+

WO2010119753A1 - Photoresist remover composition and method for removing photoresist - Google Patents

Photoresist remover composition and method for removing photoresist Download PDF

Info

Publication number
WO2010119753A1
WO2010119753A1 PCT/JP2010/055034 JP2010055034W WO2010119753A1 WO 2010119753 A1 WO2010119753 A1 WO 2010119753A1 JP 2010055034 W JP2010055034 W JP 2010055034W WO 2010119753 A1 WO2010119753 A1 WO 2010119753A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
photoresist
water
weight
copper alloy
Prior art date
Application number
PCT/JP2010/055034
Other languages
French (fr)
Japanese (ja)
Inventor
秀国 安江
Original Assignee
ナガセケムテックス株式会社
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 ナガセケムテックス株式会社 filed Critical ナガセケムテックス株式会社
Priority to KR1020117002294A priority Critical patent/KR101668126B1/en
Priority to JP2010550981A priority patent/JP4725905B2/en
Priority to CN201080002286.7A priority patent/CN102124414B/en
Publication of WO2010119753A1 publication Critical patent/WO2010119753A1/en

Links

Images

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
    • 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
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • 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
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

Definitions

  • the present invention relates to a photoresist remover composition, and in particular, is preferably used for a flat panel display (hereinafter also referred to as FPD) substrate represented by a liquid crystal display or a copper or copper alloy wiring substrate of a semiconductor substrate.
  • FPD flat panel display
  • the present invention relates to a photoresist stripping composition excellent in corrosion resistance and stripping property, and a photoresist stripping method for a metal wiring board having a copper layer or a copper alloy layer using the composition.
  • An FPD substrate or a semiconductor substrate has an electrode structure with fine wiring, and a photoresist is used in the manufacturing process.
  • a photoresist is applied on a conductive metal layer such as aluminum, aluminum alloy, copper, or copper alloy formed on a substrate, or an insulating film such as SiO 2 film, and the resist is subjected to exposure and development. It is manufactured by forming a pattern, etching the conductive metal layer, insulating film, etc. using the patterned resist as a mask, forming fine wiring, and then removing the unnecessary photoresist layer with a release agent .
  • a photoresist stripping composition a single solvent such as an organic alkali, an inorganic alkali, an organic acid, an inorganic acid, a polar solvent, or a mixed solution thereof has been used. It is also well known to use a mixed liquid of amine and water in order to improve photoresist peelability.
  • the photoresist remover composition is required not to corrode fine wiring.
  • aluminum has been widely used as a wiring material, and therefore various studies have been made on corrosion inhibition against aluminum.
  • Patent Document 1 discloses a photoresist stripping composition mainly comprising an alkyl or alkanolamine, a polar organic solvent, water, and a heterocyclic hydroxyl group-containing compound in which the elements constituting the ring are nitrogen and carbon. Is disclosed.
  • Patent Document 2 discloses an anticorrosive containing a heterocyclic compound having a 5- or 6-membered heterocyclic ring containing an atomic group of —C (OH) ⁇ N— or —CONH— and an alkanolamine as a semiconductor. In some cases, a metal layer such as copper formed on a wafer is prevented from being corroded.
  • Patent Document 3 discloses a photoresist stripping composition containing a specific heterocyclic compound, a primary or secondary alkanolamine and a primary or secondary alkylamine, a polar organic solvent, a sugar alcohol, copper and a copper alloy.
  • the photoresist can be peeled off without corroding.
  • the conventional anticorrosive agent for copper or copper alloy has not always had sufficient anticorrosion properties.
  • numerator are excellent in the anticorrosive property of copper or a copper alloy, when the board
  • this deposit cannot be removed by ordinary washing, there is a problem that a separate deposit removal treatment is required.
  • the present invention is excellent for copper or copper alloy wiring formed on a substrate without containing any of benzotriazoles and compounds having a thiol group in a copper or copper alloy wiring manufacturing process of a semiconductor substrate and an FPD substrate.
  • An object of the present invention is to provide a photoresist stripping composition having anticorrosion properties and a photoresist stripping method using the composition.
  • a photoresist remover composition containing cytosine and / or creatinine has excellent anticorrosive properties for copper or copper alloy wiring without inhibiting the photoresist peelability.
  • the present invention has been completed.
  • the present invention is a photoresist stripper composition containing cytosine and / or creatinine as a corrosion inhibitor for copper or a copper alloy together with a resist stripper.
  • the present invention also includes (A) an alkanolamine, (B) a water-soluble organic solvent, and (C) water, and a photo containing cytosine and / or creatinine as an anticorrosive (D) for copper or a copper alloy. It is also a resist remover composition.
  • the content of alkanolamine (A) is 1 to 50% by weight
  • the content of water-soluble organic solvent (B) is 10 to 88.998% by weight.
  • the water (C) content is 10 to 88.998% by weight, and the total content of the water-soluble organic solvent (B) and water (C) is 49.998 to 98.998.
  • the content of the anticorrosive (D) is 0.002 to 1.0% by weight.
  • the alkanolamine (A) is at least one selected from the group consisting of isopropanolamine, N-methylethanolamine, diethanolamine, N-methyldiethanolamine, and triethanolamine. You can.
  • the water-soluble organic solvent (B) may be at least one selected from the group consisting of glycols, sulfoxides and amides.
  • the present invention also provides a photoresist that is no longer necessary to prevent corrosion of the copper layer or the copper alloy layer when forming a metal wiring having a copper layer or a copper alloy layer on the substrate using the photoresist. It is also a photoresist stripping method for a metal wiring board having a copper layer or a copper alloy layer, in which stripping is removed using the photoresist stripping composition of the present invention.
  • the present invention is not particularly distinguished.
  • the present invention has the above configuration. (1) In the manufacturing process of copper or copper alloy wiring of a semiconductor substrate and an FPD substrate, it has excellent releasability from a photoresist. (2) Excellent corrosion resistance to copper or copper alloy wiring. (3) By using cytosine and / or creatinine, copper or a copper alloy that does not generate precipitates that are difficult to remove by ordinary cleaning as in the case of using a compound having a benzotriazole and a thiol group is used. An anticorrosive having excellent anticorrosive properties for wiring can be provided, and by providing a release agent using such an anticorrosive, excellent anticorrosion performance and resist stripping performance for copper or copper alloy wiring It is possible to provide a resist remover composition that exhibits both of the above.
  • FIG. 1 The drawing substitute photograph which shows the remaining condition of the copper film of the board
  • FIG. 1 The drawing substitute photograph which shows the remaining condition of the copper film of the board
  • the photoresist remover composition of the present invention contains cytosine and / or creatinine as an anticorrosive agent for copper or a copper alloy together with the resist remover.
  • the resist stripping agent is not particularly limited, and those using conventionally known stripping agent components can be applied.
  • such a photoresist stripping composition contains (A) an alkanolamine, (B) a water-soluble organic solvent, and (C) water, and a copper or copper alloy corrosion inhibitor (D It is preferable to contain cytosine and / or creatinine as
  • the alkanolamine (A) in the present invention may be only a primary alkanolamine, only a secondary alkanolamine, or only a tertiary alkanolamine, and any combination thereof, for example, a primary alkanolamine and a secondary alkanol.
  • a combination with an amine a combination of a primary alkanolamine, a secondary alkanolamine and a tertiary alkanolamine, or the like may be used. Of these, only secondary alkanolamines, only tertiary alkanolamines, or combinations containing secondary alkanolamines and tertiary alkanolamines are preferred, and only tertiary alkanolamines are more preferred.
  • alkanolamine (A) only 1 type may be used and 2 or more types may be used simultaneously.
  • the primary alkanolamine (A) is not particularly limited, and examples thereof include monoethanolamine and isopropanolamine.
  • Secondary alkanolamines are not particularly limited, and examples thereof include diethanolamine, N-methylethanolamine, N-ethylethanolamine and the like can be mentioned, and the tertiary alkanolamine is not particularly limited.
  • Specific examples of preferred alkanolamines (A) in the present invention are isopropanolamine and N-methylethanolamine from the viewpoints of availability, releasability and anticorrosion against copper or copper alloys.
  • Diethanolamine, N-methyldiethanolamine, triethanolamine, and any combination thereof are preferred. Furthermore, diethanolamine, N-methylethanolamine, N-methyldiethanolamine, triethanolamine, and any combination thereof are more preferable. N-methyldiethanolamine, triethanolamine, and combinations thereof are more preferred.
  • the content of the alkanolamine (A) is preferably 1 to 50% by weight in the release agent composition. Within this range, the peelability is sufficiently good, and the viscosity is low and the handling is good. More preferably, it is 3 to 45% by weight.
  • the water-soluble organic solvent (B) in the present invention is not particularly limited.
  • acetone monoalcohols (for example, methanol, ethanol, etc.)
  • glycols for example, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl) Ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol, propylene glycol methyl ether, dipropylene glycol, etc.
  • pyrrolidones eg, N-methyl-2-pyrrolidone
  • amides eg, N, N-dimethylacetamide, N , N-dimethylformamide
  • nitriles eg, acetonitrile, etc.
  • sulfoxides eg, dimethyl sulfoxide, etc.
  • sulfo Emissions such, sulfolane
  • glycols may be used alone or in combination of two or more.
  • at least one selected from the group consisting of glycols, sulfoxides, and amides is preferable, and diethylene glycol monobutyl ether, propylene glycol, N, N-dimethylacetamide, diethylene glycol, and dimethyl sulfoxide are more preferable.
  • the content of the water-soluble organic solvent (B) is preferably 10 to 88.998% by weight in the release agent composition. Within this range, the peelability of the photoresist and the corrosion resistance of copper or copper alloy are sufficiently satisfactorily exhibited. More preferably, it is 15 to 80% by weight.
  • the release property of the photoresist is further improved, and even when the alkanolamine (A) and the water-soluble organic solvent (B) have a flash point, the release agent composition. It has the effect of eliminating the flash point as an object.
  • water pure water used for semiconductor production is preferred.
  • the content of water (C) in the present invention is preferably 10 to 88.998% by weight in the release agent composition.
  • the content of water (C) is within the above range, the effect of improving the peelability of the photoresist is obtained, and the effect of eliminating the flash point is obtained.
  • the concentration of other components may decrease, and the peelability of the photoresist may decrease. More preferably, it is 13 to 80% by weight, and further preferably 15 to 75% by weight.
  • the total content of (B) and (C) is preferably 48.998 to 98.998% by weight, more preferably 54.998 to 94.998% by weight.
  • Cytosine and / or creatinine is used as the anticorrosive agent (D) in the present invention.
  • an anticorrosive agent (D) only cytosine may be sufficient, only creatinine may be sufficient, and the combination of cytosine and creatinine may be sufficient.
  • cytosine and creatinine can also be used in the form of a salt (for example, hydrochloride, sulfate, sulfate hydrate, etc.).
  • the content of the anticorrosive agent (D) is preferably 0.002 to 1.0% by weight in the release agent composition. When it is within this range, sufficient anticorrosion properties for copper or copper alloy can be obtained. When the content of the anticorrosive agent (D) is less than 0.002% by weight, the anticorrosive property for copper or copper alloy may not be sufficiently obtained. Although it is not necessarily inconvenient if the content of the anticorrosive agent (D) exceeds 1.0% by weight, it is uneconomical and may not be uniformly dissolved in the photoresist stripper composition. More preferably, it is 0.005 to 0.5% by weight.
  • the total content of the alkanolamine (A), the water-soluble organic solvent (B), water (C) and the anticorrosive agent (D) can occupy 100% by weight in the composition.
  • the photoresist stripper composition of the present invention has, in addition to the above components, a surfactant (for example, an alkylbenzene sulfonate, polyoxyethylene alkyl ether), an antifoaming agent (in the range not impairing the object of the present invention).
  • a surfactant for example, an alkylbenzene sulfonate, polyoxyethylene alkyl ether
  • an antifoaming agent in the range not impairing the object of the present invention.
  • additives such as silicone oil
  • the content of each additive depends on the type of the additive and is not generally determined.
  • the content is preferably 0.001 to 5% by weight, more preferably 0.01 to 1% by weight.
  • the photoresist remover composition of the present invention can be prepared by mixing the required amounts of the above components by a conventional method.
  • the photoresist remover composition of the present invention can be used to remove a photoresist that is no longer necessary after an etching treatment of a metal wiring or the like in a manufacturing process of a semiconductor substrate or an FPD substrate.
  • the photoresist remover composition of the present invention can be used by heating to room temperature, for example, 30 ° C. to 80 ° C.
  • the time required for stripping depends on the degree of alteration of the photoresist, but is generally about 30 seconds to 10 minutes, for example. After the treatment, washing with water, air blow drying and the like can be performed as necessary.
  • the method for removing a photoresist of a metal wiring board having a copper layer or a copper alloy layer using the photoresist remover composition of the present invention is a metal wiring having a copper layer or a copper alloy layer using a photoresist.
  • the photoresist that is no longer needed is stripped and removed using the photoresist stripper composition of the present invention.
  • the copper layer or the copper alloy layer is excessively corroded and the line width of the copper wiring or copper alloy wiring can be reduced, and the cross-sectional shape formed by etching is not impaired, and it is good.
  • Metal wiring is formed.
  • copper or copper alloy / two-layer wiring having a composition different from the upper layer, copper or copper alloy / molybten
  • a cap metal such as titanium
  • a cap metal / copper such as molybdenum or titanium / copper alloy / molybten
  • a three-layer wiring of a cap metal such as titanium, or the like.
  • a metal layer forming step including a step of forming a copper or copper alloy film on a substrate is performed, and then, after etching through a patterned photoresist, it becomes unnecessary.
  • a multilayer metal wiring board having a copper layer or a copper alloy layer, in which the corrosion of the copper layer or the copper alloy layer is prevented, is produced by peeling and removing the photoresist using the photoresist remover composition of the present invention. be able to.
  • Evaluation 1 Copper corrosion resistance A substrate on which a 50 nm thick copper film was formed on glass by sputtering was used as an evaluation object.
  • the substrate was immersed in a photoresist remover composition adjusted to 50 ° C., and the treatment time was about 10 minutes or less, and the treatment was performed for 3 times that of 30 minutes. After the immersion treatment, the substrate was washed with water and air-dried. The remaining state of the copper film on the substrate was visually observed.
  • This evaluation method can evaluate the result more directly than the method for obtaining the etching rate. As typical results, the results of Example 1 are shown in FIG. 1, the results of Comparative Example 11 are shown in FIG. 2, and the results of Comparative Example 19 are shown in FIG. FIG.
  • FIG. 1 shows that the disappearance of the copper film was not observed.
  • FIG. 2 shows the disappearance of the copper film in the lower left part of the substrate. In FIG. 3, the disappearance of the copper film is shown except for the upper left of the substrate.
  • Judgment criteria Pass
  • ⁇ The entire copper film remains (Failure)
  • ⁇ It can be clearly seen that a part of the copper film has disappeared, but approximately 50% or more of the copper film remains.
  • ⁇ Approximately 50% or more of the copper film has disappeared.
  • Evaluation 2 Photoresist releasability A SiN film is formed on a glass substrate by CVD, a photoresist is formed, the photoresist is patterned by UV exposure and development, and then SiN is used with a fluorine-based gas.
  • the substrate subjected to dry etching was evaluated. The substrate was immersed in a photoresist remover composition adjusted to 40 ° C. and treated for 30 seconds. After the immersion treatment, the substrate was washed with water and air-dried. The substrate was observed using an electron microscope to confirm the peeling of the photoresist. Judgment criteria (pass) ⁇ : No peeling residue (Failure) ⁇ : Peeling remaining
  • evaluation 1 was performed, and evaluation 2 was performed for those having a determination of “ ⁇ ”.
  • the photoresist stripper composition consisting only of BDG (Comparative Example 1) had a copper anticorrosion property of Evaluation 1 with a ⁇ evaluation, but a photoresist stripping property of Evaluation 2 with an x evaluation.
  • Photoresist stripper composition (Comparative Examples 2 to 8) containing alkanolamine, water-soluble organic solvent and water but not containing cytosine or creatinine, alkanolamine, water-soluble organic solvent, water and A photoresist stripper composition containing no compound but containing cytosine or creatinine (Comparative Examples 9 to 11), an alkanolamine, a water-soluble organic solvent, water, and a compound described in Patent Document 2, The photoresist stripping compositions containing no cytosine or creatinine (Comparative Examples 12 to 16) had poor copper corrosion resistance as evaluated 1.
  • a photoresist stripping composition (Comparative Examples 17 to 22) containing alkanolamine, a water-soluble organic solvent, water and a compound described in Patent Document 3 but containing neither cytosine nor creatinine was evaluated as described above. Copper corrosion resistance due to was bad.
  • the photoresist stripping compositions of the present invention have very good copper anticorrosion properties in Evaluation 1, and the photoresist stripping properties in Evaluation 2 are the same in any composition. Also good results were obtained. From these results, it was found that the photoresist stripper containing cytosine or creatinine as a corrosion inhibitor significantly improved the corrosion resistance against copper and copper alloys as compared to the composition containing the conventional corrosion inhibitor. .

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Detergent Compositions (AREA)

Abstract

Disclosed is a photoresist remover composition which does not contain a benzotriazole compound and a thiol group-containing compound, and is capable of removing a resist without eroding copper or copper alloy wiring lines during a step for forming copper or copper alloy wiring lines for a semiconductor substrate or an FPD substrate. Also disclosed is a method for removing a photoresist, wherein the photoresist remover composition is used. The photoresist remover composition contains an alkanol amine in an amount of 1-50% by weight, a water-soluble organic solvent in an amount of 10-88.998% by weight and water in an amount of 10-88.998% by weight, with the total of the water-soluble organic solvent and water being 49.998-98.998% by weight. The photoresist remover composition also contains cytosine and/or creatinine as an anti-corrosive agent for copper or copper alloys in an amount of 0.002-1.0% by weight.

Description

フォトレジスト剥離剤組成物及びフォトレジスト剥離方法Photoresist stripper composition and photoresist stripping method
　本発明はフォトレジスト剥離剤組成物に関し、詳細には、液晶ディスプレイに代表されるフラットパネルディプレイ（以下、ＦＰＤともいう。）基板や半導体基板の銅又は銅合金配線基板に好適に使用される、防食性及び剥離性に優れるフォトレジスト剥離剤組成物、並びにそれを用いた銅層又は銅合金層を有する金属配線基板のフォトレジスト剥離方法に関する。 The present invention relates to a photoresist remover composition, and in particular, is preferably used for a flat panel display (hereinafter also referred to as FPD) substrate represented by a liquid crystal display or a copper or copper alloy wiring substrate of a semiconductor substrate. The present invention relates to a photoresist stripping composition excellent in corrosion resistance and stripping property, and a photoresist stripping method for a metal wiring board having a copper layer or a copper alloy layer using the composition.
　ＦＰＤ基板や半導体基板は微細な配線を施した電極構造を有しており、その製造工程でフォトレジストが使用されている。例えば、基板上に形成されたアルミニウム、アルミニウム合金、銅、銅合金等の導電性金属層やＳｉＯ２膜等の絶縁膜上にフォトレジストを塗布し、これに露光、現像の処理を施してレジストパターンを形成し、このパターニングされたレジストをマスクとして上記導電性金属層や絶縁膜等をエッチングし、微細配線を形成した後、不要となったフォトレジスト層を剥離剤で除去して製造される。 An FPD substrate or a semiconductor substrate has an electrode structure with fine wiring, and a photoresist is used in the manufacturing process. For example, a photoresist is applied on a conductive metal layer such as aluminum, aluminum alloy, copper, or copper alloy formed on a substrate, or an insulating film such as SiO 2 film, and the resist is subjected to exposure and development. It is manufactured by forming a pattern, etching the conductive metal layer, insulating film, etc. using the patterned resist as a mask, forming fine wiring, and then removing the unnecessary photoresist layer with a release agent .
　従来、フォトレジスト剥離剤組成物としては、有機アルカリ、無機アルカリ、有機酸、無機酸、極性溶剤等の単一溶剤、又はこれらの混合溶液が用いられてきた。また、フォトレジスト剥離性を向上させるために、アミンと水との混合液を用いることもよく知られている。フォトレジスト剥離剤組成物には、微細配線を腐食しないことが求められる。配線材料としては、従来アルミニウムが多用されてきたため、アルミニウムに対する腐食抑止についてはさまざまな検討がなされてきた。例えば、特許文献１には、アルキル又はアルカノールアミンと、極性有機溶剤と、水と、環を構成する元素が窒素と炭素からなる複素環式水酸基含有化合物を主成分とするフォトレジスト剥離剤組成物が開示されている。 Conventionally, as a photoresist stripping composition, a single solvent such as an organic alkali, an inorganic alkali, an organic acid, an inorganic acid, a polar solvent, or a mixed solution thereof has been used. It is also well known to use a mixed liquid of amine and water in order to improve photoresist peelability. The photoresist remover composition is required not to corrode fine wiring. Conventionally, aluminum has been widely used as a wiring material, and therefore various studies have been made on corrosion inhibition against aluminum. For example, Patent Document 1 discloses a photoresist stripping composition mainly comprising an alkyl or alkanolamine, a polar organic solvent, water, and a heterocyclic hydroxyl group-containing compound in which the elements constituting the ring are nitrogen and carbon. Is disclosed.
　しかし近年、基板の大型化や配線パターンの微細化に伴い、アルミニウムよりも抵抗率の低い銅又は銅合金を配線材料として用いることが試みられている。銅はアルカリ含有の溶液に腐食しやすい金属である上、アルミニウムと腐食溶解機構が異なり、アルミニウムで有効であった腐食抑止策はほとんど効果がない。そのため、銅又は銅合金に有効な防食剤が検討されている。例えば、特許文献２には、－Ｃ（ＯＨ）＝Ｎ－又は－ＣＯＮＨ－なる原子団を含む五員ないし六員の複素環を有する複素環式化合物とアルカノールアミンとを含有する防食剤が半導体ウエハ上に形成された銅等の金属層を防食するとある。 However, in recent years, attempts have been made to use copper or a copper alloy having a resistivity lower than that of aluminum as a wiring material with an increase in the size of a substrate and the miniaturization of a wiring pattern. Copper is a metal that is easily corroded by alkali-containing solutions, and the corrosion dissolution mechanism is different from that of aluminum. Corrosion suppression measures that were effective with aluminum are almost ineffective. Therefore, anticorrosives effective for copper or copper alloys have been studied. For example, Patent Document 2 discloses an anticorrosive containing a heterocyclic compound having a 5- or 6-membered heterocyclic ring containing an atomic group of —C (OH) ═N— or —CONH— and an alkanolamine as a semiconductor. In some cases, a metal layer such as copper formed on a wafer is prevented from being corroded.
　特許文献３には、特定の複素環式化合物、一級又は二級のアルカノールアミン及び一級又は二級のアルキルアミン、極性有機溶剤、糖アルコールを含有するフォトレジスト剥離剤組成物が、銅及び銅合金を腐食することなくフォトレジストを剥離可能とある。 Patent Document 3 discloses a photoresist stripping composition containing a specific heterocyclic compound, a primary or secondary alkanolamine and a primary or secondary alkylamine, a polar organic solvent, a sugar alcohol, copper and a copper alloy. The photoresist can be peeled off without corroding.
　また、銅に対する強力な腐食抑止剤として、分子中にチオール基を有する化合物及びベンゾトリアゾール類が知られている。 Also, compounds having a thiol group in the molecule and benzotriazoles are known as strong corrosion inhibitors for copper.
　しかし、従来の銅又は銅合金用の防食剤では防食性が必ずしも充分ではなかった。また、分子内にチオール基を有する化合物及びベンゾトリアゾール類は、銅又は銅合金の防食性は優れているものの、これらを含有するフォトレジスト剥離剤組成物で銅又は銅合金を含む基板を処理すると、銅又は銅合金表面に析出物が発生する。しかしながら、この析出物は通常の洗浄では除去できないため、別途、析出物除去処理が必要になるという問題があった。 However, the conventional anticorrosive agent for copper or copper alloy has not always had sufficient anticorrosion properties. Moreover, although the compound and benzotriazole which have a thiol group in a molecule | numerator are excellent in the anticorrosive property of copper or a copper alloy, when the board | substrate containing copper or a copper alloy is processed with the photoresist stripping composition containing these, A precipitate is generated on the surface of copper or copper alloy. However, since this deposit cannot be removed by ordinary washing, there is a problem that a separate deposit removal treatment is required.
特開２００１－３５０２７６号公報JP 2001-350276 A 特開２００２－９７５８４号公報JP 2002-97584 A 特開２００８－２８６８８１号公報JP 2008-286881 A
　本発明は、半導体基板及びＦＰＤ基板の銅又は銅合金配線製造工程において、ベンゾトリアゾール類及びチオール基を有する化合物のいずれをも含有せずに基板上に形成された銅又は銅合金配線に対する優れた防食性を持つフォトレジスト剥離剤組成物、それを使用したフォトレジスト剥離方法を提供することを目的とする。 The present invention is excellent for copper or copper alloy wiring formed on a substrate without containing any of benzotriazoles and compounds having a thiol group in a copper or copper alloy wiring manufacturing process of a semiconductor substrate and an FPD substrate. An object of the present invention is to provide a photoresist stripping composition having anticorrosion properties and a photoresist stripping method using the composition.
　本発明者は鋭意検討を行った結果、シトシン及び／又はクレアチニンを含有するフォトレジスト剥離剤組成物が、フォトレジスト剥離性を阻害することなく、銅又は銅合金配線に対して優れた防食性を示すことを見出し、本発明を完成させた。 As a result of intensive studies, the present inventors have found that a photoresist remover composition containing cytosine and / or creatinine has excellent anticorrosive properties for copper or copper alloy wiring without inhibiting the photoresist peelability. The present invention has been completed.
　すなわち、本発明は、レジスト剥離剤とともに、銅又は銅合金の防食剤としてシトシン及び／又はクレアチニンを含有するフォトレジスト剥離剤組成物である。
　本発明はまた、（Ａ）アルカノールアミン、（Ｂ）水溶性有機溶剤、及び（Ｃ）水を含有するとともに、銅又は銅合金の防食剤（Ｄ）としてのシトシン及び／又はクレアチニンを含有するフォトレジスト剥離剤組成物でもある。
　本発明のフォトレジスト剥離剤組成物の１態様においては、アルカノールアミン（Ａ）の含有量が１～５０重量％であり、水溶性有機溶剤（Ｂ）の含有量が１０～８８．９９８重量％であって、水（Ｃ）の含有量が１０～８８．９９８重量％であって、かつ、水溶性有機溶剤（Ｂ）と水（Ｃ）との合計含有量が４９．９９８～９８．９９８重量％であり、防食剤（Ｄ）の含有量が０．００２～１．０重量％である。
　本発明のフォトレジスト剥離剤組成物においては、アルカノールアミン（Ａ）が、イソプロパノールアミン、Ｎ－メチルエタノールアミン、ジエタノールアミン、Ｎ－メチルジエタノールアミン及びトリエタノールアミンからなる群から選択される少なくとも１種であってよい。
　本発明のフォトレジスト剥離剤組成物においては、水溶性有機溶剤（Ｂ）が、グリコール類、スルホキシド類及びアミド類からなる群から選択される少なくとも１種であってよい。
　本発明はまた、フォトレジストを使用して銅層又は銅合金層を有する金属配線を基板上に形成する際に、銅層又は銅合金層の腐食を防止するために、不要となったフォトレジストを本発明のフォトレジスト剥離剤組成物を使用して剥離除去する、銅層又は銅合金層を有する金属配線基板のフォトレジスト剥離方法でもある。
　以下、単に「本発明」というときは、これらの本発明をとくに区別することなく指す。 That is, the present invention is a photoresist stripper composition containing cytosine and / or creatinine as a corrosion inhibitor for copper or a copper alloy together with a resist stripper.
The present invention also includes (A) an alkanolamine, (B) a water-soluble organic solvent, and (C) water, and a photo containing cytosine and / or creatinine as an anticorrosive (D) for copper or a copper alloy. It is also a resist remover composition.
In one embodiment of the photoresist stripping composition of the present invention, the content of alkanolamine (A) is 1 to 50% by weight, and the content of water-soluble organic solvent (B) is 10 to 88.998% by weight. The water (C) content is 10 to 88.998% by weight, and the total content of the water-soluble organic solvent (B) and water (C) is 49.998 to 98.998. The content of the anticorrosive (D) is 0.002 to 1.0% by weight.
In the photoresist stripper composition of the present invention, the alkanolamine (A) is at least one selected from the group consisting of isopropanolamine, N-methylethanolamine, diethanolamine, N-methyldiethanolamine, and triethanolamine. You can.
In the photoresist stripping composition of the present invention, the water-soluble organic solvent (B) may be at least one selected from the group consisting of glycols, sulfoxides and amides.
The present invention also provides a photoresist that is no longer necessary to prevent corrosion of the copper layer or the copper alloy layer when forming a metal wiring having a copper layer or a copper alloy layer on the substrate using the photoresist. It is also a photoresist stripping method for a metal wiring board having a copper layer or a copper alloy layer, in which stripping is removed using the photoresist stripping composition of the present invention.
Hereinafter, when simply referring to “the present invention”, the present invention is not particularly distinguished.
　本発明は、上述の構成により、
（１）半導体基板及びＦＰＤ基板の銅又は銅合金配線製造工程において、フォトレジストに対する優れた剥離性を有する。
（２）銅又は銅合金配線に対して優れた防食性を有する。
（３）シトシン及び／又はクレアチニンを使用することにより、ベンゾトリアゾール類及びチオール基を有する化合物を使用した場合のように通常の洗浄では除去困難な析出物が発生することのない、銅又は銅合金配線に対して優れた防食性を持つ防食剤を提供することができ、このような防食剤を用いた剥離剤を提供することにより、銅又は銅合金配線に対する優れた防食性能とレジスト剥離性能とをともに発揮するレジスト剥離剤組成物を提供することができる。
（４）本発明のフォトレジスト剥離剤組成物を使用すると、配線パターン化された銅又は銅合金配線において、銅又は銅合金配線の腐食を防止することにより、銅層又は銅合金層の腐食による配線幅のやせ細り等のない良好な金属配線を形成することができる。 The present invention has the above configuration.
(1) In the manufacturing process of copper or copper alloy wiring of a semiconductor substrate and an FPD substrate, it has excellent releasability from a photoresist.
(2) Excellent corrosion resistance to copper or copper alloy wiring.
(3) By using cytosine and / or creatinine, copper or a copper alloy that does not generate precipitates that are difficult to remove by ordinary cleaning as in the case of using a compound having a benzotriazole and a thiol group is used. An anticorrosive having excellent anticorrosive properties for wiring can be provided, and by providing a release agent using such an anticorrosive, excellent anticorrosion performance and resist stripping performance for copper or copper alloy wiring It is possible to provide a resist remover composition that exhibits both of the above.
(4) When the photoresist stripping composition of the present invention is used, in the copper or copper alloy wiring that has been subjected to wiring patterning, the corrosion of the copper layer or copper alloy layer is prevented by preventing the corrosion of the copper or copper alloy wiring. It is possible to form a good metal wiring without a thin wiring width.
実施例１における基板の銅膜の残り具合を示す図面代用写真。The drawing substitute photograph which shows the remaining condition of the copper film of the board | substrate in Example 1. FIG. 比較例１１における基板の銅膜の残り具合を示す図面代用写真。The drawing substitute photograph which shows the remaining condition of the copper film of the board | substrate in the comparative example 11. FIG. 比較例１９における基板の銅膜の残り具合を示す図面代用写真。The drawing substitute photograph which shows the remaining condition of the copper film of the board | substrate in the comparative example 19. FIG.
　本発明のフォトレジスト剥離剤組成物は、レジスト剥離剤とともに、銅又は銅合金の防食剤としてシトシン及び／又はクレアチニンを含有する。上記レジスト剥離剤としては特に限定されず、従来公知の剥離剤成分を用いたものを適用することができる。
　本発明においては、このようなフォトレジスト剥離剤組成物としては、（Ａ）アルカノールアミン、（Ｂ）水溶性有機溶剤、及び（Ｃ）水を含有するとともに、銅又は銅合金の防食剤（Ｄ）としてのシトシン及び／又はクレアチニンを含有するものが好ましい。
　本発明におけるアルカノールアミン（Ａ）としては、１級アルカノールアミンのみ、２級アルカノールアミンのみ、３級アルカノールアミンのみであってもよく、これらの任意の組み合わせ、例えば、１級アルカノールアミンと２級アルカノールアミンとの組み合わせ、１級アルカノールアミンと２級アルカノールアミンと３級アルカノールアミンとの組み合わせ、等であってもよい。これらのうち、２級アルカノールアミンのみ、３級アルカノールアミンのみ、又は、２級アルカノールアミンと３級アルカノールアミンとを含む組み合わせ、が好ましく、３級アルカノールアミンのみがより好ましい。アルカノールアミン（Ａ）としては１種のみ用いてもよく、２種以上を同時に用いてもよい。 The photoresist remover composition of the present invention contains cytosine and / or creatinine as an anticorrosive agent for copper or a copper alloy together with the resist remover. The resist stripping agent is not particularly limited, and those using conventionally known stripping agent components can be applied.
In the present invention, such a photoresist stripping composition contains (A) an alkanolamine, (B) a water-soluble organic solvent, and (C) water, and a copper or copper alloy corrosion inhibitor (D It is preferable to contain cytosine and / or creatinine as
The alkanolamine (A) in the present invention may be only a primary alkanolamine, only a secondary alkanolamine, or only a tertiary alkanolamine, and any combination thereof, for example, a primary alkanolamine and a secondary alkanol. A combination with an amine, a combination of a primary alkanolamine, a secondary alkanolamine and a tertiary alkanolamine, or the like may be used. Of these, only secondary alkanolamines, only tertiary alkanolamines, or combinations containing secondary alkanolamines and tertiary alkanolamines are preferred, and only tertiary alkanolamines are more preferred. As alkanolamine (A), only 1 type may be used and 2 or more types may be used simultaneously.
　１級アルカノールアミン（Ａ）としては特に限定されず、例えば、モノエタノールアミン、イソプロパノールアミン等を挙げることができ、２級アルカノールアミンとしては特に限定されず、例えば、ジエタノールアミン、Ｎ－メチルエタノールアミン、Ｎ－エチルエタノールアミン等を挙げることができ、３級アルカノールアミンとしては特に限定されず、例えば、Ｎ－メチルジエタノールアミン、Ｎ－エチルジエタノールアミン、Ｎ，Ｎ－ジメチルエタノールアミン、Ｎ，Ｎ－ジエチルエタノールアミン、トリエタノールアミン等が挙げられる。本発明におけるアルカノールアミン（Ａ）の好適な例を具体的にあげれば、この中でも入手の容易さ及び剥離性と銅又は銅合金に対する防食性の兼備の点から、イソプロパノールアミン、Ｎ－メチルエタノールアミン、ジエタノールアミン、Ｎ－メチルジエタノールアミン、トリエタノールアミン、これらの任意の組み合わせ、が好ましい。さらに、ジエタノールアミン、Ｎ－メチルエタノールアミン、Ｎ－メチルジエタノールアミン、トリアエタノールアミン、これらの任意の組み合わせ、がより好ましい。Ｎ－メチルジエタノールアミン、トリエタノールアミン、これらの組み合わせ、がさらに好ましい。 The primary alkanolamine (A) is not particularly limited, and examples thereof include monoethanolamine and isopropanolamine. Secondary alkanolamines are not particularly limited, and examples thereof include diethanolamine, N-methylethanolamine, N-ethylethanolamine and the like can be mentioned, and the tertiary alkanolamine is not particularly limited. For example, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine And triethanolamine. Specific examples of preferred alkanolamines (A) in the present invention are isopropanolamine and N-methylethanolamine from the viewpoints of availability, releasability and anticorrosion against copper or copper alloys. , Diethanolamine, N-methyldiethanolamine, triethanolamine, and any combination thereof are preferred. Furthermore, diethanolamine, N-methylethanolamine, N-methyldiethanolamine, triethanolamine, and any combination thereof are more preferable. N-methyldiethanolamine, triethanolamine, and combinations thereof are more preferred.
　アルカノールアミン（Ａ）の含有量は、剥離剤組成物中の１～５０重量％であることが好ましい。この範囲内であると剥離性が充分良好であり、低粘度で取扱いが良好である。より好ましくは３～４５重量％である。 The content of the alkanolamine (A) is preferably 1 to 50% by weight in the release agent composition. Within this range, the peelability is sufficiently good, and the viscosity is low and the handling is good. More preferably, it is 3 to 45% by weight.
　本発明における水溶性有機溶剤（Ｂ）としては特に限定されず、例えば、アセトン、モノアルコール類（例えば、メタノール、エタノール等）、グリコール類（例えば、エチレングリコール、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールジメチルエーテル、プロピレングリコール、プロピレングリコールメチルエーテル、ジプロピレングリコール等）、ピロリドン類（例えば、Ｎ－メチル－２－ピロリドン）、アミド類（例えば、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド）、ニトリル類（例えば、アセトニトリル等）、スルホキシド類（例えば、ジメチルスルホキシド等）、スルホン類（例えば、スルホラン等）、エチレンカーボネート等が挙げられる。これらは１種のみ用いてもよく、２種以上を同時に用いてもよい。この中でも、グリコール類、スルホキシド類、及びアミド類からなる群から選択される少なくとも１種が好ましく、ジエチレングリコールモノブチルエーテル、プロピレングリコール、Ｎ，Ｎ－ジメチルアセトアミド、ジエチレングリコール、ジメチルスルホキシド、がより好ましい。 The water-soluble organic solvent (B) in the present invention is not particularly limited. For example, acetone, monoalcohols (for example, methanol, ethanol, etc.), glycols (for example, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl) Ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol, propylene glycol methyl ether, dipropylene glycol, etc.), pyrrolidones (eg, N-methyl-2-pyrrolidone), amides (eg, N, N-dimethylacetamide, N , N-dimethylformamide), nitriles (eg, acetonitrile, etc.), sulfoxides (eg, dimethyl sulfoxide, etc.), sulfo Emissions (such, sulfolane), ethylene carbonate and the like. These may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of glycols, sulfoxides, and amides is preferable, and diethylene glycol monobutyl ether, propylene glycol, N, N-dimethylacetamide, diethylene glycol, and dimethyl sulfoxide are more preferable.
　水溶性有機溶剤（Ｂ）の含有量は、剥離剤組成物中の１０～８８．９９８重量％であることが好ましい。この範囲内であるとフォトレジストの剥離性と銅又は銅合金防食性とが充分良好に発揮される。より好ましくは１５～８０重量％である。 The content of the water-soluble organic solvent (B) is preferably 10 to 88.998% by weight in the release agent composition. Within this range, the peelability of the photoresist and the corrosion resistance of copper or copper alloy are sufficiently satisfactorily exhibited. More preferably, it is 15 to 80% by weight.
　本発明においては、水（Ｃ）を配合することにより、フォトレジストの剥離性を一層向上させるとともに、アルカノールアミン（Ａ）と水溶性有機溶剤（Ｂ）が引火点を有する場合でも、剥離剤組成物としての引火点をなくす効果がある。水としては、半導体製造に用いられる、純水が好ましい。 In the present invention, by adding water (C), the release property of the photoresist is further improved, and even when the alkanolamine (A) and the water-soluble organic solvent (B) have a flash point, the release agent composition. It has the effect of eliminating the flash point as an object. As water, pure water used for semiconductor production is preferred.
　本発明における水（Ｃ）の含有量は、剥離剤組成中の１０～８８．９９８重量％であることが好ましい。水（Ｃ）の含有量が上記範囲内であると、フォトレジストの剥離性向上効果が得られ、また引火点をなくす効果を得られる。上記範囲を超えると、他成分の濃度が低下することにより、フォトレジストの剥離性が低下する場合がある。より好ましくは１３～８０重量％、さらに好ましくは１５～７５重量％である。 The content of water (C) in the present invention is preferably 10 to 88.998% by weight in the release agent composition. When the content of water (C) is within the above range, the effect of improving the peelability of the photoresist is obtained, and the effect of eliminating the flash point is obtained. When the above range is exceeded, the concentration of other components may decrease, and the peelability of the photoresist may decrease. More preferably, it is 13 to 80% by weight, and further preferably 15 to 75% by weight.
　本発明においては、上記（Ｂ）と上記（Ｃ）との合計含有量は、好ましくは４８．９９８～９８．９９８重量％、より好ましくは５４．９９８～９４．９９８重量％である。 In the present invention, the total content of (B) and (C) is preferably 48.998 to 98.998% by weight, more preferably 54.998 to 94.998% by weight.
　本発明における防食剤（Ｄ）としてシトシン及び／又はクレアチニンを用いる。防食剤（Ｄ）としては、シトシンのみであってもよく、クレアチニンのみであってもよく、シトシンとクレアチニンの組み合わせであってもよい。また、シトシンやクレアチニンは、塩（例えば、塩酸塩、硫酸塩又は硫酸塩水和物等）の形で用いることもできる。 Cytosine and / or creatinine is used as the anticorrosive agent (D) in the present invention. As an anticorrosive agent (D), only cytosine may be sufficient, only creatinine may be sufficient, and the combination of cytosine and creatinine may be sufficient. Moreover, cytosine and creatinine can also be used in the form of a salt (for example, hydrochloride, sulfate, sulfate hydrate, etc.).
　上記防食剤（Ｄ）の含有量は、剥離剤組成中の０．００２～１．０重量％であることが好ましい。この範囲内であると、銅又は銅合金に対する防食性が充分得られる。上記防食剤（Ｄ）の含有量が０．００２重量％未満の場合、銅又は銅合金に対する防食性が充分に得られない場合がある。防食剤（Ｄ）の含有量が１．０重量％を超えても必ずしも不都合はないが、不経済であるとともに、フォトレジスト剥離剤組成物中に均一に溶解しない場合がある。より好ましくは０．００５～０．５重量％である。 The content of the anticorrosive agent (D) is preferably 0.002 to 1.0% by weight in the release agent composition. When it is within this range, sufficient anticorrosion properties for copper or copper alloy can be obtained. When the content of the anticorrosive agent (D) is less than 0.002% by weight, the anticorrosive property for copper or copper alloy may not be sufficiently obtained. Although it is not necessarily inconvenient if the content of the anticorrosive agent (D) exceeds 1.0% by weight, it is uneconomical and may not be uniformly dissolved in the photoresist stripper composition. More preferably, it is 0.005 to 0.5% by weight.
　本発明においては、上記アルカノールアミン（Ａ）、水溶性有機溶剤（Ｂ）、水（Ｃ）及び上記防食剤（Ｄ）の合計含有量が組成物中の１００重量％を占めることができる。 In the present invention, the total content of the alkanolamine (A), the water-soluble organic solvent (B), water (C) and the anticorrosive agent (D) can occupy 100% by weight in the composition.
　しかしながら、本発明のフォトレジスト剥離剤組成物は、上記成分の他に、本発明の目的を阻害しない範囲で界面活性剤（例えば、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル）、消泡剤（例えばシリコーンオイル）等の添加剤を含有することができる。上記各添加剤の含有量は、その種類によるので一概に定めないが、例えば、０．００１～５重量％が好ましく、より好ましくは０．０１～１重量％である。 However, the photoresist stripper composition of the present invention has, in addition to the above components, a surfactant (for example, an alkylbenzene sulfonate, polyoxyethylene alkyl ether), an antifoaming agent (in the range not impairing the object of the present invention). For example, additives such as silicone oil) can be contained. The content of each additive depends on the type of the additive and is not generally determined. For example, the content is preferably 0.001 to 5% by weight, more preferably 0.01 to 1% by weight.
　本発明のフォトレジスト剥離剤組成物は、上記各成分の所要量を常法により混合することで調製することができる。 The photoresist remover composition of the present invention can be prepared by mixing the required amounts of the above components by a conventional method.
　本発明のフォトレジスト剥離剤組成物は、半導体基板やＦＰＤ基板等の製造工程において、金属配線等のエッチング処理後に不要となったフォトレジストを剥離するために用いることができる。本発明のフォトレジスト剥離剤組成物は常温のほか、例えば３０℃～８０℃に加熱して使用することができる。剥離に要する時間は、フォトレジストの変質度合い等によるが、一般には、例えば３０秒～１０分間程度である。処理後、必要に応じて水洗、空気ブロー乾燥等を行うことができる。 The photoresist remover composition of the present invention can be used to remove a photoresist that is no longer necessary after an etching treatment of a metal wiring or the like in a manufacturing process of a semiconductor substrate or an FPD substrate. The photoresist remover composition of the present invention can be used by heating to room temperature, for example, 30 ° C. to 80 ° C. The time required for stripping depends on the degree of alteration of the photoresist, but is generally about 30 seconds to 10 minutes, for example. After the treatment, washing with water, air blow drying and the like can be performed as necessary.
　具体的には、本発明のフォトレジスト剥離剤組成物を用いる銅層又は銅合金層を有する金属配線基板のフォトレジスト剥離方法は、フォトレジストを使用して銅層又は銅合金層を有する金属配線を基板上に形成する際に、銅層又は銅合金層の腐食を防止するために、不要となったフォトレジストを本発明のフォトレジスト剥離剤組成物を使用して剥離除去する。こうすることにより、銅層又は銅合金層が過度に腐食して銅配線又は銅合金配線の線幅がやせる等のことが抑制され、エッチングで形成された配線断面形状を損なうことなく、良好な金属配線が形成される。なお、上記金属配線の多層態様としては、上層から順に、銅又は銅合金の１層配線、銅又は銅合金／上層とは異なる組成の銅又は銅合金の２層配線、銅又は銅合金／モリブテン、チタン等のキャップメタルの２層配線、モリブデン、チタン等のキャップメタル／銅又は銅合金／モリブテン、チタン等のキャップメタルの３層配線等があり得る。 Specifically, the method for removing a photoresist of a metal wiring board having a copper layer or a copper alloy layer using the photoresist remover composition of the present invention is a metal wiring having a copper layer or a copper alloy layer using a photoresist. In order to prevent corrosion of the copper layer or the copper alloy layer, the photoresist that is no longer needed is stripped and removed using the photoresist stripper composition of the present invention. By doing so, the copper layer or the copper alloy layer is excessively corroded and the line width of the copper wiring or copper alloy wiring can be reduced, and the cross-sectional shape formed by etching is not impaired, and it is good. Metal wiring is formed. In addition, as a multilayer aspect of the metal wiring, in order from the upper layer, copper or copper alloy one-layer wiring, copper or copper alloy / two-layer wiring having a composition different from the upper layer, copper or copper alloy / molybten There can be a two-layer wiring of a cap metal such as titanium, a cap metal / copper such as molybdenum or titanium / copper alloy / molybten, a three-layer wiring of a cap metal such as titanium, or the like.
　本発明のフォトレジスト剥離方法において、基板上に、銅又は銅合金を成膜する工程を含む金属層形成工程を行い、つぎに、パターニングされたフォトレジストを介してエッチングした後、不要となったフォトレジストを本発明のフォトレジスト剥離剤組成物を使用して剥離除去することにより、銅層又は銅合金層の腐食が防止された、銅層又は銅合金層を有する積層金属配線基板を製造することができる。 In the photoresist stripping method of the present invention, a metal layer forming step including a step of forming a copper or copper alloy film on a substrate is performed, and then, after etching through a patterned photoresist, it becomes unnecessary. A multilayer metal wiring board having a copper layer or a copper alloy layer, in which the corrosion of the copper layer or the copper alloy layer is prevented, is produced by peeling and removing the photoresist using the photoresist remover composition of the present invention. be able to.
　以下に実施例によって本発明をより具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、表中の略号は次のとおりである。
ＭＤＥＡ：Ｎ－メチルジエタノールアミン
ＤＥＡ：ジエタノールアミン
ＴＥＡ：トリエタノールアミン
ＭＭＥＡ：Ｎ－メチルエタノールアミン
ＭＩＰＡ：イソプロパノールアミン
ＢＤＧ：ジエチレングリコールモノブチルエーテル
ＤＭＡＣ：Ｎ，Ｎ－ジメチルアセトアミド
ＤＭＳＯ：ジメチルスルホキシド
ＰＧ：プロピレングリコール
ＤＥＧ：ジエチレングリコール
ＰＷ：純水 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The abbreviations in the table are as follows.
MDEA: N-methyldiethanolamine DEA: diethanolamine TEA: triethanolamine MMEA: N-methylethanolamine MIPA: isopropanolamine BDG: diethylene glycol monobutyl ether DMAC: N, N-dimethylacetamide DMSO: dimethyl sulfoxide PG: propylene glycol DEG: diethylene glycol PW :Pure water
実施例１～２３、比較例１～２２
　表１及び表２の配合によりそれぞれ各成分を混合し、フォトレジスト剥離剤組成物を得た。 Examples 1 to 23, Comparative Examples 1 to 22
Each component was mixed by the mixing | blending of Table 1 and Table 2, respectively, and the photoresist peeling agent composition was obtained.
評価１：銅防食性
　ガラス上に５０ｎｍ厚の銅膜をスパッタリングにより成膜した基板を評価対象物とした。５０℃に調整したフォトレジスト剥離剤組成物に基板を浸漬し、通常の処理時間は１０分以下程度であるところ、その３倍の３０分間処理をした。浸漬処理後、基板を水洗及び空気ブロー乾燥した。基板の銅膜の残り具合を目視にて観察した。この評価方法は、エッチングレートを求める方法に比べて一層直接的に結果を評価することができる。また、典型的結果として、実施例１の結果を図１に示し、比較例１１の結果を図２に示し、比較例１９の結果を図３に示した。図１においては銅膜の消失はみられなかったことが示されている。図２においては基板左下部分の銅膜の消失がみられたことが示されている。図３においては基板左上を除き、銅膜の消失がみられたことが示されている。
判定基準
(合格)
○：銅膜の全体が残っている
(以下、不合格)
△：銅膜の一部が消失していることが明瞭に分かるが、概ね５割以上残っている
×：銅膜の概ね５割以上が消失している Evaluation 1: Copper corrosion resistance A substrate on which a 50 nm thick copper film was formed on glass by sputtering was used as an evaluation object. The substrate was immersed in a photoresist remover composition adjusted to 50 ° C., and the treatment time was about 10 minutes or less, and the treatment was performed for 3 times that of 30 minutes. After the immersion treatment, the substrate was washed with water and air-dried. The remaining state of the copper film on the substrate was visually observed. This evaluation method can evaluate the result more directly than the method for obtaining the etching rate. As typical results, the results of Example 1 are shown in FIG. 1, the results of Comparative Example 11 are shown in FIG. 2, and the results of Comparative Example 19 are shown in FIG. FIG. 1 shows that the disappearance of the copper film was not observed. FIG. 2 shows the disappearance of the copper film in the lower left part of the substrate. In FIG. 3, the disappearance of the copper film is shown except for the upper left of the substrate.
Judgment criteria
(Pass)
○: The entire copper film remains
(Failure)
Δ: It can be clearly seen that a part of the copper film has disappeared, but approximately 50% or more of the copper film remains. ×: Approximately 50% or more of the copper film has disappeared.
評価２：フォトレジスト剥離性
　ガラス基板上にＳｉＮ膜をＣＶＤで成膜した上に、フォトレジストを成膜し、ＵＶ露光及び現像によりフォトレジストのパターニングを行った後、フッ素系のガスにてＳｉＮをドライエッチングした基板を評価対象とした。４０℃に調整したフォトレジスト剥離剤組成物に基板を浸漬し、３０秒間処理をした。浸漬処理後、基板を水洗及び空気ブロー乾燥した。電子顕微鏡を用いて基板を観察し、フォトレジストの剥離具合を確認した。
判定基準
（合格）
○：剥離残りなし
(以下、不合格)
×：剥離残りあり Evaluation 2: Photoresist releasability A SiN film is formed on a glass substrate by CVD, a photoresist is formed, the photoresist is patterned by UV exposure and development, and then SiN is used with a fluorine-based gas. The substrate subjected to dry etching was evaluated. The substrate was immersed in a photoresist remover composition adjusted to 40 ° C. and treated for 30 seconds. After the immersion treatment, the substrate was washed with water and air-dried. The substrate was observed using an electron microscope to confirm the peeling of the photoresist.
Judgment criteria (pass)
○: No peeling residue
(Failure)
×: Peeling remaining
　各フォトレジスト剥離剤組成物について、まず評価１を行い、判定が「○」のものについて、評価２を行った。 For each photoresist remover composition, first, evaluation 1 was performed, and evaluation 2 was performed for those having a determination of “◯”.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　ＢＤＧのみからなるフォトレジスト剥離剤組成物（比較例１）は、評価１の銅防食性は○評価であったが、評価２のフォトレジスト剥離性が×評価であった。 The photoresist stripper composition consisting only of BDG (Comparative Example 1) had a copper anticorrosion property of Evaluation 1 with a ◯ evaluation, but a photoresist stripping property of Evaluation 2 with an x evaluation.
　アルカノールアミン、水溶性有機溶剤および水を含有するが、シトシンもクレアチニンも含有しないフォトレジスト剥離剤組成物（比較例２～８）、アルカノールアミン、水溶性有機溶剤、水及び特許文献１に記載のある化合物を含有するが、シトシンもクレアチニンも含有しないフォトレジスト剥離剤組成物（比較例９～１１）、アルカノールアミン、水溶性有機溶剤、水及び特許文献２に記載のある化合物を含有するが、シトシンもクレアチニンも含有しないフォトレジスト剥離剤組成物（比較例１２～１６）は、評価１の銅防食性が悪かった。また、アルカノールアミン、水溶性有機溶剤、水及び特許文献３に記載のある化合物を含有するが、シトシンもクレアチニンも含有しないフォトレジスト剥離剤組成物（比較例１７～２２）は、上述の評価１による銅防食性が悪かった。 Photoresist stripper composition (Comparative Examples 2 to 8) containing alkanolamine, water-soluble organic solvent and water but not containing cytosine or creatinine, alkanolamine, water-soluble organic solvent, water and A photoresist stripper composition containing no compound but containing cytosine or creatinine (Comparative Examples 9 to 11), an alkanolamine, a water-soluble organic solvent, water, and a compound described in Patent Document 2, The photoresist stripping compositions containing no cytosine or creatinine (Comparative Examples 12 to 16) had poor copper corrosion resistance as evaluated 1. Further, a photoresist stripping composition (Comparative Examples 17 to 22) containing alkanolamine, a water-soluble organic solvent, water and a compound described in Patent Document 3 but containing neither cytosine nor creatinine was evaluated as described above. Copper corrosion resistance due to was bad.
　これに対して、本発明のフォトレジスト剥離剤組成物（実施例１～２３）は、評価１の銅防食性は非常に良好であり、評価２のフォトレジスト剥離性は、いずれの組成物においても、良好な結果が得られた。これらの結果から、シトシン又はクレアチニンを防食剤として含有するフォトレジスト剥離剤は、従来技術の防食剤を含有する組成物に比べて、銅及び銅合金に対する防食性が顕著に向上したことがわかった。 On the other hand, the photoresist stripping compositions of the present invention (Examples 1 to 23) have very good copper anticorrosion properties in Evaluation 1, and the photoresist stripping properties in Evaluation 2 are the same in any composition. Also good results were obtained. From these results, it was found that the photoresist stripper containing cytosine or creatinine as a corrosion inhibitor significantly improved the corrosion resistance against copper and copper alloys as compared to the composition containing the conventional corrosion inhibitor. .

Claims (6)

  1. 　レジスト剥離剤とともに、銅又は銅合金の防食剤としてシトシン及び／又はクレアチニンを含有することを特徴とするフォトレジスト剥離剤組成物。 A photoresist stripper composition containing cytosine and / or creatinine as a corrosion inhibitor for copper or copper alloy together with a resist stripper.
  2. 　（Ａ）アルカノールアミン、（Ｂ）水溶性有機溶剤、及び（Ｃ）水を含有するとともに、銅又は銅合金の防食剤（Ｄ）としてのシトシン及び／又はクレアチニンを含有することを特徴とするフォトレジスト剥離剤組成物。 A photo containing (A) an alkanolamine, (B) a water-soluble organic solvent, and (C) water, and containing cytosine and / or creatinine as a corrosion inhibitor (D) for copper or a copper alloy Resist remover composition.
  3. 　アルカノールアミン（Ａ）の含有量が１～５０重量％であり、
    水溶性有機溶剤（Ｂ）の含有量が１０～８８．９９８重量％であって、水（Ｃ）の含有量が１０～８８．９９８重量％であって、かつ、水溶性有機溶剤（Ｂ）と水（Ｃ）との合計含有量が４９．９９８～９８．９９８重量％であり、
    防食剤（Ｄ）の含有量が０．００２～１．０重量％である、請求項２記載のフォトレジスト剥離剤組成物。     The alkanolamine (A) content is 1 to 50% by weight,
    The water-soluble organic solvent (B) content is 10 to 88.998% by weight, the water (C) content is 10 to 88.998% by weight, and the water-soluble organic solvent (B) And the total content of water (C) is 49.998 to 98.998% by weight,
    The photoresist stripping composition according to claim 2, wherein the content of the anticorrosive (D) is 0.002 to 1.0% by weight.
  4. 　アルカノールアミン（Ａ）が、イソプロパノールアミン、ジエタノールアミン、Ｎ－メチルエタノールアミン、Ｎ－メチルジエタノールアミン、及びトリエタノールアミンからなる群から選択される少なくとも１種である、請求項２又は３記載のフォトレジスト剥離剤組成物。 The photoresist stripping according to claim 2 or 3, wherein the alkanolamine (A) is at least one selected from the group consisting of isopropanolamine, diethanolamine, N-methylethanolamine, N-methyldiethanolamine, and triethanolamine. Agent composition.
  5. 　水溶性有機溶剤（Ｂ）が、グリコール類、スルホキシド類、及びアミド類からなる群から選択される少なくとも１種である、請求項２～４のいずれか記載のフォトレジストレジスト剥離剤組成物。 5. The photoresist resist remover composition according to claim 2, wherein the water-soluble organic solvent (B) is at least one selected from the group consisting of glycols, sulfoxides, and amides.
  6. 　フォトレジストを使用して銅層又は銅合金層を有する金属配線を基板上に形成する際に、銅層又は銅合金層の腐食を防止するために、不要となったフォトレジストを請求項１～５のいずれか記載のフォトレジスト剥離剤組成物を使用して剥離除去することを特徴とする、銅層又は銅合金層を有する金属配線基板のフォトレジスト剥離方法。 A photoresist that is no longer needed to prevent corrosion of the copper layer or the copper alloy layer when forming a metal wiring having a copper layer or a copper alloy layer on the substrate using the photoresist. A method for removing a photoresist from a metal wiring board having a copper layer or a copper alloy layer, wherein the photoresist remover composition according to any one of 5 is removed.
PCT/JP2010/055034 2009-04-17 2010-03-24 Photoresist remover composition and method for removing photoresist WO2010119753A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020117002294A KR101668126B1 (en) 2009-04-17 2010-03-24 Photoresist remover composition and method for removing photoresist
JP2010550981A JP4725905B2 (en) 2009-04-17 2010-03-24 Photoresist stripper composition and photoresist stripping method
CN201080002286.7A CN102124414B (en) 2009-04-17 2010-03-24 Photoresist remover composition and method for removing photoresist

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-100579 2009-04-17
JP2009100579 2009-04-17

Publications (1)

Publication Number Publication Date
WO2010119753A1 true WO2010119753A1 (en) 2010-10-21

Family

ID=42982418

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/055034 WO2010119753A1 (en) 2009-04-17 2010-03-24 Photoresist remover composition and method for removing photoresist

Country Status (5)

Country Link
JP (1) JP4725905B2 (en)
KR (1) KR101668126B1 (en)
CN (1) CN102124414B (en)
TW (1) TWI617901B (en)
WO (1) WO2010119753A1 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012225959A (en) * 2011-04-15 2012-11-15 Panasonic Corp Photoresist stripping liquid
WO2012160721A1 (en) * 2011-05-20 2012-11-29 パナソニック株式会社 Photoresist stripping solution, stripping solution recycling system and operating method, and method for recycling stripping solution
JP2012242696A (en) * 2011-05-20 2012-12-10 Panasonic Corp Stripping liquid for photoresist
JP5575318B1 (en) * 2013-09-02 2014-08-20 パナソニック株式会社 Resist stripper
WO2014208088A1 (en) * 2013-06-27 2014-12-31 パナソニックＩｐマネジメント株式会社 Remover liquid for photoresists
US20150007933A1 (en) * 2013-06-21 2015-01-08 Sanmina Corporation Method of forming a laminate structure having a plated through-hole using a removable cover layer
JP2015011356A (en) * 2014-07-18 2015-01-19 パナソニックＩｐマネジメント株式会社 Stripping liquid for photoresist
JP2015113379A (en) * 2013-12-10 2015-06-22 花王株式会社 Detergent composition for removing solder flux residue
WO2017065154A1 (en) * 2015-10-13 2017-04-20 ナガセケムテックス株式会社 Photoresist remover solution
JPWO2017208767A1 (en) * 2016-06-03 2019-03-28 富士フイルム株式会社 Processing solution, substrate cleaning method and resist removal method

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI518467B (en) * 2013-11-15 2016-01-21 達興材料股份有限公司 Photoresist stripper composition, electronic device and method of fabricating the same
WO2017065153A1 (en) * 2015-10-13 2017-04-20 ナガセケムテックス株式会社 Photoresist stripping solution

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002351095A (en) * 2002-04-03 2002-12-04 Hitachi Chem Co Ltd Method of stripping water soluble resist and stripping liquid
JP2004511917A (en) * 2000-10-16 2004-04-15 マリンクロッド・ベイカー・インコーポレイテッド Stabilized alkaline composition for cleaning microelectronic substrates
JP2007510307A (en) * 2003-10-29 2007-04-19 マリンクロッド・ベイカー・インコーポレイテッド Alkaline plasma etching / ashing residue remover and photoresist stripping composition containing metal halide corrosion inhibitors
JP2007188082A (en) * 2006-01-12 2007-07-26 Air Products & Chemicals Inc PH buffer aqueous cleaning composition and method for removing photoresist residue
JP2008286881A (en) * 2007-05-15 2008-11-27 Nagase Chemtex Corp Photoresist stripping agent composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB652339A (en) * 1947-12-09 1951-04-18 Procter & Gamble Compositions for inhibiting metal tarnish
JP2001350276A (en) 2000-06-05 2001-12-21 Nagase Kasei Kogyo Kk Photoresist remover composition and method for using the same
JP3402365B2 (en) 2000-06-28 2003-05-06 日本電気株式会社 Anticorrosive
WO2008080097A2 (en) * 2006-12-21 2008-07-03 Advanced Technology Materials, Inc. Liquid cleaner for the removal of post-etch residues

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004511917A (en) * 2000-10-16 2004-04-15 マリンクロッド・ベイカー・インコーポレイテッド Stabilized alkaline composition for cleaning microelectronic substrates
JP2002351095A (en) * 2002-04-03 2002-12-04 Hitachi Chem Co Ltd Method of stripping water soluble resist and stripping liquid
JP2007510307A (en) * 2003-10-29 2007-04-19 マリンクロッド・ベイカー・インコーポレイテッド Alkaline plasma etching / ashing residue remover and photoresist stripping composition containing metal halide corrosion inhibitors
JP2007188082A (en) * 2006-01-12 2007-07-26 Air Products & Chemicals Inc PH buffer aqueous cleaning composition and method for removing photoresist residue
JP2008286881A (en) * 2007-05-15 2008-11-27 Nagase Chemtex Corp Photoresist stripping agent composition

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012225959A (en) * 2011-04-15 2012-11-15 Panasonic Corp Photoresist stripping liquid
WO2012160721A1 (en) * 2011-05-20 2012-11-29 パナソニック株式会社 Photoresist stripping solution, stripping solution recycling system and operating method, and method for recycling stripping solution
JP2012242696A (en) * 2011-05-20 2012-12-10 Panasonic Corp Stripping liquid for photoresist
CN103688222A (en) * 2011-05-20 2014-03-26 松下电器产业株式会社 Stripping solution for photoresist, stripping solution circulation system and operation method, and stripping solution circulation method
US20150007933A1 (en) * 2013-06-21 2015-01-08 Sanmina Corporation Method of forming a laminate structure having a plated through-hole using a removable cover layer
US10757819B2 (en) * 2013-06-21 2020-08-25 Sanmina Corporation Method of forming a laminate structure having a plated through-hole using a removable cover layer
JP2015011096A (en) * 2013-06-27 2015-01-19 パナソニックＩｐマネジメント株式会社 Stripping liquid for photoresist
WO2014208088A1 (en) * 2013-06-27 2014-12-31 パナソニックＩｐマネジメント株式会社 Remover liquid for photoresists
JP5575318B1 (en) * 2013-09-02 2014-08-20 パナソニック株式会社 Resist stripper
WO2015029277A1 (en) * 2013-09-02 2015-03-05 パナソニックＩｐマネジメント株式会社 Resist remover liquid
JP2015064393A (en) * 2013-09-02 2015-04-09 パナソニック株式会社 Resist stripping solution
JP2015113379A (en) * 2013-12-10 2015-06-22 花王株式会社 Detergent composition for removing solder flux residue
JP2015011356A (en) * 2014-07-18 2015-01-19 パナソニックＩｐマネジメント株式会社 Stripping liquid for photoresist
WO2017065154A1 (en) * 2015-10-13 2017-04-20 ナガセケムテックス株式会社 Photoresist remover solution
JPWO2017208767A1 (en) * 2016-06-03 2019-03-28 富士フイルム株式会社 Processing solution, substrate cleaning method and resist removal method
JP2021052186A (en) * 2016-06-03 2021-04-01 富士フイルム株式会社 Processing liquid, substrate cleaning method and resist removal method
US11397383B2 (en) 2016-06-03 2022-07-26 Fujifilm Corporation Treatment liquid, method for washing substrate, and method for removing resist
US11899369B2 (en) 2016-06-03 2024-02-13 Fujifilm Corporation Treatment liquid, method for washing substrate, and method for removing resist

Also Published As

Publication number Publication date
TW201042403A (en) 2010-12-01
CN102124414A (en) 2011-07-13
JP4725905B2 (en) 2011-07-13
TWI617901B (en) 2018-03-11
KR20120000046A (en) 2012-01-03
JPWO2010119753A1 (en) 2012-10-22
KR101668126B1 (en) 2016-10-20
CN102124414B (en) 2014-04-02

Similar Documents

Publication Publication Date Title
JP4725905B2 (en) Photoresist stripper composition and photoresist stripping method
JP5288144B2 (en) Photoresist stripper composition, photoresist stripping method and manufacturing method for laminated metal wiring board
CN102486620B (en) Photoresist stripping composition comprising primary alkanolamine for liquid crystal display manufacturing process
JP6470239B2 (en) Cleaning formulation
JP3389166B2 (en) Stripping composition for resist
JP4463054B2 (en) Photoresist stripping solution and substrate processing method using the same
KR20100032993A (en) Stripper composition for removing photoresist
JP2001022095A (en) Stripper for positive resist
CN102498197A (en) Cleaning solution composition
JP2008058624A (en) Photoresist stripping liquid, and substrate treatment method using the same
KR20080045501A (en) Photoresist stripper composition and method of stripping photoresist using same
JP2004287288A (en) Resist stripping composition and method for stripping resist
JP4442817B2 (en) Photoresist stripping solution
JP2002351093A (en) Composition for stripping resist
JP2006343604A (en) Cleaning liquid for photolithography and method of processing substrate using same
KR101292497B1 (en) Resist stripper composition and stripping method of resist using the same
JP4470328B2 (en) Resist stripper
JP5407121B2 (en) Cleaning composition
TWI438584B (en) Stripper for removing thick film photo resist
KR101374686B1 (en) Stripper Composition for removing photoresist
JP4442415B2 (en) Resist stripper
JP5321389B2 (en) Resist stripper and stripping method using the same
JP2005070230A (en) Resist stripping composition and resist stripping method
JP2012225959A (en) Photoresist stripping liquid
JP2008058623A (en) Photoresist stripping liquid, and substrate tratment method using the same

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080002286.7

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10764338

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010550981

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20117002294

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10764338

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载