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WO2018100595A1 - Solution d'élimination de réserve - Google Patents

Solution d'élimination de réserve Download PDF

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Publication number
WO2018100595A1
WO2018100595A1 PCT/JP2016/005013 JP2016005013W WO2018100595A1 WO 2018100595 A1 WO2018100595 A1 WO 2018100595A1 JP 2016005013 W JP2016005013 W JP 2016005013W WO 2018100595 A1 WO2018100595 A1 WO 2018100595A1
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WIPO (PCT)
Prior art keywords
mass
water
hydrazine
pyrrolidone
propylene glycol
Prior art date
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Ceased
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PCT/JP2016/005013
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English (en)
Japanese (ja)
Inventor
真一郎 淵上
佑典 鬼頭
靖紀 鈴木
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.)
Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to PCT/JP2016/005013 priority Critical patent/WO2018100595A1/fr
Priority to CN201680043525.0A priority patent/CN107980105B/zh
Priority to JP2017535457A priority patent/JP6198095B1/ja
Priority to TW106139670A priority patent/TWI629576B/zh
Publication of WO2018100595A1 publication Critical patent/WO2018100595A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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

Definitions

  • the present invention is a stripping solution for stripping a resist film used in the manufacture of display devices and semiconductors such as liquid crystal and organic EL, and more specifically, even a hard-baked resist film can be stripped. Further, the present invention relates to a resist stripping solution that can be said to substantially not corrode aluminum films and copper films.
  • a flat panel display such as a liquid crystal or an organic EL (Electro-Luminescence) is required to have a large screen.
  • FPD flat panel display
  • small high-definition screens are required for notebook PCs, tablet PCs, and smartphones.
  • a TFT Thin Film Transistor
  • Cu wiring Cu / Mo laminated wiring
  • TFTs using Al wiring are used for small high-definition screens.
  • Cu is also called copper
  • Mo is called molybdenum
  • Al is also called aluminum.
  • Some panel manufacturers may produce TFTs using Cu wiring and TFTs mixed with Cu wiring and Al wiring in one factory.
  • TFTs in which Cu wiring and Al wiring are mixed if the resist stripping process can be shared between the use of Al wiring and the use of Cu wiring in the resist film peeling process, the production cost and equipment can be reduced. Can be reduced.
  • a water-based positive photoresist stripping solution is generally composed of an alkanolamine, a polar solvent, and water, and is used after being heated to about 40 ° C. or more and 50 ° C. or less in a resist stripping apparatus.
  • Alkanolamine is an essential component for solubilizing the carbonyl group of the DNQ (diazonaphthoquinone) compound, which is an alkali insolubilizer in the positive photoresist film, in a polar solvent and water by nucleophilic action.
  • Alkanolamines are classified as primary, secondary, and tertiary depending on the number of substituents other than hydrogen bonded to the nitrogen element. Among these, it is known that the smaller the series, the stronger the basicity and the stronger the nucleophilicity.
  • the smaller the series the stronger the ability to solubilize the DNQ compound, which is an alkali insolubilizing agent, in a polar solvent or water, and a stronger resist stripping performance (also referred to as “resist stripping force”).
  • alkanolamine is known to have a chelating action on Cu.
  • the chelating action for Cu solubilizes Cu and thus corrodes the Cu film.
  • the chelating action for Cu is stronger as the alkanolamine series is smaller as is the case with basicity and nucleophilicity. Therefore, the alkanolamine with a smaller series corrodes the Cu film more strongly.
  • a-Si amorphous silicon
  • LTPS low-temperature polysilicon
  • IGZO oxide semiconductor
  • ⁇ Al wiring is not corrosive (chelating) by alkanolamine. Therefore, in order to remove the modified resist, it is common to use a primary alkanolamine having strong resist removal performance.
  • Patent Document 1 discloses a resist stripping solution containing a compound represented by the formula (1) and a solvent. It is said that this resist stripper can also be used in the resist stripping process for Cu wiring and Al wiring.
  • Patent Document 2 discloses a resist stripping solution having a stripping force equivalent to that of an Al wiring resist stripping solution using a primary alkanolamine in spite of the use of a tertiary alkanolamine.
  • the stripping solution contains a tertiary amine, a polar solvent, water, a cyclic amine, a sugar alcohol, and a reducing agent, and the five-membered cyclic amine has a composition having pyrrolidine or pyrrolidine having a substituent at the 3-position. is there.
  • JP 2012-514765 A Patent No. 5279921
  • JP 2016-085378 A Patent No. 5885041
  • Patent Document 2 The stripping solution of Patent Document 2 can be shared in the resist stripping process for Cu wiring (including Cu / Mo laminated wiring) and Al wiring. Further, even if hard baking is applied to the resist film, the resist film can be peeled off.
  • the present invention has been conceived in view of the above-described problems, and provides a resist stripping solution that can strip even a resist film baked at a higher temperature than conventional ones.
  • a resist stripping solution that can strip even a resist film baked at a higher temperature than conventional ones.
  • the resist peeling force is strong, but also that the corrosiveness to metals such as Cu, Mo and Al is low.
  • the resist stripper is: At least one of primary or secondary amines as amines, As a polar solvent, At least one of 2-pyrrolidone (2P) and 1-methyl-2-pyrrolidone (NMP); Propylene glycol (PG), Including water, Containing hydrazine as an additive,
  • the amines are more than 3% by weight and 40% by weight or less,
  • the propylene glycol is more than 10% by weight and less than 40% by weight;
  • the water is more than 5.0% by mass and less than 30.0% by mass.
  • these composition ratios are prepared with the sum total of each material being 100 mass%.
  • the resist stripping solution according to the present invention uses a secondary amine or a primary amine, even a resist baked at a higher temperature than before can be surely stripped. Furthermore, since the resist stripping solution according to the present invention contains 2-pyrrolidone or 1-methyl-2-pyrrolidone as a polar solvent, it contains Cu, Mo, Al even though it contains secondary amine or primary amine. Corrosion to the metal is suppressed.
  • the resist stripping solution according to the present invention uses amines having a high boiling point, it can be recycled after use.
  • the resist stripping solution according to the present invention is excellent in bath life, and the resist stripping ability does not change even if it is left for 12 hours or more in an open air state or stored in a sealed state for 4 days.
  • the resist film from which the resist stripper according to the present invention is peeled is assumed to be a positive resist.
  • the positive resist includes a novolac resin as a resin, and a diazonaphthoquinone (DNQ) compound is used as a photosensitive agent.
  • DNQ diazonaphthoquinone
  • This exposure turns the DNQ compound into indenketene.
  • indenketene associates with water, it turns into indenecarboxylic acid and dissolves in water.
  • the novolac resin originally has a property of being dissolved in an alkaline solution, but the melting point is protected by a DNQ compound.
  • the DNQ compound is altered by exposure and is dissolved in a developer containing water, so that the novolak resin is also dissolved. In this way, patterning of the resist film is completed.
  • the substrate on which the patterning is completed with the resist film is subjected to wet etching or dry etching processing after post-baking.
  • Post bake is performed in order to advance polymerization of the novolak resin and the DNQ compound in the resist film to some extent.
  • the heat treatment is performed at 140 ° C. for about 5 minutes.
  • hard baking means heating conditions at 170 ° C. for 30 minutes or more. When the baking temperature rises, the novolak resin and the DNQ compound rapidly polymerize and firmly adhere to the underlying metal film, making it difficult to dissolve.
  • the resist stripping solution according to the present invention is also intended for a resist film that has undergone such hard baking.
  • the resist stripping solution according to the present invention contains secondary amines having no primary or cyclic structure, a polar solvent, and a reducing agent as an additive.
  • amines those having a boiling point higher than that of water and not azeotropic with water are desirable. This is because when the resist stripping solution is recycled, it is separated from water.
  • monoethanolamine hereinafter also referred to as “MEA”, boiling point is 170 ° C., CAS No. 141-43-5
  • MEA monoethanolamine
  • Secondary amines include N-methylethanolamine (hereinafter also referred to as “MMA”, boiling point 155 ° C., CAS number 109-83-1), N-ethylethanolamine (hereinafter also referred to as “EEA”, boiling point 170 ° C.).
  • MMA N-methylethanolamine
  • EOA N-ethylethanolamine
  • CAS number 110-73-6 can be preferably used. These may be mixed.
  • composition ratio of amines is more than 3.0% by mass and preferably 40.0% by mass or less, preferably 5.0% by mass or more and 20.0% by mass or less, most preferably with respect to the total amount of the stripping solution. Is preferably 8.0% by mass or more and 12.0% by mass or less.
  • an organic solvent having an affinity for water referred to as a water-soluble organic solvent
  • a water-soluble organic solvent it is more suitable if the mixability with said primary and secondary amine is favorable.
  • a water-soluble organic solvent a mixture of 2-pyrrolidone (hereinafter also referred to as “2P”, CAS number 616-45-5) and propylene glycol (hereinafter also referred to as “PG”, CAS number 57-55-6).
  • a liquid can be suitably used.
  • 2-pyrrolidone hereinafter also referred to as “2P”, CAS number 616-45-5
  • PG propylene glycol
  • a liquid can be suitably used.
  • 1-methyl-2-pyrrolidone hereinafter also referred to as “NMP”, CAS number 872-50-4
  • the polar solvent is composed of a water-soluble organic solvent and water.
  • composition ratio of the polar solvent is an amount excluding the amount of amines and a reducing agent described later with respect to the total amount of the stripping solution.
  • the composition ratio of each material in the polar solvent has the following desirable ranges.
  • water is preferably more than 5.0% by mass and less than 30.0% by mass with respect to the total amount of the resist stripping solution. If it is 10.0 mass% or more and 28.0 mass% or less, it is more suitable. This is because when the amount of water is too much, there arises a problem that Al is corroded when the metal film is Al.
  • Propylene glycol is preferably more than 10.0% by mass and less than 40% by mass, and more preferably 25% by mass to 35% by mass in order to stabilize hydrazine mixed as an additive.
  • 2-pyrrolidone (2P) and 1-methyl-2-pyrrolidone (NMP) may be the remainder of the polar solvent.
  • the reducing agent hydrazine (hereinafter also referred to as “HN”, CAS No. 302-01-2) can be suitably used.
  • the addition of the reducing agent suppresses Mo undercut by amines and surface corrosion of the metal film (an evaluation method will be described later).
  • the reducing agent is desirably in the range of 0.03% by mass to 0.4% by mass with respect to the total amount of the resist stripping solution. More preferably, it is the range of 0.06 mass% or more and 0.2 mass% or less.
  • Hydrazine may be hydrated (hydrazine monohydrate: described as “HN ⁇ H 2 O”) from the viewpoint of safe handling.
  • resist stripping solution examples and comparative examples of resist stripping solutions according to the present invention are shown below.
  • the resist stripping solution was evaluated for three points: “resist stripping property”, “corrosiveness of metal film”, and “bus life”.
  • a silicon thermal oxide film having a thickness of 100 nm was formed on a silicon substrate, and a copper film having a thickness of 300 nm was formed on the silicon thermal oxide film by sputtering.
  • a positive resist solution was applied onto the copper film by spin coating to prepare a resist film. After the resist film was dried, it was exposed using a wiring pattern mask. Then, the resist in the exposed portion was removed with a developer. That is, there is a state where there is a portion where the resist film of the wiring pattern remains on the copper film and a portion where the copper film is exposed. Thereafter, the entire silicon substrate was post-baked at 170 ° C. for 30 minutes.
  • the exposed copper film was removed by etching using an overwater copper etchant. After the etching of the copper film was completed, the remaining resist film on the copper pattern was stripped using a sample resist stripping solution (referred to as “new solution” in the table described later) immediately after preparation.
  • the treatment time for peeling was 15 minutes, and the time until peeling was measured. Judgment was made by observing with an optical microscope as to whether or not peeling was possible.
  • the corrosivity (metal film damage) of the metal film was evaluated as follows. First, a silicon thermal oxide film having a thickness of 100 nm was formed on a silicon substrate. Next, a molybdenum film is formed to a thickness of 20 nm on the silicon thermal oxide film on the silicon substrate, and a copper film is subsequently formed to a thickness of 300 nm to produce a Cu / Mo laminated film sample. did. This is referred to as “Cu / Mo”. In addition, an aluminum film was formed to a thickness of 300 nm on the silicon thermal oxide film on the silicon substrate to produce an Al film sample. This is referred to as “Al”.
  • the base material for corrosivity evaluation is composed of either a Cu / Mo film or an Al film formed on a silicon thermal oxide film on a silicon substrate, and a resist layer formed in a wiring shape thereon.
  • Etching was performed by immersing these corrosive evaluation base materials in an etchant for copper film or aluminum film for the time of just etching. Thereafter, the corrosive evaluation base material after etching was immersed in a sample resist stripper for 4 minutes to strip the resist film. After the corrosive evaluation base material immersed in the sample resist stripper for 4 minutes was washed and dried, the film surface was observed. Moreover, the wiring part was cut
  • the film surface and the cut surface were observed using SEM (Scanning Electron Microscope) (Hitachi: SU8020 type) under the conditions of an acceleration voltage of 1 kV and 30,000 to 50,000 times.
  • SEM Sccanning Electron Microscope
  • FIG. 1A shows a cut surface shape in the case of “Al”.
  • the cut surface shape of the just-etched portion has a taper angle 5 of approximately 30 ° to 60 ° with respect to the substrate 1.
  • the film part 2 is an Al film.
  • FIG. 1B shows the case of “Cu / Mo”.
  • the upper film portion 2 (Cu) has a taper angle 5.
  • the underlayer 3 (Mo) is preferably etched along the tapered surface 6 of the film part 2. However, the underlayer 3 may have an etching residue from the film portion 2 as shown in FIG.
  • Corrosion evaluation is called “Cu / Mo damage” for “Cu / Mo” and “Al damage” for “Al”. These are collectively referred to as “metal film damage”. And when corrosion is confirmed in either the film part 2 or the surface 4 of the film part 2 or the underlayer 3 by observing the above cross-sectional shape, it is judged as a cross (x), and no corrosion is observed. Was judged as a circle.
  • the resist stripping solution is a mixed composition of materials such as an amine, an organic solvent, and a reducing agent. Carbon dioxide in the air dissolves in the stripping solution and becomes carbonic acid / bicarbonate ions, or reacts with amines to generate carbamate ions. As a result, the stripping force decreases and metal damage increases.
  • the surface and cross-sectional state of “Al” were observed by SEM.
  • the evaluation method is the same as in the case of ⁇ resist peelability> and ⁇ metal corrosivity>. Note that 0 hour means immediately after preparation (that is, “new solution”).
  • the resist stripping solution is carried in a container.
  • the container cannot be stored at room temperature, the usability in the factory will be extremely poor. Therefore, the change of components was also examined by storage at room temperature.
  • Evaluation method was put in a sealed container and left at room temperature for 4 days to measure the stability of hydrazine.
  • hydrazine was reduced by 1% or more compared to immediately after preparation, it was “ ⁇ (cross evaluation)”, and when it was less than 1%, “ ⁇ (mal evaluation)”.
  • sample resist stripping solution was prepared as follows.
  • Example 1 Secondary amine N-methylethanolamine was used as amines. N-methylethanolamine (MMA) 10.0% by mass As a polar solvent, water, 2-pyrrolidone and propylene glycol were mixed. 2-pyrrolidone (2P) 39.9% by mass Propylene glycol (PG) 30.0% by mass Water 20.0% by mass The reducing agent hydrazine was used as an additive. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1% by mass The above was mixed and stirred to obtain the sample resist stripping solution of Example 1.
  • MMA N-methylethanolamine
  • 2-pyrrolidone 2-pyrrolidone
  • PG Propylene glycol
  • HN ⁇ H 2 O Hydrazine monohydrate
  • hydrazine monohydrate corresponds to 0.064% by mass of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • hydrazine monohydrate when used, it has the same meaning.
  • Example 2 Secondary amine N-methylethanolamine was used as amines.
  • N-methylethanolamine (MMA) 10.0% by mass
  • water, 1-methyl-2-pyrrolidone and propylene glycol were mixed.
  • 1-Methyl-2-pyrrolidone (NMP) 34.9% by mass
  • Propylene glycol (PG) 35.0 mass%
  • Water 20.0% by mass Hydrazine was used as a reducing agent.
  • Example 2 is a composition in which 2-pyrrolidone (2P) in Example 1 is changed to 1-methyl-2-pyrrolidone (NMP) and the amount of propylene glycol (PG) is increased.
  • the increase in PG decreased NMP.
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Example 3 Secondary amine N-methylethanolamine was used as amines.
  • N-methylethanolamine (MMA) 10.0% by mass
  • water, 1-methyl-2-pyrrolidone and propylene glycol were mixed.
  • 1-Methyl-2-pyrrolidone (NMP) 39.9% by mass
  • Propylene glycol (PG) 30.0% by mass
  • Water 20.0% by mass Hydrazine was used as a reducing agent.
  • Example 3 has a composition in which 2-pyrrolidone (2P) in Example 1 is changed to 1-methyl-2-pyrrolidone (NMP).
  • 2P 2-pyrrolidone
  • NMP 1-methyl-2-pyrrolidone
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Example 4 Secondary amine N-methylethanolamine was used as amines.
  • N-methylethanolamine (MMA) 10.0% by mass
  • water, 2-pyrrolidone, 1-methyl-2-pyrrolidone and propylene glycol were mixed.
  • 2-pyrrolidone (2P) 19.9% by mass 1-methyl-2-pyrrolidone (NMP) 20.0% by mass
  • Propylene glycol (PG) 30.0% by mass
  • Water 20.0% by mass Hydrazine was used as a reducing agent. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1 wt% The above was mixed and stirred to obtain a sample resist stripping solution of Example 4.
  • Example 4 is a composition obtained by adding 1-methyl-2-pyrrolidone (NMP) to the polar solvent of Example 1.
  • NMP 1-methyl-2-pyrrolidone
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Example 5 Secondary amine N-ethylethanolamine was used as amines. N-ethylethanolamine (EEA) 10.0% by mass As a polar solvent, water, 2-pyrrolidone and propylene glycol were mixed. 2-pyrrolidone (2P) 39.9% by mass Propylene glycol (PG) 30.0% by mass Water 20.0% by mass Hydrazine was used as a reducing agent. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1% by mass The above was mixed and stirred to obtain a sample resist stripping solution of Example 5.
  • Example 5 is a composition obtained by changing N-methylethanolamine (MMA) of Example 1 to N-ethylethanolamine (EEA).
  • MMA N-methylethanolamine
  • EOA N-ethylethanolamine
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Example 6 Primary amine monoethanolamine was used as amines. Monoethanolamine (MEA) 10.0% by mass As a polar solvent, water, 2-pyrrolidone and propylene glycol were mixed. 2-pyrrolidone (2P) 39.9% by mass Propylene glycol (PG) 30.0% by mass Water 20.0% by mass The reducing agent hydrazine was used as an additive. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1% by mass The above was mixed and stirred to obtain a sample resist stripping solution of Example 6.
  • Example 6 is a composition in which the N-methylethanolamine (MMA) of Example 1 is changed to the primary amine monoethanolamine (MEA).
  • MMA N-methylethanolamine
  • MEA primary amine monoethanolamine
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Example 7 Primary amine monoethanolamine was used as amines. Monoethanolamine (MEA) 10.0% by mass As a polar solvent, water, 1-methyl-2-pyrrolidone and propylene glycol were mixed. 1-Methyl-2-pyrrolidone (NMP) 39.9% by mass Propylene glycol (PG) 30.0% by mass Water 20.0% by mass The reducing agent hydrazine was used as an additive. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1% by mass The above was mixed and stirred to obtain a sample resist stripping solution of Example 7.
  • MEA Monoethanolamine
  • NMP 1-Methyl-2-pyrrolidone
  • PG Propylene glycol
  • HN ⁇ H 2 O Hydrazine monohydrate
  • Example 7 N-methylethanolamine (MMA) in Example 1 was changed to the primary amine monoethanolamine (MEA), and the polar solvent 2-pyrrolidone (2P) was changed to 1-methyl-2-pyrrolidone (NMP). ).
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Example 8 Secondary amine N-methylethanolamine was used as amines. N-methylethanolamine (MMA) 5.0% by mass As a polar solvent, water, 2-pyrrolidone and propylene glycol were mixed. 2-Pyrrolidone (2P) 44.9% by mass Propylene glycol (PG) 30.0% by mass Water 20.0% by mass The reducing agent hydrazine was used as an additive. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1% by mass The above was mixed and stirred to obtain a sample resist stripping solution of Example 8.
  • MMA N-methylethanolamine
  • 2-P 2-Pyrrolidone
  • PG Propylene glycol
  • HN ⁇ H 2 O Hydrazine monohydrate
  • Example 8 is a composition in which the composition ratio of N-methylethanolamine (MMA) in Example 1 was reduced. The decrease in MMA increased 2P. In addition, 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine. The remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • MMA N-methylethanolamine
  • Example 9 Secondary amine N-methylethanolamine was used as amines. N-methylethanolamine (MMA) 20.0% by mass As a polar solvent, water, 2-pyrrolidone and propylene glycol were mixed. 2-pyrrolidone (2P) 29.9% by mass Propylene glycol (PG) 30.0% by mass Water 20.0% by mass The reducing agent hydrazine was used as an additive. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1% by mass The above was mixed and stirred to obtain a sample resist stripping solution of Example 9.
  • MMA N-methylethanolamine
  • 2-pyrrolidone 2P
  • PG Propylene glycol
  • HN ⁇ H 2 O Hydrazine monohydrate
  • Example 9 is a composition in which the composition ratio of N-methylethanolamine (MMA) in Example 1 is increased.
  • the increase in MMA decreased 2P.
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Example 10 Secondary amine N-methylethanolamine was used as amines.
  • water, 2-pyrrolidone and propylene glycol were mixed.
  • 2-pyrrolidone (2P) 9.9% by mass
  • Propylene glycol (PG) 30.0% by mass
  • the reducing agent hydrazine was used as an additive.
  • Example 10 is a composition in which the composition ratio of N-methylethanolamine (MMA) in Example 1 is increased.
  • the increase in MMA decreased 2P.
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Example 11 Secondary amine N-methylethanolamine was used as amines. N-methylethanolamine (MMA) 10.0% by mass As a polar solvent, water, 2-pyrrolidone and propylene glycol were mixed. 2-Pyrrolidone (2P) 49.9% by mass Propylene glycol (PG) 30.0% by mass 10.0% by mass of water The reducing agent hydrazine was used as an additive. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1 wt% The above was mixed and stirred to obtain a sample resist stripping solution of Example 11.
  • MMA N-methylethanolamine
  • 2-pyrrolidone and propylene glycol were mixed.
  • Propylene glycol (PG) 30.0% by mass 10.0% by mass of water
  • the reducing agent hydrazine was used as an additive. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1 wt% The above was mixed and stirred to obtain
  • Example 11 is a composition in which the composition ratio of water in Example 1 was reduced. The decrease in water increased 2P. In addition, 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine. The remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 10.036% by mass including the amount of hydrazine monohydrate added.
  • Example 12 Secondary amine N-methylethanolamine was used as amines. N-methylethanolamine (MMA) 20.0% by mass As a polar solvent, water, 2-pyrrolidone and propylene glycol were mixed. 2-pyrrolidone (2P) 24.9% by mass Propylene glycol (PG) 30.0% by mass Water 25.0% by mass The reducing agent hydrazine was used as an additive. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1% by mass The above was mixed and stirred to obtain a sample resist stripping solution of Example 12.
  • MMA N-methylethanolamine
  • 2-pyrrolidone 2-pyrrolidone
  • PG Propylene glycol
  • HN ⁇ H 2 O Hydrazine monohydrate
  • Example 12 is a composition in which the composition ratio of N-methylethanolamine (MMA), which is the secondary amine of Example 1, and water is increased.
  • MMA N-methylethanolamine
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the above water is 25.036% by mass including the amount added as hydrazine monohydrate.
  • Example 13 Secondary amine N-methylethanolamine was used as amines. N-methylethanolamine (MMA) 20.0% by mass As a polar solvent, water, 2-pyrrolidone and propylene glycol were mixed. 2-pyrrolidone (2P) 21.9% by mass Propylene glycol (PG) 30.0% by mass 28.0% by weight of water The reducing agent hydrazine was used as an additive. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1% by mass The above was mixed and stirred to obtain a sample resist stripping solution of Example 13.
  • Example 13 is a composition in which the composition ratio of the secondary amine N-methylethanolamine (MMA) and water of Example 1 is increased. The increase in MMA and water decreased 2P.
  • Example 13 has a composition with more water than Example 12.
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine. The remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 28.036% by mass including the amount of hydrazine monohydrate added.
  • Example 14 Primary amine monoethanolamine was used as amines. Monoethanolamine (MEA) 10.0% by mass As a polar solvent, water, 2-pyrrolidone and propylene glycol were mixed. 2-pyrrolidone (2P) 34.9% by mass Propylene glycol (PG) 30.0% by mass Water 25.0% by mass The reducing agent hydrazine was used as an additive. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1% by mass The above was mixed and stirred to obtain a sample resist stripping solution of Example 14.
  • MEA Monoethanolamine
  • 2-pyrrolidone and propylene glycol were mixed.
  • 2-pyrrolidone (2P) 34.9% by mass
  • the reducing agent hydrazine was used as an additive. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1% by mass The above was mixed and stirred to obtain a sample resist stripping solution of Example 14.
  • Example 14 is a composition in which the secondary amine of Example 1 was changed to the primary amine monoethanolamine (MEA) and the composition ratio of water was further increased. The increase in water decreased 2P.
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the above water is 25.036% by mass including the amount added as hydrazine monohydrate.
  • Example 15 Primary amine monoethanolamine was used as amines. Monoethanolamine (MEA) 20.0% by mass As a polar solvent, water, 2-pyrrolidone and propylene glycol were mixed. 2-pyrrolidone (2P) 24.9% by mass Propylene glycol (PG) 30.0% by mass Water 25.0% by mass The reducing agent hydrazine was used as an additive. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1% by mass The above was mixed and stirred to obtain a sample resist stripping solution of Example 15.
  • Example 15 is a composition in which the secondary amine of Example 1 was changed to the primary amine monoethanolamine (MEA), the composition ratio was increased, and the composition ratio of water was further increased. In contrast to Example 14, the MEA composition ratio was further increased. The increase in MEA and water decreased 2P. In addition, 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine. The remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the above water is 25.036% by mass including the amount added as hydrazine monohydrate.
  • MEA primary amine monoethanolamine
  • Example 16 Primary amine monoethanolamine was used as amines. Monoethanolamine (MEA) 40.0% by mass As a polar solvent, water, 2-pyrrolidone and propylene glycol were mixed. 2-pyrrolidone (2P) 9.9% by mass Propylene glycol (PG) 30.0% by mass Water 20.0% by mass The reducing agent hydrazine was used as an additive. Hydrazine monohydrate (HN ⁇ H 2 O) 0.1% by mass The above was mixed and stirred to obtain a sample resist stripping solution of Example 16.
  • Example 16 is a composition in which the secondary amine of Example 1 is changed to monoethanolamine (MEA), which is a primary amine, and the composition ratio is also increased.
  • MEA monoethanolamine
  • the MEA composition ratio was further increased.
  • the increase in MEA decreased 2P.
  • the composition ratio of water was decreased with respect to Examples 14 and 15, and the same as in Example 1.
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Comparative Example 1 has a composition in which the polar solvent 2-pyrrolidone (2P) of Example 1 is changed to 1-ethyl-2-pyrrolidone (NEP).
  • 2P polar solvent 2-pyrrolidone
  • NEP 1-ethyl-2-pyrrolidone
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Comparative Example 2 is a composition excluding propylene glycol (PG) as the polar solvent of Example 1.
  • PG propylene glycol
  • the amount of PG increased 2P.
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Comparative Example 3 is a composition in which the composition ratio of propylene glycol (PG), which is the polar solvent of Example 1, is decreased. The decrease in PG increased 2P.
  • PG propylene glycol
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Comparative Example 4 is a composition in which the composition ratio of propylene glycol (PG), which is the polar solvent of Example 1, is increased.
  • PG propylene glycol
  • 2P 2P
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Comparative Example 5 is a composition obtained by changing the polar solvent 2-pyrrolidone (2P) of Example 1 to N-methylformamide (NMF).
  • 2P polar solvent 2-pyrrolidone
  • NMF N-methylformamide
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Comparative Example 6 has a composition in which the polar solvent 2-pyrrolidone (2P) of Example 1 is changed to N, N-dimethylformamide (DMF).
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Comparative Example 7 is a composition in which the polar solvent 2-pyrrolidone (2P) of Example 1 was changed to diethylene glycol monobutyl ether (BDG).
  • BDG diethylene glycol monobutyl ether
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Comparative Example 8 has a composition obtained by changing the polar solvent 2-pyrrolidone (2P) of Example 1 to ethylene carbonate (EC).
  • 2P polar solvent 2-pyrrolidone
  • EC ethylene carbonate
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Comparative Example 9 is a composition obtained by changing the secondary amine N-methylethanolamine (MMA) of Example 1 to the cyclic amine pyrrolidine (PRL).
  • MMA secondary amine N-methylethanolamine
  • PRL cyclic amine pyrrolidine
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Comparative Example 10 is a composition obtained by changing the secondary amine N-methylethanolamine (MMA) of Example 1 to the cyclic amine hydroxyethylpiperazine (OH-PIZ).
  • MMA secondary amine N-methylethanolamine
  • OH-PIZ cyclic amine hydroxyethylpiperazine
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Comparative Example 11 is a composition obtained by changing the secondary amine N-methylethanolamine (MMA) of Example 1 to a tertiary amine N-methyldiethanolamine (MDEA).
  • MMA secondary amine N-methylethanolamine
  • MDEA tertiary amine N-methyldiethanolamine
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Comparative Example 12 Secondary amine N-methylethanolamine was used as amines. N-methylethanolamine (MMA) 10.0% by mass As a polar solvent, water, 2-pyrrolidone and propylene glycol were mixed. 2-pyrrolidone (2P) 40.0% by mass Propylene glycol (PG) 30.0% by mass Water 20.0% by mass The reducing agent hydrazine as an additive was not added. The above was mixed and stirred to obtain a sample resist stripping solution of Comparative Example 12. Comparative Example 11 is a composition obtained by removing hydrazine (HN) from the composition of Example 1.
  • HN hydrazine
  • Comparative Example 15 Secondary amine N-methylethanolamine was used as amines. N-methylethanolamine (MMA) 10.0% by mass As a polar solvent, water, 2-pyrrolidone and propylene glycol were mixed. 2-pyrrolidone (2P) 39.5% by mass Propylene glycol (PG) 30.0% by mass Water 20.0% by mass Saccharin (: o-sulfobenzimide, CAS No. 81-07-2) was used as an additive. Saccharin 0.5% by mass The above was mixed and stirred to obtain a sample resist stripping solution of Comparative Example 15. Comparative Example 15 is a composition in which the additive of Example 1 (reducing agent: hydrazine (HN)) was changed to saccharin.
  • reducing agent hydrazine (HN)
  • Comparative Example 16 is a composition in which the composition ratio of water in Example 1 is increased. The increase in water decreased 2P. In addition, 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine. The remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the above water is 30.036% by mass including the amount added as hydrazine monohydrate.
  • Comparative Example 17 is a composition in which the composition ratio of N-methylethanolamine (MMA) and water in Example 1 is increased.
  • the increase in MMA and water decreased 2P.
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the above water is 30.036% by mass including the amount added as hydrazine monohydrate.
  • Comparative Example 18 is a composition in which the composition ratio of N-methylethanolamine (MMA) in Example 1 is increased and the composition ratio of water is decreased.
  • MMA N-methylethanolamine
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 5.036% by mass including the amount of hydrazine monohydrate added.
  • Comparative Example 19 is a composition in which the composition ratio of N-methylethanolamine (MMA) in Example 1 was reduced. The decrease in MMA increased 2P.
  • MMA N-methylethanolamine
  • 0.1 mass% of hydrazine monohydrate corresponds to 0.064 mass% of hydrazine.
  • the remaining 0.036% by mass of hydrazine monohydrate is water. Therefore, it can be said that the composition ratio of the water is 20.036% by mass including the amount of hydrazine monohydrate added.
  • Table 1 shows the compositions and results of Examples 1 to 4
  • Table 2 shows the compositions and evaluation results of Examples 1 and Comparative Examples 1 to 8.
  • Table 3 shows the compositions and evaluation results of Examples 1 and 5 to 7 and Comparative Examples 9 to 11.
  • Table 4 shows the compositions and evaluation results of Example 1 and Comparative Examples 12 to 15.
  • the compositions and evaluation results of Examples 1 and 8 to 16 are shown in Table 5, and the compositions and evaluation results of Example 1 and Comparative Examples 16 to 19 are shown in Table 6.
  • Table 1 shows the compositions and results of Examples 1 to 4, and Table 2 shows the compositions and evaluation results of Example 1 and Comparative Examples 1 to 8.
  • Example 1 in Table 1 By using a secondary amine N-methylethanolamine (MMA) as an amine and using a mixed solution of 2-pyrrolidone (2P), propylene glycol (PG) and water as a polar solvent, baking is performed at 170 ° C. for 30 minutes. The (hard-baked) resist film could be removed in 5 minutes. Moreover, the damage of the films of “Cu / Mo” and “Al” was also evaluated as being poor.
  • MMA secondary amine N-methylethanolamine
  • 2P 2-pyrrolidone
  • PG propylene glycol
  • the peeling force did not change even after 12 hours had elapsed in the bath life when the peeling solution was left open to the atmosphere. Furthermore, no decrease in hydrazine was observed even after 4 days of sealed storage.
  • Example 2 A secondary amine N-methylethanolamine (MMA) was used as the amine, and a mixture of 1-methyl-2-pyrrolidone (NMP), propylene glycol (PG) and water was used as the polar solvent.
  • Example 2 is a composition in which the polar solvent 2-pyrrolidone (2P) of Example 1 was changed to 1-methyl-2-pyrrolidone (NMP).
  • Example 2 propylene glycol (PG) was increased from 30.0% by mass to 35.0% by mass as compared with Example 1. This increase reduced the amount of 1-methyl-2-pyrrolidone (NMP). In this composition as well as in Example 1, the resist baked at 170 ° C. for 30 minutes could be removed in 5 minutes. Moreover, the damage of the films of “Cu / Mo” and “Al” was also evaluated as being poor.
  • PG propylene glycol
  • NMP 1-methyl-2-pyrrolidone
  • the resist stripping power did not change even after 12 hours had elapsed in the bath life when the stripper was left open to the atmosphere. Furthermore, no decrease in hydrazine was observed even after 4 days of sealed storage.
  • Example 3 A secondary amine N-methylethanolamine (MMA) was used as the amine, and a mixture of 1-methyl-2-pyrrolidone (NMP), propylene glycol (PG) and water was used as the polar solvent.
  • NMP 1-methyl-2-pyrrolidone
  • PG propylene glycol
  • water was used as the polar solvent.
  • the resist baked at 170 ° C. for 30 minutes could be removed in 5 minutes.
  • the damage of the films of “Cu / Mo” and “Al” was also evaluated as being poor.
  • Example 3 the 2-pyrrolidone (2P) in Example 1 was changed to 1-methyl-2-pyrrolidone (NMP), and the composition ratio was the same. Therefore, it can be said that 2-pyrrolidone (2P) and 1-methyl-2-pyrrolidone (NMP) can be replaced in this system.
  • Example 4 in addition to 2-pyrrolidone (2P) used in Example 1, 1-methyl-2-pyrrolidone (NMP) was used as a polar solvent. In this composition as well as in Example 1, the resist baked at 170 ° C. for 30 minutes could be removed in 5 minutes. Moreover, the damage of the films of “Cu / Mo” and “Al” was also evaluated as being poor.
  • Example 4 had a composition ratio in which the polar solvent 2-pyrrolidone (2P) and 1-methyl-2-pyrrolidone (NMP) were used in combination. Therefore, it can be said that at least one of 2-pyrrolidone (2P) and 1-methyl-2-pyrrolidone (NMP) may be used.
  • Comparative Example 1 is a composition obtained by replacing 2-pyrrolidone (2P), which is the polar solvent of Example 1, with 1-ethyl-2-pyrrolidone (NEP).
  • 2P 2-pyrrolidone
  • NEP 1-ethyl-2-pyrrolidone
  • Comparative Example 1 the resist film baked at 170 ° C. for 30 minutes immediately after preparation (new solution) could not be peeled off.
  • Comparative Example 1 the same N-methylethanolamine (MMA) as in Examples 1 and 2 was used as the amine. That is, it can be seen that the hard-baked resist film cannot be removed by using a secondary amine, and a combination with a polar solvent is necessary.
  • MMA N-methylethanolamine
  • Comparative Example 2 is a composition excluding propylene glycol (PG) as the polar solvent of Example 1.
  • PG propylene glycol
  • Comparative Example 3 has a composition in which the amount of propylene glycol (PG), which is the polar solvent of Example 1, is reduced from 30.0% by mass to 10.0% by mass.
  • PG propylene glycol
  • Comparative Example 3 no problem occurred due to the resist peeling force immediately after preparation (new solution) and damage to the metal film after being left in the atmosphere for 12 hours.
  • a decrease in hydrazine was observed after standing for 4 days. From the above, it can be seen that propylene glycol (PG) cannot increase the stability of hydrazine at 10 mass% or less.
  • Comparative Example 4 is a composition in which the amount of propylene glycol (PG) as a polar solvent in Example 1 was increased from 30.0% by mass to 40.0% by mass. In Comparative Example 4, the hard-baked resist film could not be peeled off immediately after preparation (new solution). Considering the results of Comparative Example 3 as well, propylene glycol (PG) cannot increase the stability of hydrazine when it is 10% by mass or less, and if it is 40.0% by mass or more, it has a resist peeling force with respect to a hard-baked resist film. It turns out that it will expire.
  • PG propylene glycol
  • Comparative Example 5 is a composition obtained by replacing the polar solvent 2-pyrrolidone (2P) of Example 1 with N-methylformamide (NMF).
  • 2P polar solvent 2-pyrrolidone
  • NMF N-methylformamide
  • Comparative Example 6 has a composition obtained by replacing the polar solvent 2-pyrrolidone (2P) of Example 1 with N, N-dimethylformamide (DMF).
  • 2P polar solvent 2-pyrrolidone
  • DMF N, N-dimethylformamide
  • Comparative Example 7 is a composition obtained by replacing the polar solvent 2-pyrrolidone (2P) of Example 1 with diethylene glycol monobutyl ether (BDG).
  • BDG diethylene glycol monobutyl ether
  • Comparative Example 8 has a composition in which the polar solvent 2-pyrrolidone (2P) of Example 1 is replaced with ethylene carbonate (EC). Also in Comparative Example 8, the resist film that had already been hard-baked immediately after preparation (new solution) could not be peeled off. Therefore, no test was conducted for bus life.
  • the secondary amine N-methylethanolamine (MMA) of Example 1 was used, 2-pyrrolidone (2P) or 1-methyl-2-pyrrolidone (NMP) as a polar solvent, and propylene glycol (PG). ) And water mixture, and the hydrazine-containing stripping solution was evaluated as being poor in terms of resist stripping ability and bath life.
  • Example 5 is a composition in which N-methylethanolamine (MMA) in Example 1 was changed to N-ethylethanolamine (EEA). In Example 5, the resist stripping force, metal damage, and bath life were all evaluated in the same manner as in Example 1 in all evaluation items.
  • MMA N-methylethanolamine
  • EOA N-ethylethanolamine
  • Example 6 is a composition in which the N-methylethanolamine (MMA) of Example 1 is changed to the primary amine monoethanolamine (MEA).
  • MMA N-methylethanolamine
  • MEA primary amine monoethanolamine
  • Example 7 N-methylethanolamine (MMA) in Example 1 was changed to monoethanolamine (MEA) as a primary amine, and 2-pyrrolidone (2P) was changed to 1-methyl-2-pyrrolidone (NMP). Composition.
  • MMA monoethanolamine
  • 2P 2-pyrrolidone
  • NMP 1-methyl-2-pyrrolidone
  • N-ethylethanolamine EAA
  • EAA N-ethylethanolamine
  • MEA primary amine monoethanolamine
  • MEP 2-pyrrolidone
  • NMP 1-methyl-2-pyrrolidone
  • Comparative Examples 9 to 11 are compositions using other amines.
  • pyrrolidine (PRL) which is a cyclic amine
  • Comparative Example 10 is a case where the cyclic amine hydroxyethylpiperazine (OH-PIZ) is used
  • Comparative Example 11 is a case where the tertiary amine N-methyldiethanolamine (MDEA) is used.
  • PRL pyrrolidine
  • MDEA tertiary amine N-methyldiethanolamine
  • Comparative Example 12 is a composition that does not contain hydrazine (hydrazine monohydrate (HN ⁇ H 2 O)). In Comparative Example 12, the hard-baked resist film could not be removed immediately after preparation (new solution). Further, film damage of “Cu / Mo” occurred. Al damage was not observed. The bus life was not implemented.
  • Comparative Example 13 sorbitol (Stol) was added instead of the hydrazine of Example 1.
  • Comparative Example 14 diglycerin was added instead of the hydrazine of Example 1.
  • saccharin was added instead of the hydrazine of Example 1.
  • the hard-baked resist film could not be peeled off immediately after preparation (new solution). Further, Cu / Mo damage occurred. Al damage was not observed. The bus life was not implemented.
  • hydrazine hydrazine monohydrate (HN ⁇ H 2 O)
  • HN ⁇ H 2 O hydrazine monohydrate
  • Table 5 shows the compositions and evaluation results of Examples 1 and 8 to 16.
  • Table 6 shows the compositions and evaluation results of Example 1 and Comparative Examples 16 to 19.
  • Example 5 shows examples when the composition ratio of amines and water is changed. Since Example 1 is shown again, it is shown in parentheses. In Example 8, the N-methylethanolamine (MMA) ratio in Example 1 was reduced from 10% by mass to 5% by mass. The decrease in MMA increased 2P. In Example 8, the resist film hard-baked immediately after preparation (new solution) could be removed in 7 minutes. Also, there was no problem with the metal film damage and the bus life, and the evaluation was “maru”. In addition, no decrease in hydrazine was observed even after 4 days of sealing.
  • MMA N-methylethanolamine
  • Example 9 is a composition in which the ratio of N-methylethanolamine (MMA) in Example 1 was increased from 10.0% by mass to 20.0% by mass. The increase in MMA decreased 2P.
  • the resist film hard-baked immediately after preparation (new solution) could be peeled off in 5 minutes. Also, there was no problem with the metal film damage and the bus life, and the evaluation was “maru”. In addition, no decrease in hydrazine was observed even after 4 days of sealing. That is, the same performance as Example 1 was shown.
  • MMA N-methylethanolamine
  • Example 10 is a composition in which the ratio of N-methylethanolamine (MMA) in Example 1 is increased from 10.0% by mass to 40.0% by mass.
  • the increase in MMA decreased 2P.
  • the resist film hard-baked immediately after preparation (new solution) could be removed in 5 minutes. Also, there was no problem with the metal film damage and the bus life, and the evaluation was “maru”. In addition, no decrease in hydrazine was observed even after 4 days of sealing. That is, the same performance as Example 1 was shown.
  • MMA N-methylethanolamine
  • Example 11 has a composition in which the amount of water in Example 1 is reduced from 20.0% by mass to 10.0% by mass. The decrease in water increased 2P. In Example 11, the resist film hard-baked immediately after preparation (new solution) could be removed in 5 minutes. Also, there was no problem with the metal film damage and the bus life, and the evaluation was “maru”. In addition, no decrease in hydrazine was observed even after 4 days of sealing. That is, the same performance as Example 1 was shown.
  • Example 12 increases the amount of secondary amine N-methylethanolamine (MMA) of Example 1 from 10.0% to 20.0% by weight and the amount of water from 20.0% to 25.0%.
  • the composition is increased to mass%.
  • the increase in MMA and water decreased 2P.
  • the resist film hard-baked immediately after preparation (new solution) could be removed in 5 minutes. Also, there was no problem with the metal film damage and the bus life, and the evaluation was “maru”. In addition, no decrease in hydrazine was observed even after 4 days of sealing. That is, the same performance as Example 1 was shown.
  • Example 13 the amount of secondary amine N-methylethanolamine (MMA) of Example 1 was increased from 10.0% to 20.0% by weight, and the amount of water was increased from 20.0% to 28.0%. The composition is increased to mass%. The increase in MMA and water decreased 2P.
  • the resist film hard-baked immediately after preparation (new solution) could be removed in 5 minutes. Also, there was no problem with the metal film damage and the bus life, and the evaluation was “maru”. In addition, no decrease in hydrazine was observed even after 4 days of sealing. That is, the same performance as Example 1 was shown.
  • Example 14 is a composition in which the secondary amine of Example 1 was replaced with the primary amine monoethanolamine (MEA), and the amount of water was further increased from 20.0% by mass to 25.0% by mass. The amount of water increased decreased 2P.
  • MEA primary amine monoethanolamine
  • the resist film hard-baked immediately after preparation (new solution) could be removed in 5 minutes. Also, there was no problem with the metal film damage and the bus life, and the evaluation was “maru”. In addition, no decrease in hydrazine was observed even after 4 days of sealing. That is, the same performance as Example 1 was shown.
  • Example 15 is a composition in which the secondary amine of Example 1 is replaced with the primary amine monoethanolamine (MEA), and the composition ratio is also increased from 10.0% by mass to 20.0% by mass. Water was also increased from 20.0% by mass to 25.0% by mass. The increase in MEA and water decreased 2P.
  • MEA primary amine monoethanolamine
  • Example 15 the resist film hard-baked immediately after preparation (new solution) could be removed in 4 minutes. Also, there was no problem with the metal film damage and the bus life, and the evaluation was “maru”. In addition, no decrease in hydrazine was observed even after 4 days of sealing. That is, the peelability higher than that of Example 1 and the performance of the bus life similar to that of Example 1 were shown.
  • Example 16 is a composition in which the secondary amine of Example 1 is replaced with the primary amine monoethanolamine (MEA), and the composition ratio is also increased from 10.0% by mass to 40.0% by mass. In addition, the composition ratio of water is 20.0 mass% similarly to Example 1.
  • the increase in MEA decreased 2P.
  • the resist film hard-baked immediately after preparation (new solution) could be removed in 4 minutes. Also, there was no problem with the metal film damage and the bus life, and the evaluation was “maru”. In addition, no decrease in hydrazine was observed even after 4 days of sealing. That is, the peelability higher than that of Example 1 and the performance of the bus life similar to that of Example 1 were shown.
  • Table 6 is a comparative example in which the composition ratio of amine and the composition ratio of water are changed. Since Example 1 is shown again, it is shown in parentheses.
  • Comparative Example 16 has a composition in which the amount of water in Example 1 is increased from 20.0% by mass to 30.0% by mass. The increase in water decreased 2P. In Comparative Example 16, the hard-baked resist film could not be removed immediately after preparation (new solution). When there is too much water compared with Example 1, peeling force will fall.
  • Comparative Example 17 the amount of N-methylethanolamine (MMA) in Example 1 was increased from 10.0% by mass to 20.0% by mass, and the amount of water was increased from 20.0% by mass to 30.0% by mass. The composition is increased. These increases decreased 2P. In Comparative Example 17, the hard-baked resist film could be peeled off in 5 minutes immediately after preparation (new solution). Moreover, the damage to Co / Mo was also "maru" evaluation. However, damage to Al occurred.
  • MMA N-methylethanolamine
  • Example 13 In the secondary amine ratio, Example 13 and Comparative Example 17 are the same.
  • the water was 28.0% by mass, and the water was 30 in consideration of the “mal” evaluation for all evaluation items. If it is 0.0% by mass or more, it is not possible to obtain a round evaluation regarding the peeling force.
  • Example 10 was a composition containing 40.0% by mass of secondary amine N-methylethanolamine (MMA), and Example 16 was a composition containing 40.0% by mass of primary ethanol monoethanolamine (MEA). It was. In these examples, water was 20.0% by mass. Therefore, it is considered that the primary amine and the secondary amine exhibit almost the same behavior with respect to water. Therefore, even if the amine is a primary amine or a secondary amine, if the water content is 5.0% by mass or less and 30.0% by mass or more, the hard-baked resist film cannot be removed. I can say that.
  • MMA secondary amine N-methylethanolamine
  • MEA primary ethanol monoethanolamine
  • Comparative Example 19 is a composition obtained by reducing the N-methylethanolamine (MMA) of Example 1 from 10.0% by mass to 3.0% by mass. Loss of N-methylethanolamine (MMA) increased 2P. In Comparative Example 19, the hard-baked resist film could not be peeled off immediately after preparation (new solution). Accordingly, when the composition ratio of N-methylethanolamine (MMA) is 3.0% by mass or less, it is not possible to obtain a mal evaluation regarding the peeling force. That is, if it is more than 3.0% by mass, it is considered that a round evaluation is obtained regarding the peeling force. Moreover, since the primary amine is higher than the secondary amine in terms of peel strength, it can be said that if the primary amine is more than 3.0% by mass, it is possible to obtain a mal evaluation regarding the peel strength.
  • the resist stripping solution according to the present invention can surely strip a hard-baked resist film, and can be suitably used in a situation where a photoresist is used.

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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)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

Selon l'invention, dans des procédés permettant de fabriquer des dispositifs à semi-conducteur, etc., un durcissement est effectué à une température supérieure à celle du passé afin d'éviter un durcissement défectueux de réserves. Une solution d'élimination ayant une puissance d'élimination supérieure à celle du passé est par conséquent exigée. Une solution d'élimination de réserve contient une amine primaire et/ou secondaire faisant office d'amine, du 2-pyrrolidone (2P) et/ou du 1-méthyl-2-pyrrolidone (NMP) servant de solvant polaire, du propylèneglycol (PG), et de l'eau, et elle contient de l'hydrazine faisant office d'additif. L'amine contenue représente une quantité supérieure à 3 % en masse et jusqu'à 40 % en masse, le propylèneglycol contenu représente une quantité supérieure à 10 % en masse et inférieure à 40 % en masse, et l'eau contenue représente une quantité supérieure à 5,0 % en masse et inférieure à 30,0 % en masse. La solution d'élimination de réserve peut éliminer un film de réserve soumis à une cuisson à haute température, et elle ne corrode ni une surface ni une section transversale de film métallique.
PCT/JP2016/005013 2016-11-29 2016-11-29 Solution d'élimination de réserve Ceased WO2018100595A1 (fr)

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PCT/JP2016/005013 WO2018100595A1 (fr) 2016-11-29 2016-11-29 Solution d'élimination de réserve
CN201680043525.0A CN107980105B (zh) 2016-11-29 2016-11-29 抗蚀剂剥离液
JP2017535457A JP6198095B1 (ja) 2016-11-29 2016-11-29 レジスト剥離液
TW106139670A TWI629576B (zh) 2016-11-29 2017-11-16 Photoresist stripper

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021108531A (ja) * 2019-12-27 2021-07-29 株式会社三若純薬研究所 被覆樹脂剥離液、被覆樹脂剥離用処理液及び被覆樹脂剥離処理方法
WO2024253140A1 (fr) * 2023-06-07 2024-12-12 花王株式会社 Composition d'agent de nettoyage pour éliminer un masque en résine

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002196509A (ja) * 2000-12-25 2002-07-12 Nagase Kasei Kogyo Kk フォトレジスト剥離剤組成物及びその使用方法
JP2004502980A (ja) * 2000-07-10 2004-01-29 イーケイシー　テクノロジー　インコーポレーテッド 半導体デバイスの有機及びプラズマエッチング残さの洗浄用組成物
JP2014078009A (ja) * 2012-10-08 2014-05-01 Air Products And Chemicals Inc 厚いフィルム・レジストを除去するための剥離及びクリーニング用組成物
JP2014534627A (ja) * 2011-10-05 2014-12-18 アバンター・パフォーマンス・マテリアルズ・インコーポレイテッド 銅／アゾールポリマー阻害剤を含むマイクロ電子基板洗浄組成物

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI275903B (en) * 2001-03-13 2007-03-11 Nagase Chemtex Corp A composition for stripping photo resist
CN1875326A (zh) * 2003-10-29 2006-12-06 长濑化成株式会社 光致抗蚀剂剥离用组合物及剥离光致抗蚀剂的方法
KR100950779B1 (ko) * 2009-08-25 2010-04-02 엘티씨 (주) Ｔｆｔ―ｌｃｄ 통합공정용 포토레지스트 박리제 조성물
JP6277511B2 (ja) * 2013-10-18 2018-02-14 パナソニックＩｐマネジメント株式会社 レジスト剥離液
CN104946429A (zh) * 2014-03-26 2015-09-30 安集微电子科技(上海)有限公司 一种低蚀刻的去除光阻蚀刻残留物的清洗液
KR102009545B1 (ko) * 2015-03-05 2019-10-21 동우 화인켐 주식회사 레지스트 박리액 조성물

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004502980A (ja) * 2000-07-10 2004-01-29 イーケイシー　テクノロジー　インコーポレーテッド 半導体デバイスの有機及びプラズマエッチング残さの洗浄用組成物
JP2002196509A (ja) * 2000-12-25 2002-07-12 Nagase Kasei Kogyo Kk フォトレジスト剥離剤組成物及びその使用方法
JP2014534627A (ja) * 2011-10-05 2014-12-18 アバンター・パフォーマンス・マテリアルズ・インコーポレイテッド 銅／アゾールポリマー阻害剤を含むマイクロ電子基板洗浄組成物
JP2014078009A (ja) * 2012-10-08 2014-05-01 Air Products And Chemicals Inc 厚いフィルム・レジストを除去するための剥離及びクリーニング用組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021108531A (ja) * 2019-12-27 2021-07-29 株式会社三若純薬研究所 被覆樹脂剥離液、被覆樹脂剥離用処理液及び被覆樹脂剥離処理方法
JP7590752B2 (ja) 2019-12-27 2024-11-27 株式会社三若純薬研究所 被覆樹脂剥離液、被覆樹脂剥離用処理液及び被覆樹脂剥離処理方法
WO2024253140A1 (fr) * 2023-06-07 2024-12-12 花王株式会社 Composition d'agent de nettoyage pour éliminer un masque en résine

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