WO2018020837A1 - レジスト剥離液組成物 - Google Patents

レジスト剥離液組成物 Download PDF

Info

Publication number
WO2018020837A1
WO2018020837A1 PCT/JP2017/020777 JP2017020777W WO2018020837A1 WO 2018020837 A1 WO2018020837 A1 WO 2018020837A1 JP 2017020777 W JP2017020777 W JP 2017020777W WO 2018020837 A1 WO2018020837 A1 WO 2018020837A1
Authority
WO
WIPO (PCT)
Prior art keywords
resist stripping
resist
surfactant
mass
oxyalkylene
Prior art date
Application number
PCT/JP2017/020777
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
伸一 川野
秀収 大日向
Original Assignee
野村マイクロ・サイエンス株式会社
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 野村マイクロ・サイエンス株式会社 filed Critical 野村マイクロ・サイエンス株式会社
Priority to KR1020187035608A priority Critical patent/KR20190034148A/ko
Priority to JP2018529402A priority patent/JP7061962B2/ja
Priority to CN201780038336.9A priority patent/CN109313400A/zh
Publication of WO2018020837A1 publication Critical patent/WO2018020837A1/ja

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
    • 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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • 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
    • G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
    • 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

Definitions

  • the present invention relates to a resist stripping composition.
  • a silicon semiconductor layer a gate insulating film such as a silicon oxide film, an indium tin oxide film is formed on a substrate such as a silicon wafer or glass by vacuum deposition or chemical vapor deposition.
  • An electrode film such as (ITO film) or a protective insulating film such as a silicon nitride film is formed.
  • a photoresist is uniformly applied on the gate insulating film and the protective insulating film, and then the photoresist is selectively exposed and developed to form a photoresist pattern.
  • the gate insulating film and the protective insulating film are selectively etched using this pattern as a mask to form a fine circuit, and then an unnecessary photoresist layer is removed with a resist stripper to manufacture a liquid crystal panel element. .
  • a resist film stripping solution made of a novolak resin has been used as an amine-based compound such as monoethanolamine (MEA), N-methylaminoethanol, N-methyl-2-pyrrolidone, and a water-soluble solution such as dimethyl sulfoxide (DMSO).
  • MEA monoethanolamine
  • DMSO dimethyl sulfoxide
  • Known resist stripping solutions other than amine-based resist stripping solutions include a corrosion inhibitor having reducibility and adsorptivity, a water-soluble organic solvent, water, and a surfactant (see, for example, Patent Document 1). .)
  • a rinsing step of cleaning and removing the resist stripping solution adhering to the substrate with pure water is performed following the resist stripping step after etching.
  • the resist stripping solution dissolved in the resist stripping solution is deposited on the substrate surface or dispersed in the resist stripping solution in the rinsing step with pure water.
  • Patent Document 2 A resist stripping solution in which glycerol carbonate is added to at least one selected from ethylene carbonate, propylene carbonate, ⁇ -butyrolactone and cyclopentanone has also been proposed (see, for example, Patent Document 3).
  • the present invention has been made in order to solve the above-described problems, and has excellent resist stripping performance and reattachment of a resist stripped material to a substrate (resist residue) during pure water rinsing after resist stripping.
  • An object of the present invention is to provide a resist stripping composition having a very small amount.
  • the resist stripping composition of the present invention comprises (A) 100 parts by weight of resist stripping solution and (B) 0.01 to 10 parts by weight of a surfactant having an oxyalkylene group in the molecule.
  • ITO indium tin oxide
  • the method for producing a resist remover composition of the present invention comprises producing a resist remover composition by blending 0.01 to 10 parts by mass of (B) oxyalkylene surfactant with 100 parts by mass of (A) resist remover.
  • the measurement target component is 1 nmol / cm 2 or more on an indium tin oxide film surface formed on a crystal resonator measurement substrate.
  • the resist stripping composition of the present invention has excellent resist stripping performance, and can extremely reduce the reattachment (resist residue) of the stripped resist to the substrate during rinsing with pure water after stripping the resist.
  • Surfactant No. used in Examples 18 is a graph showing the results of 18 QCM detergency tests.
  • Surfactant No. used in Examples 13 is a graph showing the results of thirteen QCM detergency tests.
  • the resist stripping solution composition of the present invention is a liquid composition used for stripping a resist film.
  • the resist remover composition of the present invention contains (A) a resist remover and (B) an oxyalkylene surfactant.
  • the oxyalkylene surfactant is the surface active material attached to the indium tin oxide (ITO) film surface on the crystal resonator measurement substrate in the crystal resonator microbalance method.
  • ITO indium tin oxide
  • the transmission frequency is 4.95 MHz.
  • the component (A) is a component that mainly develops resist stripping properties.
  • (B) component is a component which suppresses that the resist residue resulting from the resist stripping thing produced by peeling a resist arises.
  • the resist stripping composition of the present invention comprising the component (A) and the component (B) has excellent resist stripping performance and is dissolved in the resist stripping composition in the pure water rinsing step after stripping the resist. Resist strips are deposited on the surface of the substrate, or fine particles of the resist strip that are dispersed in the resist stripping liquid composition are reattached to the substrate surface. An effect of significantly suppressing the occurrence is obtained.
  • the resist stripping liquid composition of the present invention greatly suppresses the resist residue when stripping a resist film formed on a hydrophilic film such as an ITO film on a silicon substrate or a hydrophobic film such as a silicon nitride film. Effects can be obtained.
  • the resist stripping composition of the present invention is highly soluble in both a negative resist film and a positive resist film as a resist film, and exhibits excellent resist stripping performance and resist residue suppressing effect.
  • each component contained in the resist stripping composition of the present invention will be described.
  • the component (A) has an action of stripping a resist film formed on the substrate surface from the substrate.
  • the component (A) is an amine-based resist stripping solution or a hydrocarbon-based resist stripping solution described later.
  • the amine-based resist stripping solution is, for example, a solvent-based resist stripping solution containing monoethanolamine as the main component (MEA) and further containing dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP), or monoethanolamine (MEA).
  • MEA monoethanolamine
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • MEA monoethanolamine
  • An aqueous resist stripping solution containing water and ethylene glycol monobutyl ether (BDG) as main components.
  • the hydrocarbon-based resist stripping solution is a resist stripping solution containing a compound having a ring structure composed of carbon and oxygen.
  • the hydrocarbon-based resist stripping solution is, for example, a resist stripping solution containing ethylene carbonate (EC), propylene carbonate (PC), glycerin carbonate (GC), cyclopentanone (CP), ⁇ -butyrolactone (GBL) as a main component. It is.
  • the hydrocarbon-based resist stripping solution may contain a glycol compound such as ethylene glycol (EG) or propylene glycol (PG) as a resist stripping component in addition to the main component.
  • the component (A) is preferably a hydrocarbon resist stripping solution. More specifically, the component (A) preferably comprises (A1) ethylene carbonate and (A2) one or more selected from propylene carbonate, ⁇ -butyrolactone, cyclopentanone and glycerol carbonate. These components (A1) and (A2) have a five-membered ring structure in the molecular structure, and one of the carbon atoms constituting the five-membered ring has a common molecular structure constituting a carbonyl group. . Therefore, the components (A1) and (A2) are compatible with each other and can be easily mixed. The components (A1) and (A2) are highly soluble in resist films, particularly novolak resin-based resist films, and are excellent in resist stripping performance.
  • (A) component consists of said (A1) component and (A2) component
  • the resist stripping composition of the present invention exhibits extremely excellent stripping performance by using (A) a resist stripping solution containing 20% by mass or more of ethylene carbonate. According to the resist stripping solution having an ethylene carbonate content of 80% by mass or less, the resist residue is extremely reduced.
  • the component (A) when the component (A) is composed of the above components (A1) and (A2), the component (A) preferably contains ⁇ -butyrolactone as the component (A2). In this case, the component (A) preferably contains 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 50% by mass or less of ⁇ -butyrolactone based on the total amount of the component (A).
  • the resist stripping composition of the present invention exhibits a more excellent resist residue suppressing effect by using (A) resist stripping solution containing 20% by mass or more of ⁇ -butyrolactone.
  • the component (A) when the component (A) is composed of the components (A1) and (A2), the component (A) preferably contains ⁇ -butyrolactone and glycerol carbonate as the component (A2).
  • the resist stripping performance can be improved and the resist residue can be further reduced.
  • ethylene carbonate, ⁇ -butyrolactone and glycerol carbonate are preferably contained in an amount of 30% by mass or more based on the total amount of component (A).
  • the component (A) when the component (A) is composed of the component (A1) and the component (A2), the component (A) preferably contains glycerol carbonate as the component (A2). In this case, the component (A) preferably contains glycerol carbonate in an amount of more than 0% by mass and 50% by mass or less based on the total amount.
  • the resist residue By using the (A) resist stripping solution containing glycerol carbonate, the resist residue is extremely reduced.
  • the content of glycerol carbonate is preferably 30% by mass or less, and more preferably 10% by mass or less, based on the total amount of component (A).
  • (A) component contains a propylene carbonate as a (A2) component
  • (A) component contains 5 mass% or more and 30 mass% or less of propylene carbonate with respect to the whole quantity. More preferably, it is contained at 15% by mass or less.
  • the component (A) when the component (A) contains cyclopentanone as the component (A2), the component (A) preferably contains cyclopentanone in an amount of 5% by mass or more and 50% by mass or less based on the total amount of the component. More preferably, the content is 5% by mass or more and 35% by mass or less.
  • the content of cyclopentanone is in the above-described range, a resist stripping liquid composition having excellent resist stripping performance and excellent resist residue reduction effect and excellent safety can be obtained.
  • (A) component consists of said (A1) component and (A2) component
  • (A) resist stripping solution is 50 mass% or more and 70 mass% or less of (A1) ethylene carbonate with respect to the whole quantity
  • (gamma) -It is preferable that 30% by mass or more and 50% by mass or less of butyrolactone and more than 0% by mass and 30% by mass or less of glycerol carbonate are contained. If it is the said range, while improving resist stripping performance, a resist residue can further be reduced and the resist stripping liquid composition excellent in workability
  • the component (B) in the present invention suppresses the generation of resist residues in the pure water rinsing step after resist removal.
  • the present inventors have found that the component (B) having such an action can be specified by the quartz crystal microbalance method (QCM method). That is, a thin film made of indium tin oxide (ITO) is formed on a quartz crystal measurement substrate of the quartz crystal microbalance method, and a predetermined amount of a measurement target component is adhered to the surface of the ITO thin film.
  • QCM method quartz crystal microbalance method
  • the measurement target component adhering to the surface of the ITO thin film When the measurement target component adhering to the surface of the ITO thin film is washed away by (1), the measurement target component does not reattach to the ITO thin film surface, but decreases and disappears monotonously within 1000 seconds. I found out to play.
  • “monotonically decreasing” means that when the measurement target component is washed away, it generally shows a decreasing tendency until the measurement target component disappears, and the case where there is a temporary increase in the measurement target component is excluded. Not intended. That is, “monotonically decreasing” means that there is no significant increase / decrease due to irregular repetition of redeposition.
  • the QCM method uses a QCM device including a weighing balance (measurement substrate) having a crystal resonator and measures a minute weight change that occurs on the surface of the crystal resonator by using a piezoelectric effect of the crystal resonator described later. It is.
  • the QCM device is, for example, an intermolecular interaction quantitative measurement device (model name: QCM-D300) manufactured by Q-sense.
  • the surface of the crystal unit may be coated with a heavy metal such as gold, platinum, silver, iron, or titanium, or a compound such as stainless steel or silicon dioxide.
  • the measurement principle by the QCM method is as follows.
  • the crystal crystal is distorted and the crystal vibrates regularly (piezoelectric effect).
  • the frequency changes.
  • the amount of change in frequency is proportional to the mass of adhering foreign matter. Therefore, by measuring the amount of change in the frequency, the mass of the foreign matter adhering to the surface of the crystal resonator can be measured.
  • the change in frequency ( ⁇ f) of the crystal resonator is measured by applying an alternating electric field to the crystal resonator using a QCM apparatus.
  • a liquid or slurry having a solid content concentration of about 5% or less is brought into contact with the measurement substrate surface and the amount of the solid content adhering to the measurement substrate surface is measured by a wet method
  • the frequency change ⁇ f and the crystal resonator The relationship of the following formula (5) is established between the mass changes ⁇ m. As shown in the equation (5), ⁇ f is proportional to the mass of the foreign matter attached to the surface of the crystal unit.
  • Equation (6) The proportionality constant in the above equation (5) is obtained by the Sauerbrey equation (equation (6)) as follows.
  • the QCM-D 300 automatically switches four stages of frequencies of 5, 15, 25, and 35 MHz and measures each ⁇ f.
  • ⁇ f 1 is a mass obtained by dividing the change in frequency ⁇ f measured at the four stages of frequencies by 1, 3, 5 and 7, respectively, and converting it to a value at 5 MHz. A change ⁇ m is calculated.
  • FIG. 1 is a diagram schematically showing a QCM apparatus.
  • a QCM apparatus 1 shown in FIG. 1 supplies a sample solution into a sample measurement chamber 2, a measurement substrate 3 arranged in the sample measurement chamber 2, and a sample measurement chamber 2, and then for sample measurement.
  • a flow module 4 for discharging out of the chamber 2 and a frequency detector 5 for measuring a change in the frequency of a crystal resonator provided in the measurement substrate 3 are provided.
  • the frequency detector 5 is an oscillation / dissipation detector or the like.
  • the sample measurement chamber 2 is an airtight container in which the sample liquid is brought into contact with the surface of the measurement substrate 3 inside.
  • the sample measurement chamber 2 may be provided with temperature adjusting means by electronic control or the like.
  • the flow module 4 is a peristaltic pump or the like for feeding a sample liquid, and is connected to the sample measurement chamber 2 by a tube 6.
  • the QCM detergency test using the above QCM apparatus can be performed, for example, as follows.
  • (Washing step) (c) The state of decrease in the measurement target component to be washed away and the time until the measurement target component disappears are measured.
  • an ITO thin film having a thickness of 10 to 1000 nm is formed on the surface of the measurement substrate 3 by, for example, sputtering.
  • the measurement substrate 3 on which the ITO thin film is formed is placed in the sample measurement chamber 2.
  • the inside of the sample measuring chamber 2 is adjusted to a predetermined temperature by the temperature adjusting means.
  • the temperature at the time of measurement is maintained at 15 to 80 ° C. ⁇ 0.1 ° C., for example.
  • pure water is passed as blank water from the flow module 4 into the sample measurement chamber 2 to confirm the stability.
  • an attaching step is performed as follows.
  • a sample solution obtained by adding the measurement target component to the blank water at a predetermined concentration is passed through the sample measurement chamber 2. While confirming that the frequency detected by the frequency detector 5 is stable, first, the sample liquid containing the measurement target component is passed at an arbitrary concentration. When the sample solution is continuously passed, the frequency measured by the frequency detector 5 is not substantially changed, and the amount of the measurement target component adhering to the surface of the ITO film becomes the saturated adhesion amount at the concentration of the sample solution. Become. Next, when the concentration of the measurement target component in the sample liquid is slightly increased and the sample liquid is continuously passed again, the adhesion amount of the measurement target component becomes the saturated adhesion amount at the increased concentration of the sample liquid. In this manner, the sample solution was passed through while sequentially increasing the concentration, for example, the amount of saturation adhesion, and ends the adhesion step when it is 1 nmol / cm 2 or more 20 nmol / cm 2 or less.
  • the adhesion step is performed using a dilute aqueous solution having a concentration of the measurement target component in the sample solution of 0.1 to 100 ⁇ mol / mL.
  • the oscillation frequency of the frequency detector 5 at the time of measuring the frequency is, for example, 4.95 ⁇ 0.1 MHz.
  • the flow rate of blank water on the surface of the measurement substrate 3 in the cleaning step is, for example, 0.01 mL / min to 0.5 mL / min.
  • the adhering substance of the measurement target component decreases substantially monotonously from the saturated adsorption amount at the end of the attaching step by blank water flow and disappears within 1000 seconds after the blank water flow starts, the resist residue suppressing effect Can be determined.
  • the time from the start of passing the blank water to the disappearance of the deposit of the measurement target component is preferably within 900 seconds, more preferably within 600 seconds, further preferably within 300 seconds, and particularly preferably within 200 seconds. The shorter the time until disappearance, the more the resist residue suppressing effect tends to be improved.
  • the amount to be measured decreases when the adhesion amount of the component to be measured decreases according to a gentle decrease curve from the start of blank water flow. It can be determined that the deposits of the components decrease monotonously.
  • the differential coefficient of the decrease amount of the measurement target component deposition amount per passing time is a positive value within the period of the cleaning process. At this time, the differential coefficient may be zero in a part of the period of the cleaning process. The differential coefficient may temporarily be a negative value during the cleaning step. Further, it can be determined that the deposit of the measurement target component has disappeared when the amount of the deposit of the measurement target component becomes equal to or lower than the measurement lower limit value by the QCM device within the period of the cleaning process.
  • the component (B) having the QCM cleaning property suppresses the resist residue because the component (B) adheres to the substrate surface after the resist stripping composition strips the resist in the pure water rinsing step. It is considered that this is for suppressing contact between the resist stripped and dissolved in the resist stripping solution composition after stripping the resist and the substrate surface. At this time, since the adhesion force of the component (B) to the substrate surface is reasonably small, the component (B) itself is also washed away by pure water rinsing while suppressing contact between the resist and the substrate surface. Therefore, the resist residue on the substrate surface after rinsing with pure water can be extremely reduced. In addition, it is considered that the component (B) adheres to the entire surface of the resist exfoliated material and surrounds the resist exfoliated material, thereby making the resist exfoliated product difficult to contact the substrate surface.
  • the component (B) having QCM detergency is specifically a surfactant having an oxyalkylene group (oxyalkylene surfactant), preferably having a hydrophilic group, or having a hydrophobic group and a hydrophilic group. It is an oxyalkylene surfactant having both of the above.
  • the surfactant is a nonionic surfactant, an anionic surfactant, a cationic surfactant, or the like.
  • the component (B) surfactant does not necessarily have sufficient surface activity in the action of reducing micelle formation and surface tension.
  • the component (B) is ITO via its hydrophilic group. Any material can be used as long as it adheres to the surface of the membrane plate and expresses the QCM cleaning properties.
  • the component (B) is preferably a nonionic surfactant in terms of exhibiting excellent QCM detergency. This is because nonionic surfactants do not have a charge, and even if they adhere to the substrate after cleaning, they are easy to clean with pure water, and resist re-adhesion occurs based on this. This is because it can be suppressed.
  • the oxyalkylene surfactant used as the component (B) has an oxyethylene group (EO) which is a hydrophilic group, or an oxypropylene group (PO) which is a hydrophobic group in addition to the oxyethylene group (EO).
  • EO oxyethylene group
  • PO oxypropylene group
  • the oxyethylene group is a group represented by —OCH 2 CH 2 —.
  • An oxypropylene group is an oxy-i-propylene group (—OC) in which a propylene group is linear, an oxy-n-propylene group (a group represented by —OCH 2 CH 2 CH 2 —) and a propylene group are branched. 1 or more of (group represented by (CH 3 ) HCH 2 —).
  • the oxypropylene group is preferably an oxy-i-propylene group.
  • component (B) When the oxyalkylene surfactant of component (B) has EO, component (B) is sufficiently attached to the surface of a hydrophilic substrate such as ITO, and the resist strip is reattached to the substrate due to steric hindrance. Can be suppressed, and the effect of suppressing resist residue can be improved.
  • the oxyalkylene surfactant of the component (B) has PO, even when the component (B) adheres to the hydrophilic substrate surface such as ITO, it can be easily washed with pure water. It is possible to suppress the re-deposition of the resist residue at the base point.
  • the resist residue suppression effect may differ depending on the ratio of EO and PO of the oxyalkylene surfactant.
  • the component (B) having an excellent resist residue suppressing effect can be obtained by using the component (B) having the QCM cleaning property.
  • the number of oxyethylene groups and oxypropylene groups in one molecule of the oxyalkylene surfactant used as the component (B) is 0 by the ratio of the number represented by oxypropylene groups / oxyethylene groups (PO / EO). It is preferably 6 or less. Since PO / EO is 0 or more and 6 or less, an appropriate QCM detergency is expressed. Therefore, the effect of removing the component (B) with pure water and the effect of suppressing the reattachment of the resist strip to the substrate are compatible. A resist stripping composition having an excellent resist residue suppressing effect can be obtained. In this case, the number of EO is preferably 1 or more and 149 or less in one molecule.
  • the oxyalkylene surfactant used as the component (B) has an oxyethylene group (EO) and an oxypropylene group (PO)
  • the content ratio of EO and PO is a molar ratio represented by EO: PO. 0.2: 1 to 3: 1 is preferable, and 0.5: 1 to 1.5: 1 is more preferable.
  • the EO: PO molar ratio
  • an appropriate QCM detergency is exhibited, so that a resist stripping liquid composition having an excellent resist residue suppressing effect can be obtained.
  • the oxyalkylene surfactant used as the component (B) may have an alkyl group, a hydroxyl group, a hydrogen atom, or the like. These groups are connected to the carbon atom of the oxyalkylene surfactant by, for example, substituting a hydrogen atom of EO or PO, or connected between EO, POs, or between EO and PO. Or connected to the end.
  • the alkyl group, hydroxyl group, hydrogen atom, and the like are less hydrophobic than alkenyl groups, phenyl groups, and polycyclic phenyl groups, and therefore are less likely to adhere to the substrate surface and are easily washed with pure water. Therefore, the resist residue suppressing effect can be improved.
  • the alkyl group is preferably linear or branched. Since a linear or branched alkyl group has a lower hydrophobicity than a cyclic alkyl group, adhesion to the substrate surface is weak, and it is easy to clean with pure water. Therefore, the resist residue suppressing effect can be improved.
  • the oxyalkylene surfactant used as the component (B) may contain elements other than EO, PO, and optionally-containing alkyl group, carbon constituting the hydroxyl group, hydrogen, and oxygen unless the effects of the present invention are impaired. Although it is good, it is preferable to consist only of carbon, hydrogen and oxygen. When the component (B) is composed of only carbon, hydrogen, and oxygen, these elements are less likely to have an electric charge, so that the adhesion to the substrate surface is weak and easy to clean with pure water. Therefore, the resist residue suppressing effect can be improved.
  • the oxyalkylene surfactant used as the component (B) preferably has a number average molecular weight of 100 or more and 15000 or less from the viewpoint of compatibility with the resist stripping solution of the component (A).
  • the oxyalkylene surfactant preferably has 10 to 500 carbon atoms.
  • the number average molecular weight of surfactant can be measured as a polystyrene conversion value obtained by measuring by gel permeation chromatography.
  • the oxyalkylene surfactant is preferably a compound represented by the following general formula (1).
  • General formula (1) HO— (EO) x — (PO) y — (EO) z —H (In the above formula (1), EO is an oxyethylene group, PO is an oxypropylene group, x + z is a number from 1 to 150, and y is a number from 1 to 50.)
  • x + z is preferably a number from 1 to 30, and y is preferably a number from 1 to 30.
  • PO / EO number ratio
  • EO molar ratio
  • Commercial products can be used as the compound represented by the general formula (1).
  • Commercial products of the compound represented by the general formula (1) are, for example, L-31, L-62, L34, and F-88 (all are product names, manufactured by Adeka).
  • the oxyalkylene surfactant is preferably a compound represented by the following general formula (2-1).
  • R 1 is a linear, branched or cyclic alkyl group having 6 to 22 carbon atoms
  • EO is an oxyethylene group
  • PO is an oxypropylene group
  • p is (The number from 1 to 149, q is a number from 0 to 10.)
  • p is preferably a number of 1 to 40.
  • q is preferably a number from 0 to 5, more preferably a number from 0 to 3.
  • the oxyalkylene surfactant is preferably a compound represented by the following general formula (2-2).
  • R 1 is a linear, branched or cyclic alkyl group having 6 to 18 carbon atoms
  • EO is an oxyethylene group
  • PO is an oxypropylene group
  • p is 1 to 10 is a number
  • q is a number from 1 to 10.
  • R 1 is preferably linear or branched, and preferably has 8 to 16 carbon atoms, and 8 to 15 carbon atoms. It is more preferable. Further, p is preferably a number from 1 to 3, and q is preferably a number from 1 to 4. In the compounds represented by the general formulas (2-1) and (2-2), PO / EO (number ratio) is calculated as q / p, and EO: PO (molar ratio) is calculated as p: q. Calculated.
  • the oxyalkylene surfactant represented by the general formulas (2-1) and (2-2) is used as the component (B), by adding other surfactants other than these, The effect of suppressing resist residues can be improved.
  • other surfactants used in combination with the oxyalkylene surfactants represented by the general formulas (2-1) and (2-2) include anionic surfactants, cationic surfactants, nonions It is preferable that it is a system surfactant.
  • Other surfactants may be one type or two or more types.
  • the content of the (B) oxyalkylene surfactant is 0.01 to 10 parts by weight with respect to 100 parts by weight of the (A) resist stripping solution.
  • the amount is preferably 1 to 3 parts by mass, and more preferably 0.1 to 1% by mass.
  • the suppression rate of the outstanding resist residue can be acquired because the content rate of an oxyalkylene surfactant is the said range.
  • the resist stripping composition of the present invention has a viscosity at 25 ° C. of preferably 10 cP or less, and more preferably 5 cP or less.
  • glycerol carbonate when included as the component (A), glycerol carbonate has a high viscosity. Therefore, the viscosity increases when the blending amount is large, and the workability depends on the working temperature. It is also conceivable that the In such a case, it is desirable to perform the peeling operation by heating to lower the viscosity to the above range.
  • the resist stripping composition of the present invention preferably has a flash point of 100 ° C. or higher. If flash point is 100 degreeC or more, the safety
  • the flash point of the resist stripping composition of the present invention can be adjusted by changing the type and content ratio of the component (A) described above within the scope of the present invention.
  • the resist stripping composition of the present invention contains other additives other than the component (A) and the component (B), for example, a small amount of water and a water-soluble organic solvent, as long as the effects of the present invention are not impaired. You may contain.
  • the resist stripping composition of the present invention described above has excellent resist stripping performance. Also.
  • the resist stripping solution composition of the present invention can remarkably suppress the reattachment (resist residue) of the resist strip to the substrate during pure water rinsing after resist stripping.
  • the surfactant used in each example is as follows, and the general formula of each product is obtained by analysis.
  • the temperature in the sample measurement chamber was adjusted to 25 ° C., and then blank water (pure water) was passed through the sample measurement chamber.
  • the sample liquid in which the component to be measured is added to the blank water at a predetermined concentration is passed through the chamber for sample measurement, and it is confirmed that the frequency detected by the frequency detector is stable.
  • the sample solution in which the concentration of the component to be measured was increased was repeated.
  • the oscillation frequency of the frequency detector was measured by oscillating 4.95 ⁇ 0.05 MHz at 1, 3, 5, 7, 9, 11, 13 times and odd times.
  • the frequency change of the measurement substrate was measured by the frequency detector, and the mass change of the measurement substrate was calculated thereby. After the change in mass disappeared and the mass was stabilized for 300 seconds or more, the supply of the sample liquid was stopped. At this time, the measurement target component in the sample liquid is saturated and adsorbed on the measurement substrate, and when the total adhesion amount is determined from the mass change, the adhesion amount of the measurement target component to the measurement substrate is 1 nmol / cm 2. It was 20 nmol / cm 2 or more. Blank water was continuously passed through the sample measurement chamber at 0.1 mL / min. In the process, the change in the frequency was measured by the frequency detector, and the change in the mass of the measurement substrate was calculated in the same manner as in the above formulas (5) and (6).
  • a novolac resin-based positive resist (trade name: AZ SR-220 (manufactured by AZ ELECTRONIC MATERIALS) was dissolved in a predetermined amount in 50 g of the obtained resist stripping solution composition to prepare a resist solution.
  • a glass substrate having a silicon nitride (SiN x ) film formed on the surface and a glass substrate having an ITO film formed on the surface were immersed in 50 mL of a resist solution to be evaluated heated to 45 ° C. for 60 seconds, and then taken out. The glass substrate taken out was immersed in 200 mL of pure water at 60 ° C. and rinsed for 60 seconds.In the case of rinsing with pure water, pure water was supplied at a flow rate of 1.5 L / min in a container containing pure water. Rinse while supplying and overflowing.
  • CORNING trade name: Eagle 2000, 20 mm ⁇ 20 mm, thickness 0.5 mm was used.
  • the silicon nitride film and the ITO film on the glass substrate surface were both 100 nm thick and were formed by sputtering.
  • the surface of the glass substrate was dried with nitrogen gas, and then the surface of the dried glass substrate (silicon nitride film surface or ITO surface) was subjected to an optical microscope (manufactured by Olympus, trade name: Industrial Inspection Microscope MX51). ) To confirm the presence or absence of deposits on the glass substrate surface.
  • the resist concentration in the resist solution is varied in the range of 0.1 to 0.5% by mass, and the above test is performed for each concentration of the resist solution. It was. The results are shown in Table 1.
  • Examples 1 to 6, 10, 12, 13, 17, and 18 are examples, and Examples 7 to 9, 11, 14 to 16, 19, and 20 are comparative examples.
  • the resist residue suppressing effect was evaluated in the following five steps from S to D according to the allowable resist density.
  • a higher resist allowable concentration indicates that the concentration of the resist dissolved in the resist stripping solution is high, and resist adhesion (resist residue) of resist strips is less likely to occur during pure water rinsing.
  • C Allowable resist concentration is 0.00%. 1 mass% or more and less than 0.3 mass%
  • D Resist allowable concentration is less than 0.1 mass%
  • a resist stripping solution having an allowable resist concentration of about 0.1% by mass or more is suitable for practical use without causing a resist residue during pure water rinsing.
  • surfactant No. 17 (BC-40) was used as component (B) and the mixing amount thereof was changed in the same manner as in Table 2 to prepare a resist stripping solution composition, and the same resist allowable concentration as above was measured and evaluated.
  • surfactant no. 17 (BC-40) and no. 18 (BB-20) was also used, when the amount of component (B) was 0.01% by mass and 10% by mass with respect to 100% by mass of component (A), “B”; In the case of 1 mass%, 0.5 mass%, and 1.0 mass%, it is “A”. The evaluation results were the same as when 1 was used.
  • surfactant No. 17 (BC-40) was used as component (B) and the amount of the mixture was changed in the same manner as described above to prepare a resist stripping solution composition. The same resist allowable concentration as above was measured and evaluated.
  • surfactant no. 17 (BC-40) and no. 18 (BB-20) was also used, when the amount of component (B) was 0.01% by mass and 10% by mass with respect to 100% by mass of component (A), “B”; In the case of 1 mass%, 0.5 mass%, and 1.0 mass%, it is “A”. The evaluation results were the same as when 1 was used.
  • the evaluation results were the same as when 1 was used.
  • mass% “C”, 0.1 mass, 0.5 mass%, and 1.0 mass% are “A”.
  • the evaluation results were the same as when 1 was used.
  • resist stripping rate was evaluated as follows. A similar resist was coated on the same glass substrate surface as in [Evaluation of allowable resist density 1] and then baked at 110 ° C. and 130 ° C. to form a resist film having a thickness of 2 ⁇ m. The obtained glass substrate with a resist film was immersed in 50 g (normal temperature) of the resist stripping composition of each example for a predetermined time in the range of 6 to 12 seconds, and was swung once / second.
  • the resist was peeled off by immersing the glass substrate with a resist film for 10 seconds or more in any resist stripping solution composition.
  • surfactant No. 17 (BC-40) was used as component (B) and the mixing amount was changed in the same manner as described above to prepare a resist stripping solution composition, and the resist stripping rate was evaluated in the same manner as described above.
  • surfactant no. 17 (BC-40) and no. 18 (BB-20) was used, the resist stripping time was 10 to 12 seconds when the amount of the component (B) was 0.1% by mass with respect to 100% by mass of the component (A). Yes, surfactant no.
  • the evaluation results were the same as when 1 was used.
  • Example 19 and Example 25 After immersion, the amount of metal eluted in the resist stripping solution composition was measured by ICP-MS (inductively coupled plasma mass spectrometer), and the etching rate per minute of Cu, Al, and Mo was obtained from the result. The results are shown in Table 7. Moreover, in Example 19 and Example 25, it replaced with surfactant No. 1 and surfactant No.1. 17 was used (Example 93 and Example 94), surfactant No. In the case of using 18 (Example 95 and Example 96), the corrosive evaluation on the metal wiring was performed in the same manner as described above. The results are shown in the above surfactant No. Table 7 is shown together with Example 19 and Example 25 using 1.
  • SYMBOLS 1 Quartz crystal micro balance (QCM) apparatus, 2 ... Sample measurement chamber, 3 ... Measurement board
  • QCM Quartz crystal micro balance

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
PCT/JP2017/020777 2016-07-28 2017-06-05 レジスト剥離液組成物 WO2018020837A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020187035608A KR20190034148A (ko) 2016-07-28 2017-06-05 레지스트 박리액 조성물
JP2018529402A JP7061962B2 (ja) 2016-07-28 2017-06-05 レジスト剥離液組成物
CN201780038336.9A CN109313400A (zh) 2016-07-28 2017-06-05 抗蚀剂剥离液组合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-148642 2016-07-28
JP2016148642 2016-07-28

Publications (1)

Publication Number Publication Date
WO2018020837A1 true WO2018020837A1 (ja) 2018-02-01

Family

ID=61016683

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/020777 WO2018020837A1 (ja) 2016-07-28 2017-06-05 レジスト剥離液組成物

Country Status (5)

Country Link
JP (1) JP7061962B2 (zh)
KR (1) KR20190034148A (zh)
CN (1) CN109313400A (zh)
TW (1) TW201821607A (zh)
WO (1) WO2018020837A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022270333A1 (ja) * 2021-06-24 2022-12-29 日油株式会社 回路基板用樹脂膜の剥離剤および回路基板の製造方法
JP7467156B2 (ja) 2020-02-19 2024-04-15 株式会社カネカ 薄膜デバイスの製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113777895A (zh) * 2021-09-17 2021-12-10 宏伟建设工程股份有限公司 抗蚀剂剥离液组合物

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5139607A (en) * 1991-04-23 1992-08-18 Act, Inc. Alkaline stripping compositions
JPH0545894A (ja) * 1991-01-25 1993-02-26 Act Inc 有機ストリツピング組成物
JP2000267302A (ja) * 1999-03-18 2000-09-29 Kao Corp 剥離剤組成物
JP2001350275A (ja) * 2000-06-02 2001-12-21 Toppan Printing Co Ltd レジスト用剥離液
JP2003122027A (ja) * 2001-10-16 2003-04-25 Sumitomo Chem Co Ltd 剥離剤組成物
JP2004348103A (ja) * 2003-03-27 2004-12-09 Sumitomo Chem Co Ltd フォトレジスト剥離剤
JP2008058624A (ja) * 2006-08-31 2008-03-13 Tokyo Ohka Kogyo Co Ltd フォトレジスト用剥離液およびこれを用いた基板の処理方法
JP2010153851A (ja) * 2008-12-24 2010-07-08 Samsung Electronics Co Ltd フォトレジストパターン除去用組成物及びこれを利用した金属パターンの形成方法
JP2012094702A (ja) * 2010-10-27 2012-05-17 Fujifilm Corp 多剤型半導体基板用洗浄剤、それを用いた洗浄方法及び半導体素子の製造方法
WO2014002151A1 (ja) * 2012-06-26 2014-01-03 野村マイクロ・サイエンス株式会社 レジスト剥離剤

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3501675A1 (de) * 1985-01-19 1986-07-24 Merck Patent Gmbh, 6100 Darmstadt Mittel und verfahren zur entfernung von fotoresist- und stripperresten von halbleitersubstraten
US5507978A (en) * 1995-05-08 1996-04-16 Ocg Microelectronic Materials, Inc. Novolak containing photoresist stripper composition
US6248506B1 (en) * 1998-12-04 2001-06-19 Nichigo-Morton Aqueous developing solutions for reduced developer residue
US6900003B2 (en) * 2002-04-12 2005-05-31 Shipley Company, L.L.C. Photoresist processing aid and method
JP2006011054A (ja) 2004-06-25 2006-01-12 Shin Etsu Chem Co Ltd リンス液及びこれを用いたレジストパターン形成方法
JP2009014938A (ja) * 2007-07-03 2009-01-22 Toagosei Co Ltd レジスト剥離剤組成物
EP2677271B1 (en) 2012-06-18 2017-04-26 Mitutoyo Corporation Broadband interferometer for determining a property of a thin film

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0545894A (ja) * 1991-01-25 1993-02-26 Act Inc 有機ストリツピング組成物
US5139607A (en) * 1991-04-23 1992-08-18 Act, Inc. Alkaline stripping compositions
JP2000267302A (ja) * 1999-03-18 2000-09-29 Kao Corp 剥離剤組成物
JP2001350275A (ja) * 2000-06-02 2001-12-21 Toppan Printing Co Ltd レジスト用剥離液
JP2003122027A (ja) * 2001-10-16 2003-04-25 Sumitomo Chem Co Ltd 剥離剤組成物
JP2004348103A (ja) * 2003-03-27 2004-12-09 Sumitomo Chem Co Ltd フォトレジスト剥離剤
JP2008058624A (ja) * 2006-08-31 2008-03-13 Tokyo Ohka Kogyo Co Ltd フォトレジスト用剥離液およびこれを用いた基板の処理方法
JP2010153851A (ja) * 2008-12-24 2010-07-08 Samsung Electronics Co Ltd フォトレジストパターン除去用組成物及びこれを利用した金属パターンの形成方法
JP2012094702A (ja) * 2010-10-27 2012-05-17 Fujifilm Corp 多剤型半導体基板用洗浄剤、それを用いた洗浄方法及び半導体素子の製造方法
WO2014002151A1 (ja) * 2012-06-26 2014-01-03 野村マイクロ・サイエンス株式会社 レジスト剥離剤

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7467156B2 (ja) 2020-02-19 2024-04-15 株式会社カネカ 薄膜デバイスの製造方法
WO2022270333A1 (ja) * 2021-06-24 2022-12-29 日油株式会社 回路基板用樹脂膜の剥離剤および回路基板の製造方法

Also Published As

Publication number Publication date
CN109313400A (zh) 2019-02-05
TW201821607A (zh) 2018-06-16
JP7061962B2 (ja) 2022-05-02
KR20190034148A (ko) 2019-04-01
JPWO2018020837A1 (ja) 2019-05-09

Similar Documents

Publication Publication Date Title
WO2018020837A1 (ja) レジスト剥離液組成物
KR101132533B1 (ko) 알칼리성, 플라즈마 에칭/애싱 후 잔류물 제거제 및금속-할라이드 부식 억제제를 함유한 포토레지스트스트리핑 조성물
JP4741315B2 (ja) ポリマー除去組成物
JP4272676B2 (ja) フルクトース含有非水性マイクロエレクトロニクス洗浄組成物
JP2002038197A (ja) ポリマーリムーバー
WO2006107517A2 (en) Composition for cleaning ion implanted photoresist in front end of line applications
JP6033314B2 (ja) 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
KR100288769B1 (ko) 포토레지스트용스트리퍼조성물
KR20100074583A (ko) 포토레지스트 패턴 제거용 조성물 및 이를 이용한 금속 패턴의 형성 방법
JP4902898B2 (ja) 超小型電子基板のための、安定化された非水性洗浄組成物
EP2718767A1 (en) Composition of solutions and conditions for use enabling the stripping and complete dissolution of photoresists
KR20140048817A (ko) 세정 조성물 및 세정방법
JP2023118736A (ja) 除去液、及びＳｎ含有金属レジストを備えた支持体の洗浄方法
TWI839502B (zh) 洗淨液及具備金屬阻劑之支撐體的洗淨方法
CA2606849A1 (en) Compositions for the removal of post-etch and ashed photoresist residues and bulk photoresist
KR101366904B1 (ko) 드라이 에칭 잔사 제거를 위한 박리액 조성물 및 이를이용한 박리방법
KR20200120527A (ko) 세정액, 및 금속 레지스트를 구비한 지지체의 세정 방법
JP2007034067A (ja) リソグラフィー用洗浄液
TWI812342B (zh) 移除光阻之剝離劑組成物以及使用其之剝離光阻方法
JP7179146B1 (ja) 金属レジスト除去用洗浄液、及び該洗浄液を用いた洗浄方法
JP2000200766A (ja) 電子部品用洗浄液
JP2007034066A (ja) リソグラフィー用洗浄液
JP2005055886A (ja) 感光性樹脂組成物除去用洗浄剤組成物
KR20230075339A (ko) 포토레지스트 제거용 스트리퍼 조성물 및 이를 이용한 포토레지스트의 박리방법
KR20060121360A (ko) 저기포성 수계세정제 조성물

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018529402

Country of ref document: JP

Kind code of ref document: A

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

Ref document number: 17833847

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20187035608

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: 17833847

Country of ref document: EP

Kind code of ref document: A1