WO2021121552A1 - Composition de décapage de résine photosensible - Google Patents

Composition de décapage de résine photosensible Download PDF

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Publication number
WO2021121552A1
WO2021121552A1 PCT/EP2019/085474 EP2019085474W WO2021121552A1 WO 2021121552 A1 WO2021121552 A1 WO 2021121552A1 EP 2019085474 W EP2019085474 W EP 2019085474W WO 2021121552 A1 WO2021121552 A1 WO 2021121552A1
Authority
WO
WIPO (PCT)
Prior art keywords
photoresist stripping
photoresist
stripping composition
composition
organic solvent
Prior art date
Application number
PCT/EP2019/085474
Other languages
English (en)
Inventor
Atsushi Otake
Original Assignee
Henkel Ag & Co. Kgaa
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 Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Priority to PCT/EP2019/085474 priority Critical patent/WO2021121552A1/fr
Publication of WO2021121552A1 publication Critical patent/WO2021121552A1/fr

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides

Definitions

  • the present invention relates to a photoresist stripping composition.
  • a microelectronic circuit is produced, for example, by the following steps: a conductive metal film or a dielectric film is formed on a silicon, glass, or ceramic substrate; subsequently, after the surface of the conductive metal film or the dielectric film is coated with a photosensitive polymer composition called a photoresist, a photomask is used for selective exposure to form a resist pattern; and dry etching or wet etching is then performed using the obtained resist pattern as an etching mask. Further, a process of forming an electronic circuit by wet plating or vacuum deposition using, as a template, a resist pattern formed on a substrate, is also known.
  • a photoresist stripping agent is used to strip the remaining photoresist and dry etching residue from the substrate after the dry etching step.
  • a photoresist stripping agent is also used to strip the photoresist from the substrate after an electronic circuit is formed by wet etching, wet plating, or vacuum deposition.
  • a multi-level interconnect structure is widely applied. Copper interconnects are mainly used in a multi-level interconnect structure of advanced semiconductor devices. Considering the economics of the manufacturing process, it is desirable that one kind of photoresist stripping composition is used not only for copper interconnect structures, but also for other types of interconnect structures.
  • TMAH tetramethylammonium hydroxide
  • organic solvent such as dimethyl sulfoxide
  • An object of the present invention is to provide a photoresist stripping composition that causes reduced damage on copper interconnects while retaining sufficient stripping ability.
  • the present inventor conducted extensive research to solve the above problem. As a result, the inventor found that known photoresist stripping compositions comprising an organic solvent, tetramethylammonium hydroxide (TMAH), and alkanolamine have problems regarding either insufficient photoresist stripping ability, or damage on copper. Surprisingly, however, a photoresist stripping composition comprising an organic solvent, choline hydroxide, and triethanolamine significantly suppressed damage on copper.
  • the present invention has been accomplished by further research based on this finding, and includes the following embodiments.
  • a photoresist stripping composition comprising:
  • the photoresist stripping composition according to Item 1 containing the choline hydroxide in an amount of 0.8 to 20 wt% based on the total weight of the photoresist stripping composition.
  • the photoresist stripping composition according to Item 1 or 2 containing triethanolamine in an amount of 5 to 20 wt% based on the total weight of the photoresist stripping composition.
  • the photoresist stripping composition according to any one of Items 1 to 3, containing the organic solvent in an amount of 50 wt% or more based on the total weight of the photoresist stripping composition.
  • the photoresist stripping composition according to any one of Items 1 to 4, wherein the organic solvent is an aprotic polar solvent.
  • the photoresist stripping composition according to any one of Items 1 to 5, wherein the organic solvent is dimethyl sulfoxide and/or N-methylpyrrolidone.
  • a photoresist stripping method comprising applying a composition to a photoresist on an electronic device having copper interconnects, the composition comprising:
  • a photoresist stripping composition that causes reduced damage on copper interconnects, while retaining sufficient stripping ability, can be provided.
  • the photoresist stripping composition of the present invention comprises:
  • the photoresist stripping composition of the present invention comprises at least one organic solvent.
  • the photoresist stripping composition of the present invention may comprise only one kind of organic solvent; or may comprise a combination of two or more kinds of organic solvent.
  • the photoresist stripping composition of the present invention may comprise at least one organic solvent preferably selected from aprotic polar solvents, more preferably selected from aprotic polar solvents having a relative permittivity measured at 20 °C and 1 kHz of 20 to 50, even more preferably selected from the group consisting of N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), methyl diglycol (MDG), buthyl diglycol (BDG), N,N- dimethylformamide, N,N-dimethylacetamide, g-butyrolactone, ethylene glycol, propylene glycol, and mixtures thereof.
  • NMP N-methylpyrrolidone
  • DMSO dimethyl sulfoxide
  • MDG methyl diglycol
  • BDG buthyl diglycol
  • N,N- dimethylformamide N,N-dimethylacetamide
  • g-butyrolactone ethylene glycol, propylene glycol, and mixture
  • the photoresist stripping composition of the present invention may preferably comprise at least one organic solvent selected from N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), and mixtures thereof.
  • NMP N-methylpyrrolidone
  • DMSO dimethyl sulfoxide
  • DMSO is preferred in view of the fact that DMSO promotes solubility of etching residue, residual photoresist, and photoresist by-products on a semiconductor, a display substrate, and the like.
  • DMSO is, for example, but not limited to, a product commercially available from Toray Fine Chemicals Co., Ltd.
  • the total content of the organic solvent(s) in the photoresist stripping composition of the present invention is preferably more than 50 wt%, and more preferably more than 60 wt%, based on the total weight of the composition.
  • the upper limit of the total content of the organic solvent(s) in the composition is not limited as long as a sufficient level of photoresist stripping ability is achieved, and damage on metals such as copper is sufficiently suppressed when the photoresist stripping composition is used.
  • the upper limit is preferably 95 wt% or less, and more preferably 90 wt% or less, in view of suppression of damage on metals such as copper.
  • the photoresist stripping composition of the present invention comprises choline hydroxide.
  • Choline hydroxide is also known as (2-hydroxyethyl)trimethylammonium hydroxide. Choline hydroxide is, for example, but not limited to, a product commercially available from Huntsman Corporation.
  • the content of the choline hydroxide in the photoresist stripping composition of the present invention is preferably 1 wt% or more, based on the total weight of the composition.
  • the upper limit is preferably 10 wt% or less, and more preferably 5 wt% or less.
  • the photoresist stripping composition of the present invention comprises triethanolamine. Because of the presence of triethanolamine in the photoresist stripping composition of the present invention, damage on metals such as copper can be suppressed when the photoresist stripping composition is used.
  • the content of the triethanolamine in the photoresist stripping composition of the present invention is usually 0.1 wt% or more, preferably 1 wt% or more, and more preferably 5 wt% or more, based on the total weight of the composition.
  • the upper limit is preferably 50 wt% or less, and more preferably 30 wt% or less.
  • Triethanolamine is, for example, but not limited to, a product commercially available from Dow Chemical Company and Nippon Shokubai Co., Ltd.
  • the photoresist stripping composition of the present invention may further contain, in addition to the above components, components commonly used as components of a photoresist stripping agent, which are at least one component selected from the group consisting of surfactants, organic acids, hydrogen fluoride or salts thereof, chelating agents, corrosion inhibition agents, anti-foaming agents, and preservative agents. Such components may be commercially available products.
  • the photoresist stripping composition of the present invention is used to strip the remaining photoresist and dry etching residue from a substrate after a dry etching step in the production of semiconductor devices, such as semiconductor integrated circuits (IC) and large-scale integrated circuits (LSI); display devices, such as liquid crystal displays (LCD) and light- emitting diode (LED) displays; MEMS (Micro Electro Mechanical Systems) and sensor devices; or other electronic equipment.
  • semiconductor devices such as semiconductor integrated circuits (IC) and large-scale integrated circuits (LSI)
  • display devices such as liquid crystal displays (LCD) and light- emitting diode (LED) displays
  • MEMS Micro Electro Mechanical Systems
  • sensor devices or other electronic equipment.
  • the photoresist stripping method of the present invention is a method for stripping a photoresist using the photoresist stripping composition of the present invention.
  • the photoresist stripping method of the present invention may be performed by any cleaning system.
  • the cleaning system to be used can be selected, for example, from ultrasonic cleaning, shower cleaning, spray cleaning, high-pressure jet cleaning, brush cleaning, immersion cleaning, swing cleaning, single-wafer cleaning system, and combinations thereof. In view of cleaning effects and work efficiency, the cleaning system is preferably immersion cleaning by an ultrasound system.
  • the photoresist stripping method of the present invention comprises a step of applying the photoresist stripping composition of the present invention to the surface comprising a photoresist, and further comprises a step of stripping the photoresist by a cleaning system as described above.
  • the photoresist stripping method of the present invention can be performed using the photoresist stripping composition of the present invention at various temperatures.
  • This temperature can usually be from 10°C to 90°C. When the temperature is 10°C or higher, freezing of the photoresist stripping composition can be avoided. When the temperature is 90°C or less, evaporation of the photoresist stripping composition can be avoided.
  • the temperature of the photoresist stripping composition at the time of cleaning is preferably 40°C to 80°C, in view of the photoresist stripping effect.
  • a commercially available THMR-iP5700 photoresist composition provided by Tokyo Ohka Kogyo Co., Ltd., was used to prepare test wafers.
  • a photoresist composition was coated on 6-inch silicon wafers treated with 1,1,1,3,3,3-hexamethyldisilazane.
  • the photoresist coated on the wafers was exposed to 365 nm UV light through a line-hole pattern mask using an i- line stepper. After development and post-baking steps, the test wafers were cut into small pieces for a photoresist stripping test.
  • Test wafer pieces coated with THMR-iP5700 were individually immersed in the compositions for 5 minutes. Afterward, the test wafer pieces were rinsed with deionized water, and dried by nitrogen stream. The photoresist stripping results were determined by visual inspection.
  • etching rate of photoresist stripping compositions for Cu film formed on Si substrates.
  • Commercially available test wafers formed with Cu films used for the examples were provided by Philtech Inc.
  • the etching rate of copper (Cu ER) was determined from process time and thickness loss of copper film formed on silicon wafer.
  • the thickness of copper film was measured by using an RT-70 four-point probe, manufactured by Napson Corporation. After determining the initial copper thickness, test wafers were immersed in the test solution at 60°C. After 30 minutes, the test wafers were removed from the test solution, rinsed with deionized water, and dried completely under nitrogen. Subsequently, the copper thickness was measured to determine the thickness loss by immersion in the test solutions.
  • DMSO Dimethyl sulfoxide, produced by Toray Fine Chemicals Co., Ltd.
  • TEA Triethanolamine, produced by Dow Chemical Company.
  • Choline hydroxide produced by Tokyo Chemical Industry Co., Ltd., in the form of a 49 wt% aqueous solution of 2-hydroxyethyltrimethylammonium hydroxide.
  • TMAH Tetramethylammonium hydroxide
  • test wafers used in the above examples are shown below.
  • Cu-coated wafer 8-inch silicon wafers coated with 300 nm vapor-deposited copper film, provided by Philtech Inc.
  • composition of Comparative Example 1 which contained a small amount of choline hydroxide, showed insufficient photoresist stripping ability.
  • compositions of Examples 1 to 4 which contained a suitable amount of choline hydroxide, showed sufficient photoresist stripping ability and controlled Cu ER.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

Un objectif de la présente invention est de fournir une composition de décapage de résine photosensible qui cause moins de dommage aux interconnexions en cuivre tout en conservant une capacité de décapage suffisante. La solution de l'invention concerne une composition de décapage de résine photosensible comprenant (A) au moins un solvant organique, (B) de l'hydroxyde de choline et (C) de la triéthanolamine.
PCT/EP2019/085474 2019-12-17 2019-12-17 Composition de décapage de résine photosensible WO2021121552A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2019/085474 WO2021121552A1 (fr) 2019-12-17 2019-12-17 Composition de décapage de résine photosensible

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2019/085474 WO2021121552A1 (fr) 2019-12-17 2019-12-17 Composition de décapage de résine photosensible

Publications (1)

Publication Number Publication Date
WO2021121552A1 true WO2021121552A1 (fr) 2021-06-24

Family

ID=69056019

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2019/085474 WO2021121552A1 (fr) 2019-12-17 2019-12-17 Composition de décapage de résine photosensible

Country Status (1)

Country Link
WO (1) WO2021121552A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1573207A (en) * 1975-11-26 1980-08-20 Tokyo Shibaura Electric Co Surface treating agent adapted of intermediate products ofa semiconductor device
WO2000002238A1 (fr) * 1998-07-06 2000-01-13 Ekc Technology, Inc. Composition et procede de nettoyage post-gravure destines a un systeme de double damasquinage
JP2004093678A (ja) * 2002-08-29 2004-03-25 Jsr Corp フォトレジスト用剥離液組成物
US20060115970A1 (en) * 2001-12-04 2006-06-01 Lee Wai M Compositions and processes for photoresist stripping and residue removal in wafer level packaging
JP2008060377A (ja) * 2006-08-31 2008-03-13 Sanyo Chem Ind Ltd 半導体洗浄用洗浄剤
US20100104824A1 (en) 2006-10-23 2010-04-29 Phenis Michael T Dynamic multi-purpose composition for the removal of photoresists
EP2281867A1 (fr) * 2009-08-05 2011-02-09 Air Products And Chemicals, Inc. Formulation de décapage et de nettoyage semi-aqueuse pour substrat métallique et procédés d'utilisation correspondants
CN102141743A (zh) * 2010-08-25 2011-08-03 上海飞凯光电材料股份有限公司 具有金属保护的光刻胶剥离液组合物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1573207A (en) * 1975-11-26 1980-08-20 Tokyo Shibaura Electric Co Surface treating agent adapted of intermediate products ofa semiconductor device
WO2000002238A1 (fr) * 1998-07-06 2000-01-13 Ekc Technology, Inc. Composition et procede de nettoyage post-gravure destines a un systeme de double damasquinage
US20060115970A1 (en) * 2001-12-04 2006-06-01 Lee Wai M Compositions and processes for photoresist stripping and residue removal in wafer level packaging
JP2004093678A (ja) * 2002-08-29 2004-03-25 Jsr Corp フォトレジスト用剥離液組成物
JP2008060377A (ja) * 2006-08-31 2008-03-13 Sanyo Chem Ind Ltd 半導体洗浄用洗浄剤
US20100104824A1 (en) 2006-10-23 2010-04-29 Phenis Michael T Dynamic multi-purpose composition for the removal of photoresists
EP2281867A1 (fr) * 2009-08-05 2011-02-09 Air Products And Chemicals, Inc. Formulation de décapage et de nettoyage semi-aqueuse pour substrat métallique et procédés d'utilisation correspondants
CN102141743A (zh) * 2010-08-25 2011-08-03 上海飞凯光电材料股份有限公司 具有金属保护的光刻胶剥离液组合物

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