include a highly volatile ingredient even if the ingredient is generally contained in an etchant.
  • highly volatile ingredient include carboxylic acids such as a formic acid and acetic acid and the salts thereof, as well as polyfunctional carboxylic acids such as citric acid and tartaric acid and the salts thereof.
  • the etchant composition of the present invention is used for batch etching treatment of tungsten film and titanium nitride film.
  • the etchant composition of the present invention is used for forming a pattern having a three-dimensional structure by batch etching treatment of tungsten film and titanium nitride film.
  • the etchant composition of the present invention may be used for batch etching of a laminate body comprising at least one layer of tungsten film and at least one layer of titanium nitride film. Furthermore, controlling of the selection ratio to approximately 1 enables batch etching of tungsten film and titanium nitride film in a refined shape, for examples, in a pattern having a three-dimensional structure. In order to form a refined structure, the selection ratio is preferably between 0.70 and 1.30, more preferably between 0.80 and 1.20.
  • the selection ratio of the etchant composition of the present invention may be adjusted as appropriate by altering the constituents of the composition. For instance, the selection ratio tends to be decreased a little by increasing the content of nitric acid in the etchant composition, whereas the selection ratio tends to be increased by increasing water content. On the other hand, the selection ratio tends to be decreased by increasing the content of either of sulfuric acid, aliphatic sulfonic acid or phosphoric acid. Because the selection ratio also depends on the film properties of the tungsten film and the titanium nitride film, the desired selection ratio can be obtained by adjusting the constituents of the composition as appropriate according to the film properties of the film to be subjected to the etching.
  • the content of a constituent of the etchant composition of the present invention is not particularly limited because it is adjusted as appropriate by the intended selection ratio and the film properties of the tungsten film and the titanium nitride film, though the content of nitric acid is preferably between 0.01 and 10.0 wt %, further preferably between 0.1 and 5.0 wt %.
  • the etching rate (nm/min) of the etchant composition in the present specification is defined as the etching amount (nm) of a film per treatment time (min).
  • the etching amount of a film can be calculated as the difference between the thickness of the film to be subjected to the etching measured before and after the etching treatment.
  • the etching rate of the etchant composition of the present invention is not particularly limited, though it is preferably in a range between 0.1 and 20.0 nm/min, more preferably in a range between 0.1 and 4.0 nm/min, and further preferably in a range between 0.1 and 2.0 nm/min, for each of the tungsten film and the titanium nitride film.
  • An etchant composition having an appropriately low etching rate as described above is suitable for the etching for manufacture of an accurate structure such as a pattern having a three-dimensional structure.
  • the etching rate for the tungsten film and the etching rate for the titanium nitride film may be modulated corresponding to the thickness or film properties of the tungsten film and the titanium nitride film. For instance, they may be modulated by adjusting as appropriate at least one of the constitution of the etchant composition of the present invention and the temperature at which the etching is carried out.
  • the tungsten film and the titanium nitride film to be subjected to batch etching by the etchant composition of the present invention may be in a form of a substrate comprising the tungsten film and the titanium nitride film each being deposited as a film onto a base material.
  • Constituents for such base material include such as silicon, glass, quartz, polyethylene terephthalate, and polyether sulfone.
  • the tungsten film and the titanium nitride film may be formed onto a silicon oxide film (SiO 2 ) which has been formed onto said base material.
  • the present invention in one embodiment, relates to a method for batch etching of tungsten film and titanium nitride film using the aforementioned etchant composition.
  • the method for etching of the present invention is preferably performed to a substrate comprising a tungsten film and a titanium nitride film.
  • substrates comprising a tungsten film and a titanium nitride film include, though being not particularly limited, for example, an embodiment in which at least one layer of titanium nitride film and at least one layer of tungsten film have been laminated onto the aforementioned base material.
  • it is a substrate in which a titanium nitride film and a tungsten film have been laminated in this order onto a base material.
  • Etching can be performed by bringing the aforementioned etchant composition into contact with the tungsten film and the titanium nitride film of said substrate by a known method, for example.
  • the temperature of the etching composition at which etching is performed is, though not particularly limited, preferably 50° C. or higher.
  • the etchant composition and method for etching of the present invention relate to an etchant composition and method for etching an electrode in manufacture of various electronic devices, specifically a semiconductor memory such as a nonvolatile memory including an NAND-type flash memory.
  • the etchant composition and method for etching of the present invention relate to an etchant composition and method for etching for generating a pattern having a three-dimensional structure, by which it becomes possible to obtain an advanced device such as a large capacity memory.
  • the present invention have been illustrated in detail based on its suitable embodiments as above, though the present invention is not limited thereto and each constitution may be substituted with any substituent which is capable of exhibiting a similar function, or any constituent may also be added.
  • a silicon substrate on which a tungsten film is deposited with 98.8 nm film thickness, and another silicon substrate on which a titanium nitride film is deposited with 81.2 nm film thickness were prepared separately.
  • Each etchant composition was kept at the temperature described in Tables 1 and 2, and each of the prepared substrates was subjected to etching treatment for 30 or 60 min under no-stirring and immersion condition.
  • the etched substrates were washed with ultrapure water and dried by nitrogen blowing.
  • the film thickness was measured using fluorescent X-ray device (Rigaku Corporation, ZSX100e). Then, for each of the tungsten film and the titanium nitride film, the etching amount was calculated from the difference in the film thickness between before and after the etching treatment.
  • Tables 1 and 2 show the constitution of the etchant compositions used in each of the Working Examples and the Comparative Examples, as well as the results of the etching of the tungsten film and the titanium nitride film.
  • the etching rates (E.R.) for the tungsten film and the titanium nitride film are each calculated from the the inclination of the straight line of the linear function derived from the relationship between the etching amount (nm) and the treatment time (min) for the tungsten film and the titanium nitride film.
  • the selection ratio (W/TiN) was calculated by dividing the etching rate for the tungsten film by the etching rate for the titanium nitride film.
  • the etchant composition of Comparative Example 1 is the etchant composition described in JP A 2004-031791.
  • the etchant compositions of Comparative Examples 2 and 3 are the etchant compositions descried in JP A 2010-010273.
  • the etchant compositions of Comparative Examples 1 to 3 cannot be used for etching for generating an accurate structure because the etching rate for at least one of the tungsten film and the titanium nitride film reaches a large value exceeding 10 nm/min (Table 2, FIG. 1 ). Furthermore, because the selection ratio is greatly apart from 1, it is difficult to perform batch etching of tungsten film and titanium nitride film in a well-controlled manner (Table 2, FIG. 2 ).
  • the etchant compositions of Working Examples 1 to 4 had appropriately low etching rate for tungsten film and titanium nitride film (Table 1, FIG. 1 ), and, at the same time, had selection ratio of approximately 1 (Table 1, FIG. 2 ). Therefore, the etchant compositions of Working Examples 1 to 4 are capable of a well-controlled batch etching of tungsten film and titanium nitride film, and furthermore are suitable for etching for generating an accurate structure such as a pattern having a three-dimensional structure.
  • FIG. 3 is a graph in which the etching amount by the etchant composition of Working Example 4 is plotted against the treatment time for each of the tungsten film (a) and the titanium nitride film (b).
  • the graph of FIG. 3 indicates that the etching amount by the etchant composition of Working Example 4 linearly increases against treatment time for both the tungsten film and the titanium nitride film. This means that the etching rate (which corresponds to the inclination of the straight line connecting between plotted points) has caused almost no change with time. Moreover, because the selection ratio of the etching composition of Working Example 4 is approximately 1 (Table 1, FIG. 2 ) and there is little change in etching rate with time ( FIG. 3 ), it is obvious that the selection ratio of the etching composition of Working Example 4 is kept at approximately 1 without changing with time.
  • the use of the etchant composition of the present invention enables batch etching treatment of a tungsten film and a titanium nitride film.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Weting (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

The etching composition of the present invention is an etchant composition comprising nitric acid and water for batch etching treatment of a tungsten film and a titanium nitride film.

Description

    TECHNICAL FIELD
  • The present invention relates to an etchant composition for batch etching treatment of tungsten film and titanium nitride film, and a method for etching using said etchant composition.
    • BACKGROUND ART
  • Tungsten and titanium nitride are both widely used for electric devices such as a semiconductor element. They are deposited as a film having film properties that are appropriate for a desired electric device, processed into a predetermined pattern, and used. As a method for processing tungsten film or titanium nitride film in a predetermined pattern, processing by etching has widely been adopted.
  • As an electric device using tungsten and titanium nitride, a semiconductor memory such as a nonvolatile memory has been known. Recently, such electric devices has remarkably advanced in high-speed processing and capacity enlargement, which in turn has resulted in a greater refinement and complication of the intended pattern shape. Consequently, there also is a growing requirement for techniques and etchants which is used for processing of a pattern.
  • Particularly, when capacity enlargement of a memory is proceeded by adopting a three-dimensional structure, such as the recently published 3D NAND technique, an etchant that is capable of an accurate manufacture of desired three-dimensional structure is required.
  • Patent References 1 and 2 disclose methods of processing a tungsten film using an etchant comprising hydrogen peroxide or ortho periodic acid.
  • Patent References 3 and 4 disclose methods of processing a titanium nitride film using an etchant comprising hydrogen peroxide.
  • However, in the above references, no investigation has been made for an etchant composition for batch etching treatment of a tungsten film and a titanium nitride film. Moreover, when a complicated shape such as a three-dimensional structure is to be formed by a batch etching treatment of a tungsten film and a titanium nitride film, it is necessary to control the etching rate of both of the tungsten film and the titanium nitride film.
  • However, no investigation has been made for such controlling.
    • PRIOR ART REFERENCES Patent References
    • [Patent Reference 1] JP A 2004-31791
    • [Patent Reference 2] JP A 2005-166924
    • [Patent Reference 3] JP A 2010-10273
    • [Patent Reference 4] JP A 2015-30809
    SUMMARY OF THE INVENTION Problems to be Solved by the Invention
  • In view of the conventional problems, an object of the present invention is to provide an etchant composition that is capable of batch etching treatment of tungsten film and titanium nitride film and a method for etching using said etchant composition. Furthermore, another object of the present invention is to provide the etchant composition that is capable of batch etching treatment of tungsten film and titanium nitride film and the method for etching using said etchant composition, while controlling the value of the quotient obtained by dividing the etching rate for the tungsten film by the etching rate for the titanium nitride film (hereinbelow, also referred to as “selection ratio”).
    • Means to Solve the Problems
  • In the course of our investigation to address the above objects, we faced problems including that conventional etchant compositions could not accurately form the desired pattern shape because their etching rate is very fast and the selection ratio is greatly departing from 1. We made a diligent investigation in order to solve such problems and found that an etchant composition comprising nitric acid and water is capable of batch etching of a tungsten film and a titanium nitride film in a favorable shape with good accuracy. We proceeded further study and finally completed the invention.
  • Namely, the present invention relates to the followings:
  • [1] Etchant composition for batch etching treatment of tungsten film and titanium nitride film comprising nitric acid and water.
    [2] The etchant composition according to [1] further comprising at least one selected from the group consisting of sulfuric acid and aliphatic sulfonic acid.
    [3] The etchant composition according to [2], wherein the aliphatic sulfonic acid is methanesulfonic acid.
    [4] The etchant composition according to any one of [1] to [3] further comprising phosphoric acid.
    [5] Method for batch etching of tungsten film and titanium nitride film using the etchant composition according to any one of [1] to [4].
    [6] The method according to [5], wherein the temperature of the etching composition at which the etching is performed is 50° C. or higher.
    [7] The method according to [5] or [6] for generating a pattern having a three-dimensional structure.
    • Effects of the Invention
  • According to the present invention, an etchant composition that is capable of batch etching treatment of tungsten film and titanium nitride film and a method for etching using said etchant composition can be provided.
  • Specifically, by including at least one selected from the group consisting of sulfuric acid and aliphatic sulfonic acid in the etchant composition of the present invention, it becomes possible to control the selection ratio at approximately 1, which makes the aforementioned effect remarkable.
    • BRIEF DESCRIPTION OF DRAWINGS
  • FIG. 1 is a graph showing the etching rate of the etchant composition (E.R.) of Working Examples 1 to 4 and Comparative Examples 1 to 3.
  • FIG. 2 is a graph showing the selection ratio of the etchant composition of Working Examples 1 to 4 and Comparative Examples 1 to 3.
  • FIG. 3 is a graph showing the change in the etching amount of the etchant composition of Working Example 4 over time.
    •  MODES FOR PRACTICING THE INVENTION
  • Hereinbelow, the present invention is illustrated in detail based on suitable embodiments of the present invention.
  • The etchant composition of the present invention is used for batch etching treatment of tungsten film and titanium nitride film.
  • The etchant composition of the present invention comprises nitric acid and water. This enables a reduction in etching rates for tungsten film and titanium nitride film to appropriate level, which in turn enables providing an etchant composition for batch etching treatment of tungsten film and titanium nitride film which has never been investigated so far.
  • In the etchant composition of the present invention, water is used as a solvent.
  • The content of water in the etchant composition is, though not being particularly limited, preferably between 2.0 and 80.0 wt %, more preferably between 5.0 and 70.0 wt %.
  • Specifically, when etching treatment is carried out under a temperature-rising condition, the content of water is made to be preferably between 8.0 and 65.0 wt % in order to suppress a change in the constitution of the etchant composition due to water evaporation. It is preferred to suppress the change in the constitution of the etchant composition because it reduces a risk of a change in the selection ratio during etching treatment due to constitution change even when the etching treatment under the temperature-rising condition requires a prolonged time. Moreover, it enables a repeated use of the etchant composition because the change in the selection ratio before and after the etching treatment is small. This is preferred from the perspective of reduction of the cost and environmental burden resulting from waste liquid processing of the etchant.
  • The etchant composition of the present invention preferably comprises at least one selected from the group consisting of sulfuric acid and aliphatic sulfonic acid.
  • When the etchant composition consists of nitric acid and water, it is difficult to decrease the water content in the etchant composition. However, the water content can further be decreased by adding at least one selected from the group consisting of sulfuric acid and aliphatic sulfonic acid.
  • This is preferred because it enables controlling of the constitution of the etchant composition in a wider range, and because it enables decreasing the water content in a case where it is desired to suppress a change in the constitution of the etchant composition due to water evaporation.
  • As mentioned later, the content of a constituent of the etchant composition of the present invention is not particularly limited because it is adjusted as appropriate by the intended selection ratio and the film properties of the tungsten film and the titanium nitride film, though the content of at least one selected from the group consisting of sulfuric acid and aliphatic sulfonic acid is preferably between 5.0 and 95.0 wt %, more preferably between 8.0 and 40.0 wt %.
  • Examples for the aliphatic sulfonic acid include an aliphatic sulfonic acid having 1 to 10 carbon atoms. More specific examples include such as methanesulfonic acid, ethanesulfonic acid and 1-propanesulfonic acid. As an aliphatic sulfonic acid used in the etchant composition of the present invention, methanesulfonic acid is preferred.
  • The etchant composition of the present invention preferably comprises phosphoric acid. It is preferred to include phosphoric acid in the etchant composition, because it enables adjusting of the constitution of the etchant composition in wider range.
  • As mentioned later, the content of a constituent of the etchant composition of the present invention is not particularly limited because it is adjusted as appropriate by the intended selection ratio and the film properties of the tungsten film and the titanium nitride film, though the content of phosphoric acid is preferably between 0.1 and 90.0 wt %, more preferably between 0.5 and 80.0 wt %.
  • The etchant composition of the present invention may comprise any ingredient in addition to the above-mentioned ingredients, as long as it does not hinder the batch etching treatment of tungsten film and titanium nitride film. Optional ingredients which may be used in the present invention include such as, for example, a surfactant.
  • Nevertheless, in a case where the formation of an accurate pattern such as a pattern having a three-dimensional structure is required, it is preferred not to include hydrogen peroxide and ortho periodic acid, as well as a fluorine-containing compound such as hydrofluoric acid which would cause an undue increase in etching rate.
  • Moreover, when it is required to suppress the change in constitution of the etchant composition under a temperature-rising condition, it is preferred not to include a highly volatile ingredient even if the ingredient is generally contained in an etchant. Specific examples for such highly volatile ingredient include carboxylic acids such as a formic acid and acetic acid and the salts thereof, as well as polyfunctional carboxylic acids such as citric acid and tartaric acid and the salts thereof.
  • As mentioned above, the etchant composition of the present invention is used for batch etching treatment of tungsten film and titanium nitride film. In another embodiment, the etchant composition of the present invention is used for forming a pattern having a three-dimensional structure by batch etching treatment of tungsten film and titanium nitride film.
  • Namely, the etchant composition of the present invention may be used for batch etching of a laminate body comprising at least one layer of tungsten film and at least one layer of titanium nitride film. Furthermore, controlling of the selection ratio to approximately 1 enables batch etching of tungsten film and titanium nitride film in a refined shape, for examples, in a pattern having a three-dimensional structure. In order to form a refined structure, the selection ratio is preferably between 0.70 and 1.30, more preferably between 0.80 and 1.20.
  • The selection ratio of the etchant composition of the present invention may be adjusted as appropriate by altering the constituents of the composition. For instance, the selection ratio tends to be decreased a little by increasing the content of nitric acid in the etchant composition, whereas the selection ratio tends to be increased by increasing water content. On the other hand, the selection ratio tends to be decreased by increasing the content of either of sulfuric acid, aliphatic sulfonic acid or phosphoric acid. Because the selection ratio also depends on the film properties of the tungsten film and the titanium nitride film, the desired selection ratio can be obtained by adjusting the constituents of the composition as appropriate according to the film properties of the film to be subjected to the etching.
  • As mentioned above, the content of a constituent of the etchant composition of the present invention is not particularly limited because it is adjusted as appropriate by the intended selection ratio and the film properties of the tungsten film and the titanium nitride film, though the content of nitric acid is preferably between 0.01 and 10.0 wt %, further preferably between 0.1 and 5.0 wt %.
  • The etching rate (nm/min) of the etchant composition in the present specification is defined as the etching amount (nm) of a film per treatment time (min). The etching amount of a film can be calculated as the difference between the thickness of the film to be subjected to the etching measured before and after the etching treatment.
  • The etching rate of the etchant composition of the present invention is not particularly limited, though it is preferably in a range between 0.1 and 20.0 nm/min, more preferably in a range between 0.1 and 4.0 nm/min, and further preferably in a range between 0.1 and 2.0 nm/min, for each of the tungsten film and the titanium nitride film. An etchant composition having an appropriately low etching rate as described above is suitable for the etching for manufacture of an accurate structure such as a pattern having a three-dimensional structure.
  • The etching rate for the tungsten film and the etching rate for the titanium nitride film may be modulated corresponding to the thickness or film properties of the tungsten film and the titanium nitride film. For instance, they may be modulated by adjusting as appropriate at least one of the constitution of the etchant composition of the present invention and the temperature at which the etching is carried out.
  • The tungsten film and the titanium nitride film to be subjected to batch etching by the etchant composition of the present invention may be in a form of a substrate comprising the tungsten film and the titanium nitride film each being deposited as a film onto a base material.
  • Constituents for such base material include such as silicon, glass, quartz, polyethylene terephthalate, and polyether sulfone. Moreover, the tungsten film and the titanium nitride film may be formed onto a silicon oxide film (SiO2) which has been formed onto said base material.
  • Moreover, the present invention, in one embodiment, relates to a method for batch etching of tungsten film and titanium nitride film using the aforementioned etchant composition.
  • The method for etching of the present invention is preferably performed to a substrate comprising a tungsten film and a titanium nitride film. Such substrates comprising a tungsten film and a titanium nitride film include, though being not particularly limited, for example, an embodiment in which at least one layer of titanium nitride film and at least one layer of tungsten film have been laminated onto the aforementioned base material. Preferably, it is a substrate in which a titanium nitride film and a tungsten film have been laminated in this order onto a base material.
  • Etching can be performed by bringing the aforementioned etchant composition into contact with the tungsten film and the titanium nitride film of said substrate by a known method, for example.
  • The temperature of the etching composition at which etching is performed is, though not particularly limited, preferably 50° C. or higher.
  • On the other hand, when the temperature of the etchant composition at which etching is performed is below 50° C., a practical etching rate may not be obtained.
  • In one embodiment of the present invention, the etchant composition and method for etching of the present invention relate to an etchant composition and method for etching an electrode in manufacture of various electronic devices, specifically a semiconductor memory such as a nonvolatile memory including an NAND-type flash memory. In one further embodiment of the present invention, the etchant composition and method for etching of the present invention relate to an etchant composition and method for etching for generating a pattern having a three-dimensional structure, by which it becomes possible to obtain an advanced device such as a large capacity memory.
  • The present invention have been illustrated in detail based on its suitable embodiments as above, though the present invention is not limited thereto and each constitution may be substituted with any substituent which is capable of exhibiting a similar function, or any constituent may also be added.
    • Working Examples
  • The present invention will be presented with the following Working Examples and Comparative Examples to further illustrate the content of the invention, though the present invention is not limited to these Working Examples.
  • Experiments were carried out using the etchant compositions of the present invention and the etchant composition for comparison according to the following methods.
  • A silicon substrate on which a tungsten film is deposited with 98.8 nm film thickness, and another silicon substrate on which a titanium nitride film is deposited with 81.2 nm film thickness were prepared separately. Each etchant composition was kept at the temperature described in Tables 1 and 2, and each of the prepared substrates was subjected to etching treatment for 30 or 60 min under no-stirring and immersion condition. The etched substrates were washed with ultrapure water and dried by nitrogen blowing.
  • For each of the tungsten film and the titanium nitride film before and after the etching treatment, the film thickness was measured using fluorescent X-ray device (Rigaku Corporation, ZSX100e). Then, for each of the tungsten film and the titanium nitride film, the etching amount was calculated from the difference in the film thickness between before and after the etching treatment.
  • Tables 1 and 2 show the constitution of the etchant compositions used in each of the Working Examples and the Comparative Examples, as well as the results of the etching of the tungsten film and the titanium nitride film. The etching rates (E.R.) for the tungsten film and the titanium nitride film are each calculated from the the inclination of the straight line of the linear function derived from the relationship between the etching amount (nm) and the treatment time (min) for the tungsten film and the titanium nitride film. The selection ratio (W/TiN) was calculated by dividing the etching rate for the tungsten film by the etching rate for the titanium nitride film.
  • TABLE 1
    Selection
    H3PO4 HNO3 H2SO4 MeSO3H H2O Temperature E.R. of W E.R. of TiN Ratio
    (wt %) (wt %) (wt %) (wt %) (wt %) (° C.) (nm/min) (nm/min) (W/TiN)
    Working 0 1.21 36.50 0 62.29 70 2.17 2.09 1.04
    Example 1
    Working 0 1.21 0 30.00 68.79 0.31 0.26 1.18
    Example 2
    Working 71.38 1.21 11.73 0 15.68 0.63 0.64 0.99
    Example 3
    Working 68.44 1.16 0 17.71 12.69 0.44 0.43 1.02
    Example 4
  • TABLE 2
    Selection
    H2O2 KOH TMAH EDTA H2O Temperature E.R. of W E.R. of TiN Ratio
    (wt %) (wt %) (wt %) (wt %) (wt %) (° C.) (nm/min) (nm/min) (W/TiN)
    Comparative 31.00 0.05 0 0 68.95 28 12.78 2.05 6.23
    Example 1
    Comparative 28.40 0 0.50 0 71.10 60 85.68 20.32 4.22
    Example 2
    Comparative 14.20 0 1.80 1.40 82.60 60 46.24 8.68 5.33
    Example 3
  • The etchant composition of Comparative Example 1 is the etchant composition described in JP A 2004-031791. The etchant compositions of Comparative Examples 2 and 3 are the etchant compositions descried in JP A 2010-010273.
  • The etchant compositions of Comparative Examples 1 to 3 cannot be used for etching for generating an accurate structure because the etching rate for at least one of the tungsten film and the titanium nitride film reaches a large value exceeding 10 nm/min (Table 2, FIG. 1). Furthermore, because the selection ratio is greatly apart from 1, it is difficult to perform batch etching of tungsten film and titanium nitride film in a well-controlled manner (Table 2, FIG. 2).
  • In contrast to these Comparative Examples, the etchant compositions of Working Examples 1 to 4 had appropriately low etching rate for tungsten film and titanium nitride film (Table 1, FIG. 1), and, at the same time, had selection ratio of approximately 1 (Table 1, FIG. 2). Therefore, the etchant compositions of Working Examples 1 to 4 are capable of a well-controlled batch etching of tungsten film and titanium nitride film, and furthermore are suitable for etching for generating an accurate structure such as a pattern having a three-dimensional structure.
  • Furthermore, FIG. 3 is a graph in which the etching amount by the etchant composition of Working Example 4 is plotted against the treatment time for each of the tungsten film (a) and the titanium nitride film (b).
  • The graph of FIG. 3 indicates that the etching amount by the etchant composition of Working Example 4 linearly increases against treatment time for both the tungsten film and the titanium nitride film. This means that the etching rate (which corresponds to the inclination of the straight line connecting between plotted points) has caused almost no change with time. Moreover, because the selection ratio of the etching composition of Working Example 4 is approximately 1 (Table 1, FIG. 2) and there is little change in etching rate with time (FIG. 3), it is obvious that the selection ratio of the etching composition of Working Example 4 is kept at approximately 1 without changing with time.
    • INDUSTRIAL APPLICABILITY
  • The use of the etchant composition of the present invention enables batch etching treatment of a tungsten film and a titanium nitride film.

Claims (7)

1. Etchant composition for batch etching treatment of tungsten film and titanium nitride film comprising a nitric acid and water.
2. The etchant composition according to claim 1, further comprising at least one selected from the group consisting of a sulfuric acid and an aliphatic sulfonic acid.
3. The etchant composition according to claim 2, wherein the aliphatic sulfonic acid is a methanesulfonic acid.
4. The etchant composition according to claim 1 further comprising a phosphoric acid.
5. Method for batch etching of tungsten film and titanium nitride film using the etchant composition according to claim 1.
6. The method according to claim 5, wherein the temperature of the etchant composition at which the etching is performed is 50° C. or higher.
7. The method according to claim 5 for generating a pattern having a three-dimensional structure.
US16/316,054 2016-07-08 2017-07-07 Etchant compositions and method for etching Abandoned US20190301026A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2016136336A JP6769760B2 (en) 2016-07-08 2016-07-08 Etching liquid composition and etching method
JP2016-136336 2016-07-08
PCT/JP2017/024971 WO2018008745A1 (en) 2016-07-08 2017-07-07 Etching liquid composition and etching method

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/024971 A-371-Of-International WO2018008745A1 (en) 2016-07-08 2017-07-07 Etching liquid composition and etching method

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US17/132,560 Division US11512397B2 (en) 2016-07-08 2020-12-23 Etchant composition and method for etching

Publications (1)

Publication Number Publication Date
US20190301026A1 true US20190301026A1 (en) 2019-10-03

Family

ID=60912793

Family Applications (2)

Application Number Title Priority Date Filing Date
US16/316,054 Abandoned US20190301026A1 (en) 2016-07-08 2017-07-07 Etchant compositions and method for etching
US17/132,560 Active US11512397B2 (en) 2016-07-08 2020-12-23 Etchant composition and method for etching

Family Applications After (1)

Application Number Title Priority Date Filing Date
US17/132,560 Active US11512397B2 (en) 2016-07-08 2020-12-23 Etchant composition and method for etching

Country Status (7)

Country Link
US (2) US20190301026A1 (en)
JP (1) JP6769760B2 (en)
KR (1) KR20190025609A (en)
CN (1) CN109328394A (en)
SG (1) SG11201811649QA (en)
TW (1) TWI758303B (en)
WO (1) WO2018008745A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210175093A1 (en) * 2019-12-04 2021-06-10 Tokyo Electron Limited Substrate processing apparatus and substrate processing method
US11427759B2 (en) * 2019-10-17 2022-08-30 Samsung Electronics Co., Ltd. Etchant compositions for metal-containing films and methods of manufacturing integrated circuit devices using the etchant compositions
US11499236B2 (en) 2018-03-16 2022-11-15 Versum Materials Us, Llc Etching solution for tungsten word line recess

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108588728A (en) * 2018-05-16 2018-09-28 深圳仕上电子科技有限公司 The method for removing workpiece surface film using aqueous solution of nitric acid
CN108707899A (en) * 2018-05-16 2018-10-26 深圳仕上电子科技有限公司 The method for removing titanium and titanium nitride film using hydrogen peroxide solution
SG11202101593YA (en) * 2018-08-31 2021-03-30 Kao Corp Etching liquid
CN112752867B (en) 2018-09-12 2024-05-24 富士胶片电子材料美国有限公司 Etching composition
JP7398969B2 (en) * 2019-03-01 2023-12-15 東京エレクトロン株式会社 Substrate processing method, substrate processing apparatus and storage medium
CN110195229B (en) * 2019-06-21 2021-05-14 湖北兴福电子材料有限公司 Etching solution for tungsten and titanium nitride metal film and use method thereof
JP7427155B2 (en) * 2019-08-23 2024-02-05 東京エレクトロン株式会社 Non-plasma etching of titanium-containing material layers with tunable selectivity to other metals and dielectrics
CN114350365A (en) * 2021-12-07 2022-04-15 湖北兴福电子材料有限公司 Etching solution for stably etching titanium nitride
CN114369462A (en) * 2021-12-16 2022-04-19 湖北兴福电子材料有限公司 Etching solution for selectively etching titanium nitride and tungsten

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060189123A1 (en) * 2003-09-04 2006-08-24 Advanced Display Inc. Etchant and method of etching
US20130178069A1 (en) * 2010-09-17 2013-07-11 Mitsubishi Gas Chemical Company, Inc. Silicon etching fluid and method for producing transistor using same
US20130203263A1 (en) * 2010-08-31 2013-08-08 Mitsubishi Gas Chemical Company, Inc. Silicon etchant and method for producing transistor by using same
US20150075850A1 (en) * 2013-09-18 2015-03-19 Kanto Kagaku Kabushiki Kaisha Metal oxide etching solution and an etching method
US20150255494A1 (en) * 2014-03-07 2015-09-10 Patrick Hogan Etch chemistries for metallization in electronic devices
US20170355882A1 (en) * 2014-12-26 2017-12-14 Fujimi Incorporated Polishing composition, polishing method, and method for manufacturing ceramic component
US20170355881A1 (en) * 2014-12-26 2017-12-14 Fujimi Incorporated Polishing composition, polishing method, and method for manufacturing ceramic component

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1640737A (en) 1922-07-15 1927-08-30 Du Pont Nitration process and nitrating mixture therefor
US4610798A (en) 1985-04-16 1986-09-09 Michael Burkus Method and composition of matter for conditioning and passivating certain metals
US5424000A (en) 1993-10-05 1995-06-13 West Agro, Inc. Acid cleanings and staining compositions
JPH07122651A (en) * 1993-10-22 1995-05-12 Hitachi Ltd Semiconductor device and fabrication thereof
TW374802B (en) 1996-07-29 1999-11-21 Ebara Densan Ltd Etching composition, method for roughening copper surface and method for producing printed wiring board
JP2001077118A (en) * 1999-06-30 2001-03-23 Toshiba Corp Semiconductor device and manufacture threof
TWI245071B (en) 2002-04-24 2005-12-11 Mitsubishi Chem Corp Etchant and method of etching
JP2004031791A (en) 2002-06-27 2004-01-29 Mitsubishi Chemicals Corp Etchant and etching method for tungsten alloy
JP4355201B2 (en) 2003-12-02 2009-10-28 関東化学株式会社 Tungsten metal removing liquid and tungsten metal removing method using the same
JP5037442B2 (en) 2008-06-25 2012-09-26 東京応化工業株式会社 Titanium nitride removing liquid, method for removing titanium nitride film, and method for producing titanium nitride removing liquid
SG173833A1 (en) * 2009-02-25 2011-09-29 Avantor Performance Mat Inc Stripping compositions for cleaning ion implanted photoresist from semiconductor device wafers
JP5396514B2 (en) * 2011-06-30 2014-01-22 富士フイルム株式会社 Etching method, etching solution used therefor, and method for manufacturing semiconductor substrate product using the same
KR20130049504A (en) * 2011-11-04 2013-05-14 동우 화인켐 주식회사 Etching solution composition for a tungsten layer and method for etching the tungsten layer using the same
US9338896B2 (en) 2012-07-25 2016-05-10 Enthone, Inc. Adhesion promotion in printed circuit boards
JP6063206B2 (en) * 2012-10-22 2017-01-18 富士フイルム株式会社 Etching solution, etching method using the same, and semiconductor device manufacturing method
KR101812085B1 (en) 2013-05-02 2017-12-27 후지필름 가부시키가이샤 Etching solution and etching solution kit, etching method using same, and production method for semiconductor substrate product
JP6174935B2 (en) 2013-08-05 2017-08-02 三和油化工業株式会社 Etching solution composition
KR102161019B1 (en) * 2013-10-31 2020-09-29 솔브레인 주식회사 Composition for etching titanium nitrate layer-tungsten layer containing laminate, method for etching using the same and semiconductor device manufactured by using the same
KR102190370B1 (en) * 2014-01-10 2020-12-11 삼성전자주식회사 Methods of forming conductive patterns and methods of manufacturing semiconductor devices using the same
JP2016017209A (en) 2014-07-08 2016-02-01 メック株式会社 Etching agent and replenishing liquid
KR101587758B1 (en) 2015-03-05 2016-01-21 동우 화인켐 주식회사 ETCHANT COMPOSITION FOR ETHCING TiN LAYER AND METHOD FOR FORMING METAL LINE USING THE SAME

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060189123A1 (en) * 2003-09-04 2006-08-24 Advanced Display Inc. Etchant and method of etching
US20130203263A1 (en) * 2010-08-31 2013-08-08 Mitsubishi Gas Chemical Company, Inc. Silicon etchant and method for producing transistor by using same
US20130178069A1 (en) * 2010-09-17 2013-07-11 Mitsubishi Gas Chemical Company, Inc. Silicon etching fluid and method for producing transistor using same
US20150075850A1 (en) * 2013-09-18 2015-03-19 Kanto Kagaku Kabushiki Kaisha Metal oxide etching solution and an etching method
US20150255494A1 (en) * 2014-03-07 2015-09-10 Patrick Hogan Etch chemistries for metallization in electronic devices
US20170355882A1 (en) * 2014-12-26 2017-12-14 Fujimi Incorporated Polishing composition, polishing method, and method for manufacturing ceramic component
US20170355881A1 (en) * 2014-12-26 2017-12-14 Fujimi Incorporated Polishing composition, polishing method, and method for manufacturing ceramic component

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11499236B2 (en) 2018-03-16 2022-11-15 Versum Materials Us, Llc Etching solution for tungsten word line recess
US11427759B2 (en) * 2019-10-17 2022-08-30 Samsung Electronics Co., Ltd. Etchant compositions for metal-containing films and methods of manufacturing integrated circuit devices using the etchant compositions
US20210175093A1 (en) * 2019-12-04 2021-06-10 Tokyo Electron Limited Substrate processing apparatus and substrate processing method
US11862474B2 (en) * 2019-12-04 2024-01-02 Tokyo Electron Limited Substrate processing apparatus and substrate processing method

Also Published As

Publication number Publication date
TWI758303B (en) 2022-03-21
SG11201811649QA (en) 2019-01-30
JP2018006715A (en) 2018-01-11
US20210123142A1 (en) 2021-04-29
US11512397B2 (en) 2022-11-29
JP6769760B2 (en) 2020-10-14
KR20190025609A (en) 2019-03-11
WO2018008745A1 (en) 2018-01-11
CN109328394A (en) 2019-02-12
TW201816187A (en) 2018-05-01

Similar Documents

Publication Publication Date Title
US11512397B2 (en) Etchant composition and method for etching
CN104614907B (en) Method for manufacturing array substrate for liquid crystal display
US8377325B2 (en) Etchant for metal wiring and method for manufacturing metal wiring using the same
KR101805187B1 (en) An etching solution composition
KR102368373B1 (en) Etchant composition and manufacturing method of an array substrate for liquid crystal display
JP2001156053A (en) Etching composition for manufacturing semiconductor elements and etching method using same
KR102419970B1 (en) Composision for etching, method for etching and electronic device
KR20160114360A (en) Etching solution composition for copper-based metal layer and method for etching copper-based metal layer using the same
KR20170068328A (en) Etchant composition, and method for etching
KR102323941B1 (en) Etching solution composition for copper-based metal layer and method for etching copper-based metal layer using the same
KR20140028446A (en) Etchant composition for etching metal wire and method for preparing metal wire using the same
KR102131393B1 (en) Manufacturing method of an array substrate for liquid crystal display
KR101978389B1 (en) Etchant composition and manufacturing method of an array substrate for image display device
KR102362460B1 (en) Etchant composition
KR20150035213A (en) Manufacturing method of an array substrate for liquid crystal display
KR102142419B1 (en) Manufacturing method of an array substrate for liquid crystal display
KR102653026B1 (en) An etchant composition and an ehting method and a mehtod for fabrication metal pattern using the same
CN107653451B (en) Etching solution composition and method for manufacturing metal pattern using the same
KR102590529B1 (en) Etchant composition for metal layer and etching method of metal layer using the same
KR102092927B1 (en) Manufacturing method of an array substrate for liquid crystal display
KR20150114248A (en) Manufacturing method of an array substrate for liquid crystal display
KR102169571B1 (en) Manufacturing method of an array substrate for liquid crystal display
KR102142420B1 (en) Manufacturing method of an array substrate for liquid crystal display
KR20180050633A (en) Manufacturing method of an array substrate for liquid crystal display
KR20190113416A (en) Etchant composition for copper-based metal layer and manufacturing method of an array substrate for liquid crystal display using thereof

Legal Events

Date Code Title Description
AS Assignment

Owner name: KANTO KAGAKU KABUSHIKI KAISHA, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KOUNO, RYOU;OHWADA, TAKUO;REEL/FRAME:048390/0634

Effective date: 20190108

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION