WO2017130932A1 - Procédé de formation de motif, procédé de fabrication de dispositif électronique - Google Patents

Procédé de formation de motif, procédé de fabrication de dispositif électronique Download PDF

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Publication number
WO2017130932A1
WO2017130932A1 PCT/JP2017/002242 JP2017002242W WO2017130932A1 WO 2017130932 A1 WO2017130932 A1 WO 2017130932A1 JP 2017002242 W JP2017002242 W JP 2017002242W WO 2017130932 A1 WO2017130932 A1 WO 2017130932A1
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Prior art keywords
group
exposure
film
acid
exposure amount
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PCT/JP2017/002242
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English (en)
Japanese (ja)
Inventor
修史 平野
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富士フイルム株式会社
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Priority to JP2017564251A priority Critical patent/JP6633103B2/ja
Publication of WO2017130932A1 publication Critical patent/WO2017130932A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C08F212/24—Phenols or alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/20—Exposure; Apparatus 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
    • 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 pattern forming method and an electronic device manufacturing method. More specifically, the present invention relates to semiconductor manufacturing processes such as IC (Integrated Circuits) and LSI (Large-Scale Integration), manufacturing of circuit boards such as liquid crystals and thermal heads, and other photofabrication lithography processes. The present invention relates to a pattern forming method and an electronic device manufacturing method.
  • Patent Document 1 proposes a double development technique using a positive developer and a negative developer as a method for stably forming a high-precision fine pattern.
  • the present inventors have found that the above problem can be solved by controlling the exposure amount in the exposure process. That is, it has been found that the above object can be achieved by the following configuration.
  • the exposed film is developed using an alkaline developer or a developer containing an organic solvent to form a pattern, and a pattern forming method comprising:
  • a pattern forming method in which, when a developer containing an organic solvent is used in Step C, exposure is performed at an exposure amount larger than the exposure amount X2 calculated by the exposure amount X2 calculation method described later in Step B.
  • the repeating unit is a repeating unit represented by the general formula (AI) described later, or a repeating unit represented by the general formula (AII) described later.
  • the pattern forming method according to (2), wherein the leaving group that decomposes and leaves by the action of an acid is one of groups represented by formulas (Y1) to (Y4) described later.
  • Any of the group represented by the formula (Y1), the group represented by the formula (Y3), and the group represented by the formula (Y4) is a leaving group that decomposes and leaves by the action of an acid.
  • the leaving group that decomposes and leaves by the action of an acid is either a group represented by the formula (Y3) or a group represented by the formula (Y4) (6) or (7 ) Pattern forming method.
  • the pattern forming method according to any one of (6) to (8), wherein the leaving group that decomposes and leaves by the action of an acid is a group represented by the formula (Y4).
  • a method for manufacturing an electronic device comprising the pattern forming method according to any one of (1) to (12).
  • the new pattern formation method which can form a fine pattern with a simple procedure can be provided.
  • the manufacturing method of an electronic device containing the said pattern formation method can be provided.
  • the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • Actinic rays” or “radiation” in the present specification refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc.
  • light means actinic rays or radiation.
  • exposure in the present specification is not limited to exposure to deep ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams and ions unless otherwise specified. Drawing with particle beams such as beams is also included in exposure.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • dispersity Mw / Mn
  • GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ l, column: TSK gel Multipore HXL-M ( ⁇ 4) manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: It is defined as a polystyrene conversion value by a differential refractive index (RI) detector.
  • FIG. 1 shows a laminated body having a substrate 10 and a film (resist film) 12 disposed on the substrate 10 and obtained using an actinic ray-sensitive or radiation-sensitive resin composition through a mask 14.
  • the schematic diagram when performing exposure using actinic rays or radiation is shown.
  • the actinic ray or radiation passing through the opening 16 of the mask 14 has a distribution of the exposure amount E. Specifically, the exposure amount E is large near the center of the opening 16 and the exposure amount E is small near the mask 14 of the opening 16.
  • the photoacid generator is decomposed and acid is generated in both the high exposure area 18 and the low exposure area 20.
  • the generated acid acts on the resin whose polarity is increased by the action of the acid to increase the solubility in the alkaline developer and the solubility in the developer containing the organic solvent is reduced.
  • the solubility of the resin is changed. Therefore, for example, when the exposed film 12 is developed with an alkaline developer, both the high exposure area 18 and the low exposure area 20 are removed.
  • the solubility of the film 12 in the high exposure region 18 in the developing solution and the solubility of the film 12 in the low exposure region 20 in the developing solution is different.
  • a resin whose polarity is increased by the action of an acid to increase the solubility in an alkaline developer and the solubility in a developer containing an organic solvent is reduced is a desorption in which a polar group is decomposed and eliminated by the action of an acid.
  • the desorbed material desorbed from the resin by the action of the acid reacts with the resin again to change its polarity.
  • a case will be described in which a resin having a repeating unit having a structure in which a polar group is decomposed by the action of an acid and is eliminated by the action of an acid is protected as follows.
  • the reaction proceeds so as to proceed from the left side in the above scheme to the middle. That is, a leaving product (styrene) is generated from the resin by the action of an acid, and a phenolic hydroxyl group is generated in the side chain of the resin. As a result, the polarity of the resin changes to hydrophilic.
  • the reaction has been completed at this stage. However, when exposure is performed with an exposure amount larger than the exposure amount X1, a large amount of acid is generated in the high exposure region 18. Therefore, as shown in the above scheme, the reaction proceeds so as to proceed further to the right from the middle.
  • the desorbed product (styrene) is replaced with a benzene ring again, and as a result, the polarity of the resin changes to hydrophobic again.
  • the reaction is completed from the left side to the middle in the above scheme, and further the reaction to the right side does not proceed. Therefore, when the exposed film 12 is developed with an alkaline developer, a resist film remains in the region covered with the mask 14 and the high exposure region 18 as shown in FIG. The film is removed, and a predetermined pattern 22 is formed.
  • a pattern having a width narrower than the width of the opening 16 is formed.
  • all of the exposed area of the resist film has been removed by development with an alkaline developer.
  • a new pattern can be formed even in a part of the exposed area. it can. As a result, the degree of freedom in pattern design is further improved than in the prior art.
  • the aspect developed with an alkali developing solution was described above, even when a developing solution containing an organic solvent is used, if the resist film is exposed with an exposure amount larger than the exposure amount X2, the high exposure region 18 is obtained.
  • the solubility of the film 12 in the developer in the film differs from the solubility of the film 12 in the low exposure area 20 in the developer. That is, the hydrophobic resist film is removed by the developer containing the organic solvent, and the hydrophilic resist film remains.
  • the film 12 in the low exposure region 20 remains and a predetermined pattern 22 is formed. In this case, a pattern having a width narrower than the width of the opening 16 is formed in the low exposure region 20.
  • a fine pattern can be formed by a single development process by adjusting the exposure amount.
  • the pattern forming method of the present invention includes at least the following steps A to C.
  • Step A Step of forming a film (resist film) having a thickness T on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition (film formation step)
  • Step B Step of exposing the film with actinic rays or radiation (exposure step)
  • Step C Step of developing the exposed film using a developer containing an alkali developer or an organic solvent to form a pattern (resist pattern) (development step)
  • the exposure in step B may be immersion exposure.
  • the pattern forming method of the present invention preferably includes a process D (heating process) after the process B and before the process C.
  • the pattern forming method of the present invention may include an exposure step a plurality of times.
  • the pattern forming method of the present invention may include a heating step a plurality of times.
  • Step A is a step of forming a film (hereinafter also referred to as “resist film”) on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also simply referred to as “resist composition”).
  • resist film a film
  • an actinic ray-sensitive or radiation-sensitive resin composition hereinafter also simply referred to as “resist composition”.
  • composition actinic ray-sensitive or radiation-sensitive resin composition
  • the substrate used in this step is not particularly limited. For example, in the case of a semiconductor wafer, a silicon wafer can be used as the substrate. In addition, other layers may be disposed on the substrate.
  • the outermost layer may be an organic antireflection film.
  • an antireflection film Before forming the resist film, an antireflection film may be disposed on the substrate in advance.
  • an inorganic antireflection film made of titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, or the like, and an organic antireflection film made of a light absorber and a polymer material. Can do.
  • commercially available organic antireflection films such as DUV30 series and DUV-40 series manufactured by Brewer Science and AR-2, AR-3, and AR-5 manufactured by Shipley are used. You can also.
  • a typical method for forming a film (resist film) using an actinic ray-sensitive or radiation-sensitive resin composition is a method of applying an actinic ray-sensitive or radiation-sensitive resin composition onto a substrate.
  • the coating method include spin coating, roll coating, flow coating, dip coating, spray coating, and doctor coating.
  • the spin coating method is preferable, and the rotation speed is preferably 1000 to 3000 rpm.
  • pre-baking at 60 to 150 ° C. for 1 to 20 minutes, preferably at 80 to 120 ° C. for 1 to 10 minutes, if necessary.
  • the thickness T of the film to be formed is not particularly limited, but an optimum thickness is appropriately selected according to the use of the pattern. Is more preferable.
  • the said thickness is an average value, and is the value which measured the thickness of the film
  • the heating temperature in the preheating step is not particularly limited, but is preferably 70 to 150 ° C.
  • the heating time in the preheating step is not particularly limited, but is preferably 30 to 900 seconds, and more preferably 30 to 180 seconds.
  • Step B is a step of exposing the film with actinic rays or radiation. Especially, it is preferable that the said exposure is performed using an extreme ultraviolet ray or an electron beam. That is, in the exposure (pattern formation step) on the resist film, it is preferable to irradiate the resist film with extreme ultraviolet rays or an electron beam in a pattern.
  • the width W A of the exposed portion and the width W B of the unexposed portion is preferably carried exposure so that the relation of the following formula (X).
  • n 0 or an integer of 1 or more.
  • Formula (X) W A W B ⁇ (3 + 2n)
  • W A and W B ⁇ (3 + 2n) are substantially identical, (W A / W B ⁇ (3 + 2n)) is preferably from 0.90 to 1.10.
  • the exposure amount in this step when an alkali developer is used in step C described later, exposure is performed with an exposure amount greater than the exposure amount X1 calculated by the exposure amount X1 calculation method described later.
  • a developer containing an organic solvent is used, exposure is performed with an exposure amount larger than the exposure amount X2 calculated by the exposure amount X2 calculation method described later.
  • the exposure amount is larger than the exposure amount X1, preferably 1.05 times or more of the exposure amount X1, and more preferably 1.2 times or more of the exposure amount X1. More preferably, the exposure amount X1 is 1.5 times or more.
  • the upper limit is not particularly limited, but is preferably within 3.0 times the exposure amount X1 in that the effect of the present invention is saturated.
  • the exposure amount is more than the exposure amount X2, preferably 1.05 times or more of the exposure amount X2, more preferably 1.2 times or more of the exposure amount X2, More preferably, the exposure amount X2 is 1.5 times or more.
  • the upper limit is not particularly limited, but is preferably within 3.0 times the exposure amount X2 in that the effect of the present invention is saturated.
  • the unit of exposure amount is (mJ / cm 2 ) when actinic rays are used, and the unit of exposure amount is ( ⁇ C / cm 2 ) when radiation is used.
  • a film 12 having a thickness T is formed on the substrate 10.
  • This thickness T is set to the same thickness as that of the film formed in the above-described film forming step.
  • the substrate to be used is not particularly limited, but when actinic light is used in the exposure step, it is preferable to use a Si substrate (manufactured by Advanced Materials Technology) subjected to hexamethyldisilazane treatment as the substrate. When used, it is preferable to use a 6-inch silicon wafer on which Cr oxide is deposited as the substrate.
  • step A of the pattern forming method of the present invention As a method for producing a film, the same method as in step A of the pattern forming method of the present invention is adopted. For example, a resist composition is applied onto a substrate by a spin coating method, and if necessary, baking is performed. A film having a thickness T is manufactured. Examples of the baking conditions include baking at 100 ° C. for 60 seconds.
  • the obtained film is exposed while increasing the exposure amount.
  • actinic rays in step B using the same type of actinic rays as the actinic rays used in step B, while increasing the exposure amount by 1 mJ / cm 2 to 1 mJ / cm 2 , More than 99 exposures are performed at different positions on the film. That is, exposure with different exposure amounts is performed on 99 or more different positions on the film surface. More specifically, as shown in FIG. 5, exposure is performed by changing the exposure amount at different portions of the film, as indicated by white arrows. In FIG. 5, exposure is performed at three different positions on the film 12. In the leftmost exposure in FIG.
  • exposure is performed with an exposure amount ZmJ / cm 2
  • in the middle exposure is performed with an exposure amount (Z + 1) mJ / cm 2
  • in the rightmost exposure exposure is performed.
  • An exposure with an amount (Z + 2) mJ / cm 2 is performed.
  • exposure is performed while increasing the exposure amount by 1 mJ / cm 2 for each exposure location.
  • the same type of radiation as that used in the process B is used, and exposure is performed at different positions on the film while increasing the exposure amount from 1 ⁇ C / cm 2 to 1 ⁇ C / cm 2. Do 99 or more. That is, exposure with different exposure amounts is performed on 99 or more different positions on the film surface.
  • the specific mode of exposure is the same as the mode described in FIG.
  • the area of the said exposure location is not restrict
  • 99 or more exposure locations are implemented.
  • the upper limit of the number of exposure locations is not particularly limited, but exposure is performed until a point at which the film thickness once reaches a minimum value (for example, 0) and the film thickness exceeds the minimum value again when calculating an exposure amount X1 described later. Is preferably carried out, more preferably 500 or less.
  • the exposed film is subjected to the above-described exposure.
  • the heat treatment is performed under the same conditions as the heating conditions performed in the heating step.
  • the heat treatment is performed at 100 ° C. for 60 seconds after Step B, the exposure amount X1 calculation method also applies to the exposed film after the exposure.
  • a heat treatment is performed at 100 ° C. for 60 seconds.
  • the obtained film is subjected to development processing using an alkali developer used in Step C described later.
  • an alkali developer it is preferable to use an aqueous tetramethylammonium hydroxide solution (2.38% by mass: “the concentration of tetramethylammonium hydroxide in the aqueous solution is 2.38% by mass”).
  • As a developing method it is preferable to perform development with an alkali developer for 60 seconds, rinse with pure water for 30 seconds, and then spin dry. When the development process is performed, the film is removed at the exposed portion. The removal amount at that time varies depending on the exposure amount.
  • FIG. 6 is a view after the development processing is performed on the film shown in FIG.
  • a plot diagram is created using the exposure amount and film thickness data at each exposure location. Specifically, the points corresponding to the film thickness and the exposure dose at each exposure location are plotted on orthogonal coordinates with the film thickness as the vertical axis and the exposure dose as the horizontal axis. That is, the graph is created with the film thickness at each exposure location on the vertical axis and the exposure amount at each exposure location on the horizontal axis.
  • the unit of film thickness is nm
  • the unit of exposure amount is mJ / cm 2 when actinic rays are used in the exposure process, and ⁇ C / cm 2 when radiation is used.
  • FIG. 7 shows an example of a plot diagram.
  • Each black circle in FIG. 7 corresponds to a result (film thickness and exposure amount) at each exposure location.
  • the number of black circle plots is less than the actual 99 points.
  • a line may be created by connecting the plotted points in the obtained plot diagram.
  • the film thickness decreases as the exposure amount increases in the region A, and the film thickness decreases in the region B even if the exposure amount increases (for example, 0). It becomes almost constant. Thereafter, the film thickness starts to increase again in the region C that is equal to or larger than the predetermined exposure amount.
  • the photoacid generator decomposition amount increases in the exposure region, and the amount of acid generated increases.
  • the generated acid acts on the resin, the polarity of the resin changes, it is easy to dissolve in an alkali developer, the film is easily removed at the exposed portion where the exposure amount is large, and the film thickness is reduced.
  • the film thickness becomes a minimum value (for example, 0).
  • the film thickness becomes a minimum value (for example, 0).
  • the exposure amount becomes a predetermined value or more, for example, the above-described resorption reaction of the desorbed material starts to progress, and as a result, the number of films that cannot be removed with an alkali developer increases. That is, the film thickness starts to increase.
  • the exposure amount X1 at the boundary point between the region B and the region C in FIG. This boundary point corresponds to the point with the largest exposure amount among the points where the film thickness shows the minimum value. That is, the exposure amount X1 is intended to be the exposure amount at the point where the exposure amount is the largest among the points where the film thickness has the minimum value. In other words, the exposure amount X1 corresponds to a point where the film thickness once rises from the minimum value after the film thickness once reaches the minimum value when the exposure amount is increased (a point at which rising starts).
  • a film 12 having a thickness T is formed on the substrate 10.
  • This thickness T is set to the same thickness as that of the film formed in the above-described film forming step.
  • the substrate to be used is not particularly limited, but when actinic light is used in the exposure step, it is preferable to use a Si substrate (manufactured by Advanced Materials Technology) subjected to hexamethyldisilazane treatment as the substrate. When used, it is preferable to use a 6-inch silicon wafer on which Cr oxide is deposited as the substrate.
  • a method for producing a film the same method as in step A of the pattern forming method of the present invention is adopted. For example, a resist composition is applied onto a substrate by a spin coating method, and if necessary, baking is performed. A film having a thickness T is manufactured. Examples of the baking conditions include baking at 100 ° C. for 60 seconds.
  • the obtained film is exposed while increasing the exposure amount.
  • actinic rays in step B using the same type of actinic rays as the actinic rays used in step B, while increasing the exposure amount by 1 mJ / cm 2 to 1 mJ / cm 2 , More than 99 exposures are performed at different positions on the film. That is, exposure with different exposure amounts is performed on 99 or more different positions on the film surface. More specifically, as shown in FIG. 9, exposure is performed by changing the exposure amount to different portions of the film, as indicated by white arrows. In FIG. 9, exposure is performed at three different positions on the film 12. In the leftmost exposure in FIG.
  • exposure is performed with an exposure amount ZmJ / cm 2
  • in the middle exposure is performed with an exposure amount (Z + 1) mJ / cm 2
  • in the rightmost exposure exposure is performed.
  • An exposure with an amount (Z + 2) mJ / cm 2 is performed.
  • exposure is performed while increasing the exposure amount by 1 mJ / cm 2 for each exposure location.
  • the same type of radiation as that used in the process B is used, and exposure is performed at different positions on the film while increasing the exposure amount from 1 ⁇ C / cm 2 to 1 ⁇ C / cm 2. Do 99 or more. That is, exposure with different exposure amounts is performed on 99 or more different positions on the film surface.
  • the specific mode of exposure is the same as the mode described in FIG.
  • the area of the said exposure location is not restrict
  • 99 or more exposure locations are implemented.
  • the upper limit of the number of exposure locations is not particularly limited, but it is preferable to perform exposure until a point at which the film thickness once reaches a maximum value and begins to decrease from the maximum value when calculating an exposure amount X2 described later, is 500. More than the place is more preferable.
  • the exposed film is subjected to the above-described exposure.
  • the heat treatment is performed under the same conditions as the heating conditions performed in the heating step.
  • the exposure amount X2 calculation method when heat treatment is performed at 100 ° C. for 60 seconds after Step B, the exposure amount X2 calculation method also applies to the exposed film after the exposure in the present exposure amount X2 calculation method.
  • a heat treatment is performed at 100 ° C. for 60 seconds.
  • FIG. 10 is a view after the development process is performed on the film shown in FIG. 9, and the thickness of the film 12 at the leftmost exposure location is the smallest and the film 12 at the rightmost exposure location. Is the thickest. That is, T1 ⁇ T2 ⁇ T3. In FIG. 10, only the film thicknesses at three points are shown, but actually the film thicknesses at the exposure points of 99 points or more are measured.
  • a plot diagram is created using the exposure amount and film thickness data at each exposure location. Specifically, the points corresponding to the film thickness and the exposure dose at each exposure location are plotted on orthogonal coordinates with the film thickness as the vertical axis and the exposure dose as the horizontal axis. That is, the graph is created with the film thickness at each exposure location on the vertical axis and the exposure amount at each exposure location on the horizontal axis.
  • the unit of film thickness is nm
  • the unit of exposure amount is mJ / cm 2 when actinic rays are used in the exposure process, and ⁇ C / cm 2 when radiation is used.
  • FIG. 11 shows an example of a plot diagram.
  • Each black circle in FIG. 11 corresponds to a result (film thickness and exposure amount) at each exposure location.
  • the number of black circle plots is less than the actual 99 points.
  • a line may be created by connecting the plotted points in the obtained plot diagram.
  • the film thickness increases as the exposure amount increases in the region A, and the film thickness becomes substantially constant at the maximum value in the region B even if the exposure amount increases. . Thereafter, the film thickness starts to decrease again in the region C that is equal to or greater than the predetermined exposure amount.
  • the photoacid generator decomposition amount increases in the exposure region, and the amount of acid generated increases.
  • the generated acid acts on the resin, the polarity of the resin changes, it becomes difficult to dissolve in a developer containing an organic solvent, and the film is difficult to be removed at an exposed portion where the amount of exposure is large. It will increase.
  • the film substantially remains, and the film thickness becomes substantially constant at the maximum value. Normally, there are a plurality of points where the film thickness shows the maximum value.
  • the region C where the exposure amount becomes a predetermined value or more for example, the above-described resorption reaction of the desorbed material starts to progress, and as a result, the number of films that cannot be removed by the developer containing the organic solvent decreases. That is, the film thickness starts to decrease.
  • the exposure amount X2 at the boundary point between the region B and the region C in FIG. This boundary point corresponds to the point with the largest exposure amount among the points where the film thickness shows the maximum value. That is, the exposure amount X2 is intended to be the exposure amount at the point where the exposure amount is the largest among the points where the film thickness has the maximum value. In other words, the exposure amount X2 corresponds to a point where the film thickness starts to decrease from the maximum value again after the film thickness once reaches the maximum value when the exposure amount is increased.
  • an immersion exposure method can be applied.
  • the immersion exposure method can be combined with a super-resolution technique such as a phase shift method and a modified illumination method.
  • a super-resolution technique such as a phase shift method and a modified illumination method.
  • the step of cleaning the surface of the resist film with an aqueous chemical may be performed before the step of heating the resist film.
  • the immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the resist film.
  • the exposure light source is an ArF excimer laser (wavelength; 193 nm)
  • water used as the immersion liquid
  • an additive liquid that decreases the surface tension of the water and increases the surface activity may be added to the water in a small proportion.
  • This additive is preferably one that does not dissolve the resist film on the substrate and can ignore the influence on the optical coating on the lower surface of the lens element.
  • an additive for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, and isopropyl alcohol.
  • the optical image projected on the resist film is distorted.
  • pure water filtered through an ion exchange filter or the like may be used.
  • the electrical resistance of water used as the immersion liquid is preferably 18.3 MQcm or more, and the TOC (organic substance concentration) is preferably 20 ppb or less.
  • the water is preferably degassed.
  • the receding contact angle of the resist film is preferably 70 ° or more at a temperature of 23 ⁇ 3 ° C. and a humidity of 45 ⁇ 5%. In such a case, it is suitable for exposure through an immersion medium.
  • the receding contact angle of the resist film is more preferably 75 ° or more, and further preferably 75 to 85 °.
  • the immersion exposure method cannot be suitably used, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited.
  • a hydrophobic resin described later in the composition it is preferable to include a hydrophobic resin described later in the composition.
  • an immersion liquid hardly soluble film (hereinafter also referred to as “top coat”) formed of a hydrophobic resin may be provided on the upper layer of the resist film.
  • a top coat may be provided as an upper layer of a resist film containing a hydrophobic resin. The necessary functions for the top coat are suitability for application on the resist film, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist film and can be disposed uniformly on the resist film.
  • the top coat examples include hydrocarbon polymers, acrylic acid ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers, and fluorine-containing polymers. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.
  • the top coat may contain a basic compound.
  • a developer When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having a small penetration into the resist film is preferable.
  • the top coat is preferably peelable with a developer containing an organic solvent in that the peeling step can be performed simultaneously with the film development step. The resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid.
  • the topcoat When water is used as the immersion liquid, the topcoat is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index of the top coat close to that of the immersion liquid, the top coat preferably has fluorine atoms. A thin film is more preferable from the viewpoint of transparency and refractive index.
  • the top coat is preferably not mixed with the resist film and further not mixed with the immersion liquid.
  • the formation of the top coat is not limited to immersion exposure, and may be performed in the case of dry exposure (exposure not involving an immersion liquid). By forming the top coat, for example, generation of outgas can be suppressed.
  • the topcoat composition used for forming the topcoat will be described.
  • the solvent contained in the topcoat composition is preferably an organic solvent. More preferred is an alcohol solvent.
  • the solvent is an organic solvent, it is preferably a solvent that does not dissolve the resist film.
  • an alcohol solvent, a fluorine solvent, and a hydrocarbon solvent are preferably used, and a non-fluorine alcohol solvent is more preferably used.
  • the alcohol solvent is preferably a primary alcohol from the viewpoint of applicability, and more preferably a primary alcohol having 4 to 8 carbon atoms.
  • the primary alcohol having 4 to 8 carbon atoms linear, branched and cyclic alcohols can be used.
  • Preferable examples include 1-butanol, 1-hexanol, 1-pentanol, 3-methyl-1-butanol, 2-ethylbutanol, and perfluorobutyltetrahydrofuran.
  • resins having an acidic group described in JP-A-2009-134177 and JP-A-2009-91798 can also be preferably used.
  • the weight average molecular weight of the resin is not particularly limited, but is preferably 2,000 to 1,000,000, more preferably 5,000 to 500,000, still more preferably 10,000 to 100,000.
  • the weight average molecular weight of the resin indicates a polystyrene-equivalent molecular weight measured by GPC (Gel permeation chromatography) (carrier: tetrahydrofuran (THF) or N-methyl-2-pyrrolidone (NMP)).
  • the pH of the top coat composition is not particularly limited, but is preferably 0 to 10, more preferably 0 to 8, and still more preferably 1 to 7.
  • the topcoat composition may contain additives such as a photoacid generator and a nitrogen-containing basic compound.
  • a nitrogen-containing basic compound US Published Patent Publication US2013 / 0244438A can be mentioned.
  • the concentration of the resin in the top coat composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.3 to 3% by mass.
  • Examples of the material for the top coat composition include components other than the resin.
  • the ratio of the resin to the solid content of the top coat composition is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
  • the solid content concentration of the top coat composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 6% by mass, and still more preferably 0.3 to 5% by mass. . By setting the solid content concentration within the above range, the topcoat composition can be uniformly applied onto the resist film.
  • a resist film can be formed on the substrate using the above composition, and a top coat can be formed on the resist film using the top coat composition.
  • the film thickness of the top coat is preferably 10 to 200 nm, more preferably 20 to 100 nm, and still more preferably 40 to 80 nm.
  • the top coat composition can be applied by the same means as the resist film forming method and dried as necessary to form the top coat.
  • the resist film having a top coat as an upper layer is usually irradiated with actinic rays or radiation through a mask, preferably baked (heated) and developed.
  • the immersion head In the immersion exposure process, the immersion head needs to move on the substrate following the movement of the exposure head scanning the substrate at high speed to form the exposure pattern, so that the dynamic state is maintained.
  • the contact angle of the immersion liquid with respect to the resist film is important. For this reason, the resist film is required to have the capability of following the high-speed scanning of the exposure head without the liquid droplets remaining.
  • Step C is a step of developing the exposed film using a developer to form a pattern.
  • the developer used in this step is appropriately selected, but it is preferable to use an alkali developer (typically an alkaline aqueous solution) or a developer containing an organic solvent (also referred to as an organic developer).
  • an alkali developer typically an alkaline aqueous solution
  • a developer containing an organic solvent also referred to as an organic developer.
  • TMAH tetramethylammonium hydroxide
  • TBAH tetrabutylammonium hydroxide
  • An appropriate amount of alcohol and / or surfactant may be added to the alkaline developer.
  • the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and Inorganic alkalis such as aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine Alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium Tetraalkylammonium hydroxide such as dimethylhydroxide, tetrahexylammonium hydroxide, te
  • the alkali concentration of the alkali developer (alkali component concentration relative to the total mass of the alkali developer) is usually from 0.1 to 20% by mass.
  • the pH of the alkali developer is usually from 10.0 to 15.0.
  • an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.
  • Pure water can be used as the rinsing liquid in the rinsing treatment performed after alkali development.
  • An appropriate amount of a surfactant may be added to pure water.
  • a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.
  • the developer in this step includes a ketone solvent, an ester solvent, Alcohol solvents, amide solvents, polar solvents such as ether solvents, and hydrocarbon solvents can be used.
  • the ester solvent is a solvent having an ester group in the molecule
  • the ketone solvent is a solvent having a ketone group in the molecule
  • the alcohol solvent is alcoholic in the molecule.
  • It is a solvent having a hydroxyl group
  • an amide solvent is a solvent having an amide group in the molecule
  • an ether solvent is a solvent having an ether bond in the molecule.
  • diethylene glycol monomethyl ether corresponds to both of the alcohol solvent and the ether solvent in the above classification.
  • the hydrocarbon solvent is a hydrocarbon solvent having no substituent.
  • a developer containing at least one solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, and an ether solvent is preferable, and an ester solvent or a ketone solvent is more preferable.
  • the developer has 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10), and the number of heteroatoms is 2 or less from the viewpoint that the swelling of the resist film can be suppressed. It is preferable to use the ester solvent.
  • the hetero atom of the ester solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom.
  • the number of heteroatoms is preferably 2 or less.
  • ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, propion Examples include heptyl acid, butyl butanoate, and isobutyl isobutanoate. Isoamyl acetate or isobutyl isobutanoate is preferable.
  • the developer may be a mixed solvent of the ester solvent and the hydrocarbon solvent, or the ketone solvent and the hydrocarbon. You may use the mixed solvent of a system solvent. Even in this case, it is effective in suppressing the swelling of the resist film.
  • an ester solvent and a hydrocarbon solvent are used in combination, isoamyl acetate is preferably used as the ester solvent.
  • the hydrocarbon solvent it is preferable to use a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, and hexadecane) from the viewpoint of adjusting the solubility of the resist film.
  • ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, 2,5-dimethyl-4-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, Examples include isophorone and propylene carbonate.
  • Ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl.
  • Examples include butyl and methyl 2-hydroxyisobutyrate.
  • alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, 4-methyl-2-pentanol, tert-butyl alcohol, isobutyl alcohol, n -Hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, alcohols such as n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol, and ethylene glycol monomethyl ether and propylene glycol monomethyl ether , Ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol Over monoethyl ether, and the like glycol monoethyl ether and methoxymethyl butanol.
  • ether solvent examples include dibutyl ether, anisole, dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
  • amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone.
  • hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and undecane.
  • the aliphatic hydrocarbon solvent that is a hydrocarbon solvent may be a mixture of compounds having the same number of carbon atoms and different structures.
  • 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane which are compounds having the same carbon number and different structures
  • isooctane which are compounds having the same carbon number and different structures
  • the compounds having the same number of carbon atoms and different structures may include only one kind or plural kinds as described above.
  • a plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than the above and / or water.
  • the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture. That is, the amount of the organic solvent used relative to the organic developer is preferably 90 to 100% by mass and more preferably 95 to 100% by mass with respect to the total amount of the developer.
  • the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents, More preferably, the developer contains at least one organic solvent selected from the group consisting of ketone solvents and ester solvents.
  • the vapor pressure of the organic developer at 20 ° C. is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less.
  • the solvent having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone and methyl isobutyl ketone, butyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol Monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, Ester solvents such as
  • the solvent having a vapor pressure of 2 kPa or less that is a particularly preferable range include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone and phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy Ester solvents such as propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate alcohol solvents such as n-but
  • the organic developer may contain a basic compound.
  • Specific examples and preferred examples of the basic compound that can be contained in the developer used in the present invention are the same as those in the basic compound that can be contained in the resist composition.
  • a surfactant can be added to the organic developer as required.
  • an ionic or nonionic fluorine type and / or silicon type surfactant etc. can be used.
  • fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in US Pat.
  • Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned.
  • it is a nonionic surfactant.
  • a fluorochemical surfactant or a silicon-type surfactant It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
  • the amount of the surfactant used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and still more preferably 0.0005 to 1% by mass, based on the total amount of the developer.
  • a development method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying a developer on the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing). Law) and the like can be applied.
  • the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm 2 or less, More preferably, it is 1.5 mL / sec / mm 2 or less, More preferably, it is 1 mL / sec / mm 2 or less.
  • There is no particular lower limit on the flow rate but 0.2 mL / sec / mm 2 or more is preferable in consideration of throughput.
  • the details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied to the resist film by the developer may be reduced, and the resist film and pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
  • the developer discharge pressure (mL / sec / mm 2 ) is a value at the developing nozzle outlet in the developing device.
  • Examples of the method of adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump and the like, and a method of changing the discharge pressure by adjusting the pressure by supply from a pressurized tank.
  • a step of stopping development may be performed while substituting with another solvent.
  • a step of washing with a rinse solution may be included, but from the viewpoint of throughput (productivity), a step of washing with a rinse solution is performed. It does not have to be included.
  • a treatment method that does not include a step of washing with a rinsing solution for example, the method described in paragraphs 0014 to 0086 of JP-A-2015-216403 can be used, and the contents thereof are incorporated in the present specification. .
  • the rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used.
  • a rinse liquid a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. It is preferable. Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.
  • ether solvents can also be suitably used as the rinsing liquid.
  • ether solvents include glycol ether solvents that contain hydroxyl groups, glycol ether solvents that do not contain hydroxyl groups, such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, and anisole.
  • aromatic ether solvents such as phenetole, dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane, cyclopentyl isopropyl ether, cyclopentyl sec-butyl ether, cyclopentyl tert-butyl ether, cyclohexyl Isopropyl ether, cyclohexyl sec-butyl ether Cyclic aliphatic ether solvents such as tellurium and cyclohexyl tert-butyl ether, linear chains such as di-n-propyl ether, di-n-butyl ether, di-n-pentyl ether and di-n-hexyl ether Acyclic aliphatic ether solvents having an alkyl group, diisohexyl ether
  • an acyclic aliphatic ether solvent having 8 to 12 carbon atoms is preferable, and an acyclic aliphatic ether solvent having a branched alkyl group having 8 to 12 carbon atoms is more preferable.
  • Particularly preferred is diisobutyl ether, diisopentyl ether or diisohexyl ether.
  • a rinse containing at least one organic solvent selected from the group consisting of ester solvents, alcohol solvents, and hydrocarbon solvents It is preferable to perform a step of washing using a liquid, and more preferably, a step of washing using a rinse liquid containing an alcohol solvent or a hydrocarbon solvent.
  • the organic solvent contained in the rinsing liquid it is also preferable to use a hydrocarbon solvent among the organic solvents, and it is more preferable to use an aliphatic hydrocarbon solvent.
  • an aliphatic hydrocarbon solvent having 5 or more carbon atoms for example, pentane, hexane, octane, decane, undecane, dodecane, And hexadecane are preferred, aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferred, and aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferred.
  • the upper limit of the carbon number of the said aliphatic hydrocarbon solvent is not specifically limited, For example, 16 or less is mentioned, 14 or less is preferable and 12 or less is more preferable.
  • decane, undecane or dodecane is preferable, and undecane is more preferable.
  • a hydrocarbon solvent especially an aliphatic hydrocarbon solvent
  • the developer slightly soaked into the resist film after development is washed away, and the pattern swells. It is further suppressed, and the effect of suppressing pattern collapse is further exhibited.
  • a plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.
  • MIBC methyl isobutyl carbinol
  • the water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.
  • the vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 to 5 kPa, more preferably 0.1 to 5 kPa, and more preferably 0.12 to 3 kPa at 20 ° C. Further preferred.
  • the substrate that has been developed using the developer containing the organic solvent is subjected to a cleaning process using the rinse containing the organic solvent.
  • the method of the cleaning process is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), and immersing the substrate in a bath filled with the rinse liquid for a certain period of time.
  • a method (dip method), a method (spray method) of spraying a rinse liquid on the substrate surface, and the like can be applied.
  • a cleaning process by a spin coating method, rotate the substrate at a rotational speed of 2000 to 4000 rpm after the cleaning, and remove the rinse liquid from the substrate.
  • a heating process PostBake
  • the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking.
  • the heating step after the rinsing step is usually carried out at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 to 90 seconds.
  • the pattern forming method of the present invention may have a developing step using an organic developer and a developing step using an alkali developer.
  • Process D heat-processes with respect to the exposed film
  • the heating temperature in this heating step is not particularly limited, but is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.
  • the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds.
  • the heating method is not particularly limited, and may be performed using, for example, a hot plate.
  • the resist composition in the present invention and various materials used in the pattern forming method of the present invention are metals and metal containing halogen. It is preferable that impurities, such as a salt, an acid, an alkali, and a component containing a sulfur atom or a phosphorus atom, are not included.
  • the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and substantially free ( Most preferably, it is below the detection limit of the measuring device.
  • Examples of methods for removing impurities such as metals from various materials include filtration using a filter and purification steps by distillation (particularly thin film distillation, molecular distillation, etc.).
  • the purification process by distillation is, for example, “ ⁇ Factory Operation Series> Augmentation / Distillation, Issued July 31, 1992, Chemical Industry Co.,” or “Chemical Engineering Handbook, Issued September 30, 2004, Asakura Shoten, 95 Page-page 102 ". These steps may be performed in combination.
  • the pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less.
  • the filter material is preferably a polytetrafluoroethylene, polyethylene, or nylon filter.
  • the filter may be a composite material obtained by combining these materials and ion exchange media.
  • a filter that has been washed in advance with an organic solvent may be used.
  • a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination.
  • various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
  • a method of reducing impurities such as metals contained in various materials a method of selecting a raw material with a low metal content as a raw material constituting various materials, a method of performing filter filtration on the raw materials constituting various materials And a method in which the inside of the apparatus is lined with Teflon (registered trademark) and distillation is performed under a condition in which contamination is suppressed as much as possible.
  • the preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
  • impurities may be removed by an adsorbent, or a combination of filter filtration and adsorbent may be used.
  • the adsorbent known adsorbents can be used, and examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
  • An organic solvent (also referred to as “organic processing solution”) that can be used for the developer and the rinsing solution is a container for storing an organic processing solution for patterning a chemically amplified or non-chemically amplified resist film having a storing portion. It is preferable to use a stored one.
  • the inner wall of the container that comes into contact with the organic treatment liquid is a resin different from any of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or rust prevention or metal elution prevention treatment is performed. It is preferably a container for an organic processing liquid for patterning a resist film, which is formed from applied metal.
  • An organic solvent to be used as an organic processing liquid for patterning a resist film is accommodated in the accommodating portion of the accommodating container, and the one discharged from the accommodating portion at the time of patterning the resist film can be used. .
  • the seal portion is also selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin. It is preferably formed from a resin different from one or more kinds of resins, or a metal subjected to rust prevention or metal elution prevention treatment.
  • the seal portion means a member capable of shutting off the accommodating portion and the outside air, and can preferably include packing or an O-ring.
  • Perfluoro resin is preferable as the resin different from one or more kinds of resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin.
  • Perfluororesins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoride.
  • PTFE tetrafluoroethylene resin
  • PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer resin
  • Ethylene-ethylene copolymer resin Ethylene-ethylene copolymer resin (ETFE), ethylene trifluoride-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), ethylene trifluoride chloride copolymer resin (PCTFE), and vinyl fluoride Resin (PVF) etc.
  • ETFE ethylene trifluoride-ethylene copoly
  • Particularly preferable perfluoro resins include tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer resin.
  • Examples of the metal in the metal subjected to rust prevention or metal elution prevention treatment include carbon steel, alloy steel, nickel chrome steel, nickel chrome molybdenum steel, chrome steel, chrome molybdenum steel, and manganese steel.
  • rust prevention or metal elution prevention treatment it is preferable to apply a coating technique.
  • the coating technology is roughly divided into three types: metal coating (various plating), inorganic coating (various chemical conversion treatment, glass, concrete, ceramics, etc.) and organic coating (rust prevention oil, paint, rubber, plastics).
  • metal coating variant plating
  • inorganic coating variant chemical conversion treatment, glass, concrete, ceramics, etc.
  • organic coating rust prevention oil, paint, rubber, plastics.
  • Preferable film technology includes surface treatment with a rust-preventing oil, a rust-preventing agent, a corrosion inhibitor, a chelate compound, a peelable plastic, or a lining agent.
  • pretreatment is a stage before the rust prevention treatment. It is also preferable to adopt.
  • a treatment for removing various corrosive factors such as chloride or sulfate existing on the metal surface by washing or polishing can be preferably mentioned.
  • the storage container includes the following.
  • FluoroPure PFA composite drum manufactured by Entegris (Wetted inner surface; PFA resin lining)
  • JFE steel drums (wetted inner surface; zinc phosphate coating)
  • Examples of the storage container that can be used in the present invention include the containers described in JP-A-11-021393 [0013] to [0030] and JP-A-10-45961 [0012] to [0024]. be able to.
  • a conductive compound may be added in order to prevent failure of chemical pipes or various parts (filters, O-rings, tubes, etc.) due to electrostatic charge and subsequent electrostatic discharge.
  • limit especially as an electroconductive compound For example, methanol is mentioned.
  • the addition amount of the conductive compound is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less from the viewpoint of maintaining preferable development characteristics.
  • chemical piping members use various piping coated with SUS (stainless steel) or antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) Can do.
  • polyethylene, polypropylene, or fluororesin such as polytetrafluoroethylene or perfluoroalkoxy resin
  • polyethylene, polypropylene, or fluororesin such as polytetrafluoroethylene or perfluoroalkoxy resin
  • the developer and the rinse liquid are stored in a waste liquid tank through a pipe after use.
  • a hydrocarbon solvent is used as the rinsing liquid
  • the resist dissolved in the developer is deposited, and these may adhere to the back of the substrate or the side of the pipe.
  • a method of passing the solvent through the piping after washing with a rinsing liquid, the back surface or side surface of the substrate is washed with a solvent in which the resist dissolves, or a solvent in which the resist dissolves without contacting the resist is connected to the piping. The method of flowing so that it may pass is mentioned.
  • the solvent to be passed through the pipe is not particularly limited as long as it can dissolve the resist, and examples thereof include the organic solvents described above, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGMEA propylene glycol monoethyl ether acetate
  • propylene glycol monopropyl propylene glycol monopropyl.
  • Ether acetate propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol mono Ethyl ether, propylene glycol monopropyl ether, propylene Glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, and, and acetone.
  • PGMEA, PGME, or cyclohexanone is preferable.
  • a pattern obtained by the pattern forming method of the present invention as a mask a semiconductor fine circuit, an imprint mold structure, a photomask, and the like can be manufactured by appropriately performing etching treatment and ion implantation.
  • the pattern formed by the above method is a guide pattern formation in DSA (Directed Self-Assembly) (for example, ACS Nano Vol. 4). No. 8 Page 4815-4823). Further, the pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.
  • the photomask manufactured using the pattern forming method of the present invention is a light reflective mask used in reflective lithography using EUV light as a light source, even if it is a light transmissive mask used in an ArF excimer laser or the like. May be.
  • the present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention.
  • the electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic device (home appliance, OA (Office Appliance) related device, media related device, optical device, communication device, etc.). It is.
  • an electric / electronic device home appliance, OA (Office Appliance) related device, media related device, optical device, communication device, etc.
  • An actinic ray-sensitive or radiation-sensitive resin composition comprises a resin and a photoacid generator that increase in polarity by the action of an acid and increase in solubility in an alkali developer, and decrease in solubility in a developer containing an organic solvent. Including. As will be described later, the photoacid generator may be carried on a resin whose polarity is increased by the action of an acid to increase the solubility in an alkali developer and the solubility in a developer containing an organic solvent is reduced. Good.
  • each component contained in the resist composition will be described in detail.
  • Resin (A) contained in the resist composition is a resin whose polarity is increased by the action of an acid to increase the solubility in an alkaline developer and the solubility in a developer containing an organic solvent is reduced. It preferably has a group that decomposes to form a polar group.
  • the resin (A) is preferably insoluble or hardly soluble in an alkali developer.
  • the resin (A) preferably has a repeating unit having a structure in which a polar group is protected by a leaving group that decomposes and leaves by the action of an acid.
  • the polar group in the repeating unit having a structure (acid-decomposable group) protected by a leaving group that decomposes and leaves by the action of an acid includes a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, and a sulfone group. An acid group etc. are mentioned.
  • the polar group is preferably a carboxyl group, an alcoholic hydroxyl group, or a phenolic hydroxyl group, and more preferably a carboxyl group or a phenolic hydroxyl group.
  • Examples of the leaving group that decomposes and leaves by the action of an acid include groups represented by formulas (Y1) to (Y4).
  • a group represented by the formula (Y1), a group represented by the formula (Y3), or a group represented by the formula (Y4) is preferable in that a finer pattern can be formed.
  • a group represented by Y3) or a group represented by formula (Y4) is more preferred, and a group represented by formula (Y4) is more preferred.
  • Formula (Y1) —C (Rx 1 ) (Rx 2 ) (Rx 3 )
  • Formula (Y2) —C ( ⁇ O) OC (Rx 1 ) (Rx 2 ) (Rx 3 )
  • Formula (Y3) —C (R 36 ) (R 37 ) (OR 38 )
  • Rx 1 to Rx 3 each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). When all of Rx 1 to Rx 3 are alkyl groups (linear or branched), it is preferable that at least two of Rx 1 to Rx 3 are methyl groups.
  • Rx 1 to Rx 3 each independently preferably represents a linear or branched alkyl group, and Rx 1 to Rx 3 each preferably independently represents a linear alkyl group. Two of Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring.
  • the alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. .
  • Examples of the cycloalkyl group of Rx 1 to Rx 3 include a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, and the like
  • the polycyclic cycloalkyl group is preferable.
  • Examples of the cycloalkyl group formed by combining two of Rx 1 to Rx 3 include a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecane group, and the like.
  • a polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.
  • the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. It may be replaced.
  • Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above cycloalkyl group. preferable.
  • R 36 to R 38 each independently represents a hydrogen atom or a monovalent organic group.
  • R 37 and R 38 may be bonded to each other to form a ring.
  • the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
  • R 36 is preferably a hydrogen atom.
  • L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
  • M represents a single bond or a divalent linking group.
  • Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.
  • one of L 1 and L 2 is preferably a hydrogen atom, and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined. At least two of Q, M, and L 1 may combine to form a ring (preferably a 5-membered or 6-membered ring).
  • L 2 is a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of the secondary alkyl group include an isopropyl group, a cyclohexyl group, and a norbornyl group.
  • tertiary alkyl group examples include a tert-butyl group and an adamantane group.
  • the glass transition temperature or activation energy is increased, fogging can be suppressed in addition to ensuring the film strength.
  • Ar represents an aromatic ring group.
  • Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
  • Rn and Ar may be bonded to each other to form a non-aromatic ring.
  • Ar is more preferably an aryl group.
  • the resin (A) has a structure in which a polar group is protected by a leaving group that decomposes and leaves by the action of an acid (having a group that decomposes by the action of an acid to generate a polar group),
  • the repeating unit represented by the following general formula (AI) or (AII) is preferred.
  • Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent.
  • T represents a single bond or a divalent linking group.
  • Y represents a leaving group that decomposes and leaves by the action of an acid.
  • Y is preferably any one of groups represented by formulas (Y1) to (Y4).
  • Examples of the optionally substituted alkyl group represented by Xa 1 include a methyl group or a group represented by —CH 2 —R 11 .
  • R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. And more preferably a methyl group.
  • Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, or the like.
  • Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like.
  • Rt represents an alkylene group or a cycloalkylene group.
  • T is preferably a single bond or a —COO—Rt— group.
  • Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH 2 — group, a — (CH 2 ) 2 — group, or a — (CH 2 ) 3 — group.
  • R 61 , R 62 and R 63 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 62 may be bonded to Ar 6 to form a ring, and R 62 in this case represents a single bond or an alkylene group.
  • X 6 represents a single bond, —COO—, or —CONR 64 —.
  • R 64 represents a hydrogen atom or an alkyl group.
  • L 6 represents a single bond or an alkylene group.
  • Ar 6 represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R 62 to form a ring.
  • Y 2 represents a hydrogen atom or a leaving group that decomposes and leaves by the action of an acid. When n ⁇ 2, Y 2 may be the same or different. However, at least one of Y 2 represents a leaving group that decomposes and leaves by the action of an acid.
  • the leaving group that decomposes and leaves by the action of an acid as Y 2 is preferably any of the groups represented by formulas (Y1) to (Y4).
  • n represents an integer of 1 to 4.
  • Each of the above groups may have a substituent.
  • substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and And an alkoxycarbonyl group (having 2 to 6 carbon atoms) and the like, and preferably having 8 or less carbon atoms.
  • an acid-decomposable (meth) acrylic acid tertiary alkyl ester-based repeating unit (a repeating unit in which Xa 1 represents a hydrogen atom or a methyl group, and T represents a single bond) Unit).
  • the repeating unit represented by the general formula (AII) is preferably a repeating unit represented by the following general formula (AIII).
  • Ar 3 represents an aromatic ring group.
  • Y 2 represents a hydrogen atom or a leaving group that decomposes and leaves by the action of an acid.
  • n ⁇ 2
  • Y 2 may be the same or different.
  • at least one of Y 2 represents a leaving group that decomposes and leaves by the action of an acid.
  • the leaving group that decomposes and leaves by the action of an acid as Y 2 is preferably any of the groups represented by formulas (Y1) to (Y4).
  • n represents an integer of 1 to 4.
  • the aromatic ring group represented by Ar 6 and Ar 3 is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.
  • repeating unit having a structure in which a polar group is protected by a leaving group that decomposes and leaves by the action of an acid are shown below, but the present invention is not limited thereto.
  • Examples of the repeating unit having a structure in which a polar group is protected by a leaving group that decomposes and leaves by the action of an acid include those described in paragraphs 0210 to 0216 and 0227 to 0232 of JP-A No. 2014-232309. Units and repeating units described in paragraphs 0270 to 0272 of JP2014-232309A can also be used.
  • Rx represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
  • Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms.
  • Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent.
  • p represents 0 or a positive integer.
  • the substituent containing a polar group represented by Z include a linear or branched alkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, or a cycloalkyl group.
  • it is an alkyl group having a hydroxyl group.
  • As the branched alkyl group an isopropyl group is preferable.
  • the repeating unit having a structure in which the polar group is protected by a leaving group that is decomposed and eliminated by the action of an acid may be one kind, or two or more kinds may be used in combination.
  • the content of repeating units having a structure in which the polar group is protected by a leaving group that is decomposed and eliminated by the action of an acid is the above resin (A)
  • the content is preferably 5 to 85 mol%, more preferably 5 to 75 mol%, still more preferably 10 to 65 mol%, based on all repeating units.
  • the repeating unit having an acid-decomposable group and an aromatic ring group corresponds to both a repeating unit having an acid-decomposable group and a repeating unit having an aromatic ring group.
  • the resin (A) preferably has a repeating unit having an aromatic ring group.
  • Preferred examples of the repeating unit having an aromatic ring group include a repeating unit having a phenolic hydroxyl group.
  • the phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic ring group with a hydroxy group.
  • the aromatic ring of the aromatic ring group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.
  • the resin (A) preferably has a repeating unit having a phenolic hydroxyl group.
  • repeating unit having a phenolic hydroxyl group examples include a repeating unit represented by the following general formula (I) or (I-1).
  • R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 42 may be bonded to Ar 4 to form a ring, and R 42 in this case represents a single bond or an alkylene group.
  • X 4 represents a single bond, —COO—, or —CONR 64 —, and R 64 represents a hydrogen atom or an alkyl group.
  • L 4 each independently represents a single bond or a divalent linking group.
  • Ar 4 represents an (n + 1) -valent aromatic ring group, and when bonded to R 42 to form a ring, represents an (n + 2) -valent aromatic ring group.
  • n represents an integer of 1 to 5.
  • X 4 is —COO— or —CONR 64 —. .
  • the alkyl groups represented by R 41 , R 42 , and R 43 in the general formulas (I) and (I-1) are preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group that may have a substituent.
  • An n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and the like more preferably an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms, Preferably, an alkyl group having 3 or less carbon atoms is used.
  • the cycloalkyl groups represented by R 41 , R 42 , and R 43 in formulas (I) and (I-1) may be monocyclic or polycyclic.
  • a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent, may be mentioned.
  • the halogen atom of R 41 , R 42 and R 43 in the general formulas (I) and (I-1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
  • R 41, R 42 in the general formula (I) and (I-1) and, as the alkyl group contained in the alkoxycarbonyl group of R 43, said R 41, R 42 and, similar to the alkyl group for R 43 Are preferred.
  • Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls.
  • the substituent preferably has 8 or less carbon atoms.
  • Ar 4 represents an (n + 1) -valent aromatic ring group.
  • the divalent aromatic ring group includes, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group, and, for example, thiophene, furan, pyrrole, benzo
  • Preferred examples include aromatic ring groups containing heterocycles such as thiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.
  • the aromatic ring group may have a substituent.
  • n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group.
  • the group formed can be preferably mentioned.
  • the (n + 1) -valent aromatic ring group may further have a substituent.
  • Examples of the substituent that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n + 1) -valent aromatic ring group may have include R 41 , R 42 , and R 43 in formula (I). And alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, and alkoxy groups such as butoxy groups; aryl groups such as phenyl groups; and the like.
  • R 64 is a hydrogen atom or an alkyl group
  • the alkyl group for R 64 in, preferably may have a substituent, a methyl group, an ethyl group , A propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and an alkyl group having 20 or less carbon atoms, preferably 8 or less carbon atoms.
  • X 4 is preferably a single bond, —COO— or —CONH—, and more preferably a single bond or —COO—.
  • the divalent linking group as L 4 is preferably an alkylene group.
  • the alkylene group include those having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group, which may preferably have a substituent.
  • Ar 4 an optionally substituted aromatic ring group having 6 to 18 carbon atoms is more preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are still more preferable.
  • the repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar 4 is preferably a benzene ring group.
  • Preferred examples of the repeating unit having a phenolic hydroxyl group that the resin (A) has include a repeating unit represented by the following general formula (p1).
  • R in the general formula (p1) represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different. As R in the general formula (p1), a hydrogen atom is particularly preferable.
  • Ar in the general formula (p1) represents an aromatic ring.
  • an aromatic ring optionally having a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring.
  • An aromatic heterocycle including a heterocycle of Of these, a benzene ring is preferred.
  • M in the general formula (p1) represents an integer of 1 to 5, preferably 1.
  • repeating unit which has the phenolic hydroxyl group which resin (A) has is shown, this invention is not limited to this.
  • a represents 1 or 2.
  • repeating unit having a phenolic hydroxyl group contained in the resin (A) the repeating units described in paragraphs 0177 and 0178 of JP-A No. 2014-232309 can also be used.
  • Resin (A) may have one type of repeating unit having a phenolic hydroxyl group or two or more types.
  • the content of the repeating unit having a phenolic hydroxyl group is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, more preferably 30 to 85 mol% based on all repeating units of the resin (A). More preferably, it is mol%.
  • the repeating unit (a) having an aromatic ring group may be a repeating unit represented by the following general formula (X).
  • R 61 , R 62 and R 63 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
  • R 63 may be bonded to Ar to form a ring, in which case R 63 represents a single bond or an alkylene group.
  • Ar represents an (n + 1) -valent aromatic ring group, and when bonded to R 63 to form a ring, represents an (n + 2) -valent aromatic ring group.
  • R 7 is each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, alkoxy group, acyloxy group, cyano group, nitro group, amino group, halogen atom, ester group (—OCOR Or —COOR: R represents an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group. n represents an integer of 0 or more.
  • the repeating unit represented by the following general formula (X) is also preferably a repeating unit represented by the following general formula (V) or the following general formula (VI).
  • n 3 represents an integer of 0 to 4.
  • n 4 represents an integer of 0 to 6.
  • X 4 represents a methylene group, an oxygen atom or a sulfur atom.
  • R 7 has the same meaning as R 7 in the general formula (X).
  • repeating unit represented by the general formula (X) are shown below, but are not limited thereto.
  • Resin (A) may have one type of repeating unit represented by general formula (X) or two or more types.
  • the content of the repeating unit represented by the general formula (X) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on all the repeating units of the resin (A). More preferably, it is 5 to 30 mol%.
  • the repeating unit having an aromatic ring group may be a repeating unit having a structure in which a polar group is protected by a leaving group that is decomposed and eliminated by the action of an acid, and may have an aromatic ring group.
  • Resin (A) may have one type of repeating unit having an aromatic ring group or two or more types.
  • the content of the repeating unit having an aromatic ring group is preferably 5 to 100 mol%, more preferably 7 to 98 mol%, more preferably 8 to 96, based on all repeating units of the resin (A). More preferably, it is mol%.
  • the resin (A) preferably contains a repeating unit having a lactone group or a sultone (cyclic sulfonate ester) group.
  • the lactone group or sultone group any group can be used as long as it contains a lactone structure or sultone structure.
  • a group containing a 5- to 7-membered ring lactone structure or a sultone structure is preferable, and other ring structures are condensed by forming a bicyclo structure or a spiro structure in the 5- to 7-membered ring lactone structure or sultone structure. What is doing is preferable.
  • a preferable lactone structure or sultone structure is a group represented by general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), or general formula (LC1-6).
  • the resin (A) may have a structure and a repeating unit described in paragraphs 0306 to 0313 of JP-A No. 2014-232309.
  • the lactone structure portion or sultone structure portion may or may not have a substituent (Rb 2 ).
  • Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group.
  • n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb 2 may be the same or different, and a plurality of Rb 2 may be bonded to form a ring.
  • repeating unit Having a lactone structure represented by any one of general formulas (LC1-1) to (LC1-17) or a sultone structure represented by any one of general formulas (SL1-1) to (SL1-3)
  • Examples of the repeating unit include a repeating unit represented by the following general formula (AI).
  • Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
  • substituents that the alkyl group represented by Rb 0 may have include a hydroxyl group and a halogen atom.
  • the halogen atom for Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Rb 0 is preferably a hydrogen atom or a methyl group.
  • Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these.
  • Preferred is a single bond or a linking group represented by —Ab 1 —CO 2 —.
  • Ab 1 is a linear, branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.
  • V represents a group represented by any one of the general formulas (LC1-1) to (LC1-17) and (general formulas SL1-1) to (SL1-3).
  • the repeating unit having a lactone group or a sultone group usually has an optical isomer, but any optical isomer may be used.
  • One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
  • the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.
  • repeating unit having a lactone group or a sultone group are given below, but the present invention is not limited thereto.
  • the content of the repeating unit having a lactone group or a sultone group is preferably 1 to 30 mol%, more preferably 5 to 25 mol%, based on all repeating units in the resin (A). More preferably, it is ⁇ 20 mol%.
  • the resin (A) preferably has a repeating unit having a silicon atom in the side chain.
  • the repeating unit having a silicon atom in the side chain is not particularly limited as long as it has a silicon atom in the side chain. Is mentioned.
  • the repeating unit having a silicon atom is preferably a repeating unit having no structure (acid-decomposable group) protected by a leaving group that is decomposed and eliminated by the action of an acid.
  • the repeating unit having a silicon atom in the side chain is typically a repeating unit having a group having a silicon atom in the side chain.
  • Examples of the group having a silicon atom include a trimethylsilyl group, a triethylsilyl group, and triphenyl.
  • Silyl group tricyclohexylsilyl group, tristrimethylsiloxysilyl group, tristrimethylsilylsilyl group, methylbistrimethylsilylsilyl group, methylbistrimethylsiloxysilyl group, dimethyltrimethylsilylsilyl group, dimethyltrimethylsiloxysilyl group, or cyclic as shown below Alternatively, linear polysiloxane, cage-type, ladder-type, or random-type silsesquioxane structures can be used.
  • R and R 1 each independently represents a monovalent substituent. * Represents a bond.
  • Suitable examples of the repeating unit having the above group include a repeating unit derived from an acrylate compound or a methacrylate compound having the above group and a repeating unit derived from a compound having the above group and a vinyl group. it can.
  • the repeating unit having a silicon atom is preferably a repeating unit having a silsesquioxane structure.
  • a silsesquioxane structure include a cage-type silsesquioxane structure, a ladder-type silsesquioxane structure (ladder-type silsesquioxane structure), a random-type silsesquioxane structure, and the like.
  • a cage-type silsesquioxane structure is preferable.
  • the cage silsesquioxane structure is a silsesquioxane structure having a cage structure.
  • the cage silsesquioxane structure may be a complete cage silsesquioxane structure or an incomplete cage silsesquioxane structure, but may be a complete cage silsesquioxane structure.
  • the ladder-type silsesquioxane structure is a silsesquioxane structure having a ladder-like skeleton.
  • the random silsesquioxane structure is a silsesquioxane structure having a random skeleton.
  • the cage silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).
  • R represents a monovalent substituent.
  • a plurality of R may be the same or different.
  • the monovalent substituent is not particularly limited, and specific examples thereof include a halogen atom, a hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, and a blocked mercapto group (for example, blocked with an acyl group ( Protected) mercapto group), acyl group, imide group, phosphino group, phosphinyl group, silyl group, vinyl group, hydrocarbon group optionally having hetero atoms, (meth) acryl group-containing group and epoxy group-containing Group and the like.
  • the repeating unit having a silicon atom is preferably a repeating unit represented by the following formula (I).
  • L represents a single bond or a divalent linking group.
  • the divalent linking group include an alkylene group, a —COO—Rt— group, a —O—Rt— group, and the like.
  • Rt represents an alkylene group or a cycloalkylene group.
  • L is preferably a single bond or a —COO—Rt— group.
  • Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH 2 — group, a — (CH 2 ) 2 — group, or a — (CH 2 ) 3 — group.
  • X represents a hydrogen atom or an organic group.
  • the alkyl group which may have substituents, such as a fluorine atom and a hydroxyl group is mentioned, for example, A hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferable.
  • A represents a silicon atom-containing group. Of these, a group represented by the following formula (a) or formula (b) is preferable.
  • R represents a monovalent substituent.
  • a plurality of R may be the same or different. Specific examples and preferred embodiments of R are the same as those in the above formula (S).
  • a in the formula (I) is a group represented by the formula (a)
  • the formula (I) is represented by the following formula (Ia).
  • R b represents a hydrocarbon group which may have a hetero atom.
  • Specific examples and preferred embodiments of the hydrocarbon group which may have a hetero atom are the same as R in the above-described formula (S).
  • the resin (A) may have one type of repeating unit having a silicon atom or two or more types.
  • the content of the repeating unit having a silicon atom is preferably 1 to 30 mol%, more preferably 1 to 20 mol%, more preferably 1 to 10 mol based on all repeating units of the resin (A). % Is more preferable.
  • the repeating unit having a silicon atom and a structure (acid-decomposable group) protected by a leaving group in which a polar group is decomposed and eliminated by the action of an acid is a repeating unit having a silicon atom.
  • the resin (A) can further have, as other repeating units, a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group.
  • a repeating unit containing an organic group having a polar group particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group.
  • the substrate adhesion and the developer compatibility are improved.
  • the alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group an adamantyl group, a diamantyl group, and a norbornane group are preferable.
  • As the polar group a hydroxyl group and a cyano group are preferable. Specific examples of the repeating unit having a polar group are listed below, but the present invention is not limited thereto.
  • the content thereof is preferably 1 to 30 mol% with respect to all repeating units in the resin (A). It is more preferably ⁇ 25 mol%, further preferably 5 to 20 mol%.
  • resin (A) can also contain the repeating unit which has the group (photo-acid generating group) which generate
  • the repeating unit having this photoacid-generating group corresponds to the compound (B) that generates an acid upon irradiation with actinic rays or radiation described later.
  • Examples of such a repeating unit include a repeating unit represented by the following general formula (4).
  • R 41 represents a hydrogen atom or a methyl group.
  • L 41 represents a single bond or a divalent linking group.
  • L 42 represents a divalent linking group.
  • W represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.
  • examples of the repeating unit represented by the general formula (4) include repeating units described in paragraphs [0094] to [0105] of JP-A No. 2014-041327.
  • the content of the repeating unit having a photoacid generating group is 1 to 40 mol% with respect to all the repeating units in the resin (A). It is preferably 5 to 35 mol%, more preferably 5 to 30 mol%.
  • Resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
  • a conventional method for example, radical polymerization
  • a monomer type and an initiator are dissolved in a solvent and polymerization is performed by heating, and a solution containing the monomer type and the initiator in the heating solvent is taken for 1 to 10 hours.
  • the dropping polymerization method is preferably added dropwise, and the dropping polymerization method is preferred.
  • reaction solvent examples include ether solvents such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; amide solvents such as dimethylformamide and dimethylacetamide; And a solvent for dissolving a resist composition such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. More preferably, polymerization is performed using the same solvent as the solvent used in the resist composition. Thereby, generation
  • the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • an inert gas atmosphere such as nitrogen or argon.
  • commercially available radical initiators azo initiators, peroxides, etc.
  • an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable.
  • Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate), and the like.
  • a polymerization initiator is added or divided, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery.
  • the concentration of the reaction is 5 to 50% by mass, preferably 10 to 45% by mass.
  • the reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.
  • Purification is a liquid-liquid extraction method that removes residual monomer or oligomer components by combining water or an appropriate solvent, a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less, In a solid state such as reprecipitation method that removes residual monomers by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent, and washing the filtered resin slurry with the poor solvent Ordinary methods such as the purification method can be applied.
  • the weight average molecular weight of the resin (A) is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, and still more preferably from 3,000 to 15,5, as converted to polystyrene by the GPC method. 000.
  • the weight average molecular weight is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, and still more preferably from 3,000 to 15,5, as converted to polystyrene by the GPC method. 000.
  • Another particularly preferable form of the weight average molecular weight of the resin (A) is 3,000 to 9,500 in terms of polystyrene by GPC method.
  • the degree of dispersion (molecular weight distribution) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and still more preferably 1.2 to 2.0.
  • the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content.
  • the resin (A) may be used alone or in combination.
  • the resist composition contains a photoacid generator (a compound that generates an acid by actinic rays or radiation) (also referred to as “compound (B)”).
  • the photoacid generator may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
  • the photoacid generator is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
  • the photoacid generator When the photoacid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) or in a resin different from the resin (A).
  • the photoacid generator is preferably in the form of a low molecular compound.
  • the photoacid generator is not particularly limited as long as it is a known one, but an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, and the like by irradiation with active light or radiation, preferably electron beam or extreme ultraviolet light, and And a compound capable of generating at least one of tris (alkylsulfonyl) methides. More preferred examples include compounds represented by the following general formula (ZI), (ZII), or (ZIII).
  • R 201 , R 202 and R 203 each independently represents an organic group.
  • the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • Examples of the group formed by combining two members out of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
  • Z ⁇ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
  • non-nucleophilic anion examples include a sulfonate anion (such as an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion).
  • aralkylcarboxylate anions examples include sulfonylimide anions, bis (alkylsulfonyl) imide anions, tris (alkylsulfonyl) methide anions, and the like.
  • the aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. Examples include 3 to 30 cycloalkyl groups.
  • the aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
  • the alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent.
  • substituents include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 carbon atoms).
  • an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably a carbon number) 2 to 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), an aryloxysulfonyl group (preferably Is an alkylaryloxysulfonyl group (preferably having a carbon number of 7 to 20), a cycloalkyl group.
  • alkyloxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), etc.
  • examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).
  • the aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.
  • Examples of the sulfonylimide anion include saccharin anion.
  • the alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
  • substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups.
  • a fluorine atom or an alkyl group substituted with a fluorine atom is preferable.
  • the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.
  • non-nucleophilic anions examples include fluorinated phosphorus (eg, PF 6 ⁇ ), fluorinated boron (eg, BF 4 ⁇ ), and fluorinated antimony (eg, SbF 6 ⁇ ). Can do.
  • fluorinated phosphorus eg, PF 6 ⁇
  • fluorinated boron eg, BF 4 ⁇
  • fluorinated antimony eg, SbF 6 ⁇
  • non-nucleophilic anion examples include an aliphatic sulfonate anion in which at least ⁇ -position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom are preferred.
  • the non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane.
  • the pKa of the generated acid is preferably ⁇ 1 or less in order to improve sensitivity.
  • an anion represented by the following general formula (AN1) can be mentioned as a preferred embodiment.
  • Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when there are a plurality of R 1 and R 2 , they may be the same or different.
  • L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
  • A represents a cyclic organic group.
  • x represents an integer of 1 to 20
  • y represents an integer of 0 to 10
  • z represents an integer of 0 to 10.
  • the alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
  • Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
  • Xf include fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 , and CH 2 CH 2 C 4 F 9 , among which fluorine atom and CF 3 is preferred.
  • both Xf are fluorine atoms.
  • the alkyl group of R 1 and R 2 may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferred is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent for R 1 and R 2 include CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , and C 7 F 15.
  • R 1 and R 2 are preferably a fluorine atom or CF 3 .
  • x is preferably from 1 to 10, and more preferably from 1 to 5.
  • y is preferably 0 to 4, more preferably 0.
  • z is preferably 0 to 5, and more preferably 0 to 3.
  • the divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, an alkylene group, a cycloalkylene group, An alkenylene group, a linking group in which a plurality of these groups are linked, and the like can be exemplified. Among these, —COO—, —OCO—, —CO—, or —O— is preferable, and —COO— or —OCO— is more preferable.
  • the cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and includes an alicyclic group, an aryl group, and a heterocyclic group (not only those having aromaticity but also aromaticity). And the like).
  • the alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, cyclohexyl group, and cyclooctyl group, norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetra
  • a polycyclic cycloalkyl group such as a cyclododecanyl group and an adamantyl group is preferred.
  • an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is a post-exposure heating step.
  • a norbornyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group
  • MEEF Mesk Error Enhancement Factor
  • Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
  • heterocyclic group examples include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
  • those derived from a furan ring, a thiophene ring, and a pyridine ring are preferable.
  • examples of the cyclic organic group also include a lactone structure, and specific examples include lactone structures represented by the above-described general formulas (LC1-1) to (LC1-17).
  • the cyclic organic group may have a substituent, and the substituent may be an alkyl group (which may be linear, branched, or cyclic, and preferably has 1 to 12 carbon atoms)
  • a cycloalkyl group (which may be monocyclic, polycyclic or spirocyclic, preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, Examples thereof include an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group.
  • the carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.
  • Examples of the organic group for R 201 , R 202, and R 203 include an aryl group, an alkyl group, and a cycloalkyl group.
  • R 201 , R 202 and R 203 at least one is preferably an aryl group, more preferably all three are aryl groups.
  • aryl group in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.
  • Preferred examples of the alkyl group and cycloalkyl group represented by R 201 to R 203 include a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. More preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. More preferable examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • These groups may further have a substituent.
  • substituents include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), and an alkoxycarbonyloxy group (preferably having a carbon number) 2-7) and the like, but are not limited thereto.
  • R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 are the same as the groups described as the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI). It is.
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent. Examples of this substituent include those that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI) may have.
  • Z ⁇ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ⁇ in formula (ZI).
  • the photoacid generator has a volume of 130 to 3 or more by irradiation with an electron beam or extreme ultraviolet rays from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution.
  • the compound generate an acid (more preferably sulfonic acid) having a size of more than 1, more preferably a compound that generates an acid having a volume of 190 3 or more (more preferably sulfonic acid).
  • more preferably 270 ⁇ 3 (more preferably sulfonic acid) or a size of the acid is a compound that generates, be (more preferably sulfonic acid) acid volume 400 ⁇ 3 or more in size is a compound capable of generating an Particularly preferred.
  • the volume is preferably 2000 3 or less, and more preferably 1500 3 or less.
  • the volume value is obtained using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. By performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.
  • One foot is 1 ⁇ 10 ⁇ 10 m.
  • the number of fluorine atoms contained in the photoacid generator is adjusted as appropriate for the purpose of adjusting the cross-sectional shape of the pattern.
  • By adjusting the number of fluorine atoms it is possible to control the surface uneven distribution of the photoacid generator in the resist film. That is, as the number of fluorine atoms contained in the photoacid generator increases, the photoacid generator tends to be unevenly distributed on the resist film surface.
  • a photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
  • the content of the photoacid generator in the resist composition is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, and still more preferably 8 to 40% by mass, based on the total solid content of the composition. %.
  • the content of the photoacid generator is preferably high, particularly preferably 10 to 40% by mass, and most preferably 10 to 35% by mass.
  • the resist composition used in the present invention preferably contains a solvent (also referred to as “resist solvent”).
  • a solvent you may use the organic solvent which may be contained in the developing solution mentioned above.
  • This solvent comprises (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable to include at least one selected from at least one selected from the group.
  • this solvent may further contain components other than component (M1) and (M2).
  • the present inventors have found that when such a solvent and the above-described resin are used in combination, the coating property of the composition is improved and a pattern with a small number of development defects can be formed. Although the reason for this is not necessarily clear, the present inventors have found that these solvents have a good balance of solubility, boiling point, and viscosity of the resin described above. It is thought that it originates in being able to suppress generation
  • Component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate, more preferably propylene glycol monomethyl ether acetate.
  • the component (M2) the following are preferable.
  • propylene glycol monoalkyl ether propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
  • lactic acid ester ethyl lactate, butyl lactate or propyl lactate is preferable.
  • acetate ester methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferable.
  • butyl butyrate is also preferred.
  • alkoxypropionate methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
  • chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, Acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone are preferred.
  • cyclic ketone methylcyclohexanone, isophorone, or cyclohexanone is preferable.
  • lactone ⁇ -butyrolactone is preferable.
  • alkylene carbonate propylene carbonate is preferable.
  • Component (M2) is more preferably propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, ⁇ -butyrolactone, or propylene carbonate.
  • an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10) and a hetero atom number of 2 or less.
  • ester solvent having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, Examples thereof include isobutyl isobutyrate, heptyl propionate and butyl butanoate, and isoamyl acetate is preferred.
  • component (M2) one having a flash point (hereinafter also referred to as fp) of 37 ° C. or higher is preferably used.
  • component (M2) include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), methyl amyl ketone (fp: 42 ° C), cyclohexanone (fp: 44 ° C), pentyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), ⁇ -butyrolactone (fp: 101 ° C), or propylene carbonate (fp: 132 ° C.) is preferred.
  • propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is more preferable, and propylene glycol monoethyl ether and ethyl lactate are more preferable.
  • flash point means a value described in a reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma Aldrich.
  • the solvent preferably contains the component (M1). It is more preferable that the solvent consists essentially of the component (M1) or a mixed solvent of the component (M1) and other components. In the latter case, it is more preferable that the solvent contains both the component (M1) and the component (M2).
  • the mass ratio of the component (M1) and the component (M2) is preferably in the range of 100: 0 to 15:85, more preferably in the range of 100: 0 to 40:60, and 100: More preferably, it is in the range of 0 to 60:40. That is, it is preferable that a solvent consists only of a component (M1) or contains both a component (M1) and a component (M2), and those mass ratios are as follows. That is, in the latter case, the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and further preferably 60/40 or more. preferable. Employing such a configuration makes it possible to further reduce the number of development defects.
  • mass ratio of the component (M1) with respect to a component (M2) shall be 99/1 or less, for example.
  • the solvent may further contain components other than the components (M1) and (M2).
  • the content of components other than components (M1) and (M2) is preferably in the range of 5 to 30% by mass with respect to the total amount of the solvent.
  • the content of the solvent in the resist composition is preferably adjusted so that the solid content concentration of all components is 0.5 to 30% by mass, more preferably 1 to 20% by mass. . If it carries out like this, the applicability
  • the resist composition of the present invention preferably contains a basic compound in order to reduce the change in performance over time from exposure to heating.
  • Preferred examples of the basic compound include compounds having a structure represented by the following formulas (A) to (E).
  • R 200 , R 201 and R 202 may be the same or different, and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably a carbon atom). 3 to 20) or an aryl group (preferably having 6 to 20 carbon atoms), wherein R 201 and R 202 may be bonded to each other to form a ring.
  • the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
  • R 203 , R 204 , R 205 and R 206 may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
  • Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium Examples thereof include a compound having a carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.
  • Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole.
  • Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5, 4,0] undec-7-ene and the like.
  • Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris (t-butyl). Phenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like.
  • the compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. It is done.
  • Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
  • the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline, and the like.
  • alkylamine derivative having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine.
  • aniline derivatives having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline.
  • Preferred examples of the basic compound further include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.
  • a primary, secondary, or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
  • the amine compound is more preferably a tertiary amine compound.
  • the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms).
  • Preferably 6 to 12 carbon atoms may be bonded to the nitrogen atom.
  • the amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
  • the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, more preferably 4 to 6.
  • an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
  • ammonium salt compound a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
  • the ammonium salt compound may be a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group, provided that at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom.
  • the ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
  • the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, more preferably 4 to 6.
  • an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
  • the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms or sulfonates are preferable.
  • the halogen atom is preferably chloride, bromide or iodide
  • the sulfonate is preferably an organic sulfonate having 1 to 20 carbon atoms.
  • the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.
  • the alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group.
  • alkyl sulfonate examples include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.
  • aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring.
  • the benzene ring, naphthalene ring, and anthracene ring may have a substituent, and the substituent may be a linear or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. preferable.
  • Specific examples of the linear or branched alkyl group or cycloalkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, i-butyl group, t-butyl group, n- A hexyl group, a cyclohexyl group, etc. are mentioned.
  • the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, and an acyloxy group.
  • the amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound.
  • the phenoxy group may have a substituent.
  • the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryl.
  • An oxy group etc. are mentioned.
  • the substitution position of the substituent may be any of the 2-6 positions.
  • the number of substituents may be any in the range of 1 to 5.
  • oxyalkylene group between the phenoxy group and the nitrogen atom.
  • the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, more preferably 4 to 6.
  • an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
  • the amine compound having a phenoxy group is prepared by reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether by heating, and then an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, and tetraalkylammonium. Can be obtained by extraction with an organic solvent such as ethyl acetate or chloroform.
  • an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, and tetraalkylammonium is added. It can be obtained by extraction with an organic solvent such as ethyl acetate or chloroform.
  • the resist composition has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease or disappearance of the proton acceptor, or a change from proton acceptor to acidic It may further contain a compound that generates the above compound [hereinafter also referred to as compound (PA)].
  • PA acidic property
  • the proton acceptor functional group is a group capable of electrostatically interacting with a proton or a functional group having an electron, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a ⁇ conjugate. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute to.
  • the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.
  • Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.
  • the compound (PA) is decomposed by irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity.
  • the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group.
  • a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.
  • Specific examples of the compound (PA) include the following compounds. Furthermore, as specific examples of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP2014-41328A and paragraphs 0108 to 0116 of JP2014-134686A can be used. The contents of which are incorporated herein.
  • the amount of the basic compound used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the resist composition.
  • the photoacid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.
  • the composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (D)” or simply “resin (D)”).
  • the hydrophobic resin (D) is preferably different from the resin (A).
  • the hydrophobic resin (D) is preferably designed to be unevenly distributed at the interface.
  • unlike the surfactant it is not always necessary to have a hydrophilic group in the molecule, and the polar / nonpolar substance is mixed uniformly. You don't have to contribute to Examples of the effect of adding the hydrophobic resin include control of the static and / or dynamic contact angle of the resist film surface with respect to water, improvement of immersion liquid followability, and suppression of outgas.
  • the hydrophobic resin (D) is selected from any one of “fluorine atom”, “silicon atom”, and “CH 3 partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have the above, and it is more preferable to have two or more.
  • the hydrophobic resin (D) contains a fluorine atom and / or a silicon atom
  • the fluorine atom and / or silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin. , May be contained in the side chain.
  • the hydrophobic resin (D) contains a fluorine atom
  • it is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
  • the alkyl group having a fluorine atom preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms
  • a cycloalkyl group having a fluorine atom and an aryl group having a fluorine atom are a cycloalkyl group in which one hydrogen atom is substituted with a fluorine atom and an aryl group having a fluorine atom, respectively, and further a substituent other than a fluorine atom is substituted. You may have.
  • alkyl group having a fluorine atom examples include groups represented by the following general formulas (F2) to (F4).
  • the invention is not limited to this.
  • R 57 to R 68 each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight or branched).
  • R 57 to R 61 , at least one of R 62 to R 64 , and at least one of R 65 to R 68 are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms). All of R 57 to R 61 and R 65 to R 67 are preferably fluorine atoms.
  • R 62 , R 63 and R 68 are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. More preferred. R 62 and R 63 may be connected to each other to form a ring.
  • the hydrophobic resin (D) may contain a silicon atom.
  • a silicon atom As the partial structure having a silicon atom, an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure is preferable.
  • the repeating unit having a fluorine atom or a silicon atom include those exemplified in US2012 / 0251948A1 [0519].
  • the hydrophobic resin (D) it is also preferred to include CH 3 partial structure side chain moiety.
  • CH 3 partial structure contained in the side chain moiety in the hydrophobic resin (D) (hereinafter, simply referred to as "side chain CH 3 partial structure")
  • The, CH 3 partial structure an ethyl group, and a propyl group having Is included.
  • a methyl group directly bonded to the main chain of the hydrophobic resin (D) (for example, an ⁇ -methyl group of a repeating unit having a methacrylic acid structure) is caused by the influence of the main chain on the surface of the hydrophobic resin (D). Since the contribution to uneven distribution is small, it is not included in the CH 3 partial structure in the present invention.
  • the hydrophobic resin (D) is a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M).
  • R 11 to R 14 are CH 3 “as is”, the CH 3 is not included in the CH 3 partial structure of the side chain moiety in the present invention.
  • CH 3 partial structure exists through some atoms from C-C backbone, and those falling under CH 3 partial structures in the present invention.
  • R 11 is an ethyl group (CH 2 CH 3 )
  • R 11 to R 14 each independently represents a side chain portion.
  • R 11 to R 14 in the side chain portion include a hydrogen atom and a monovalent organic group.
  • the monovalent organic group for R 11 to R 14 include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl.
  • Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.
  • the hydrophobic resin (D) is preferably a resin having a repeating unit having a CH 3 partial structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and It is more preferable to have at least one repeating unit (x) among repeating units represented by the following general formula (III).
  • X b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom
  • R 2 has one or more CH 3 partial structure represents a stable organic radical to acid.
  • the organic group that is stable to an acid is more specifically an organic group that does not have an acid-decomposable group (a group that decomposes by the action of an acid to generate a polar group such as a carboxy group). Is preferred.
  • the alkyl group of Xb1 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
  • X b1 is preferably a hydrogen atom or a methyl group.
  • R 2 include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH 3 partial structures.
  • R 2 is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH 3 partial structures.
  • the acid-stable organic group having one or more CH 3 partial structures as R 2 preferably has 2 or more and 10 or less CH 3 partial structures, and more preferably 2 or more and 8 or less.
  • Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. Note that the present invention is not limited to this.
  • the repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.
  • the repeating unit represented by formula (III) will be described in detail.
  • X b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom
  • R 3 represents an acid-stable organic group having one or more CH 3 partial structures
  • n represents an integer of 1 to 5.
  • the alkyl group for Xb2 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group.
  • X b2 is preferably a hydrogen atom. Since R 3 is an organic group that is stable against acid, more specifically, R 3 is preferably an organic group having no acid-decomposable group.
  • R 3 includes an alkyl group having one or more CH 3 partial structures.
  • the acid-stable organic group having one or more CH 3 partial structures as R 3 preferably has 1 or more and 10 or less CH 3 partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.
  • n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
  • the repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.
  • the repeating unit represented by the general formula (II) contains a CH 3 partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom
  • the repeating unit represented by the general formula (II) contains a CH 3 partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom
  • the content of at least one repeating unit (x) among the repeating units represented by the general formula (III) is preferably 90 mol% or more based on all repeating units of the hydrophobic resin (D). More preferably, it is 95 mol% or more. Content is 100 mol% or less normally with respect to all the repeating units of hydrophobic resin (D).
  • the hydrophobic resin (D) comprises at least one repeating unit (x) among the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III). ),
  • the surface free energy of the hydrophobic resin (D) increases.
  • the hydrophobic resin (D) is less likely to be unevenly distributed on the surface of the resist film, and the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved. it can.
  • the hydrophobic resin (D) includes the following (x) to (z) regardless of whether (i) a fluorine atom and / or a silicon atom is included or (ii) a CH 3 partial structure is included in the side chain portion. ) May have at least one group selected from the group of (X) an acid group, (Y) a group that is decomposed by the action of an alkali developer to increase the solubility in the alkali developer (hereinafter also referred to as a polar conversion group); (Z) a group decomposable by the action of an acid
  • Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkyl) Sulfonyl) methylene group and the like.
  • Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, or
  • the repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain. Furthermore, a polymerization initiator or a chain transfer agent having an acid group can be used at the time of polymerization to be introduced at the end of the polymer chain.
  • the repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
  • the content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 5%, based on all repeating units in the hydrophobic resin (D). 20 mol%.
  • Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto.
  • Rx represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
  • the group (y) that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer is preferably a group having a lactone structure, an acid anhydride group, or an acid imide group, and more preferably a group having a lactone structure.
  • the repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic ester or methacrylic ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group.
  • this repeating unit may be introduce
  • the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the resin P.
  • the content of the repeating unit having a group (y) that is decomposed by the action of the alkali developer and increases the solubility in the alkali developer is 1 to 100 mol% based on all repeating units in the hydrophobic resin (D). It is preferably 3 to 98 mol%, more preferably 5 to 95 mol%.
  • examples of the repeating unit having a group (z) capable of decomposing by the action of an acid are the same as the repeating unit having an acid-decomposable group exemplified in the resin (A).
  • the repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom.
  • the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol% with respect to all the repeating units in the resin (D). The amount is preferably 10 to 80 mol%, more preferably 20 to 60 mol%.
  • the hydrophobic resin (D) may further have a repeating unit different from the above-described repeating unit.
  • the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all repeating units contained in the hydrophobic resin (D). Further, the repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol% in all repeating units contained in the hydrophobic resin (D).
  • hydrophobic resin (D) contains a CH 3 partial structure in the side chain portion
  • a mode in which the hydrophobic resin (D) does not substantially contain a fluorine atom and a silicon atom is also preferable.
  • hydrophobic resin (D) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom.
  • the standard polystyrene equivalent weight average molecular weight of the hydrophobic resin (D) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
  • the hydrophobic resin (D) may be used alone or in combination.
  • the content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention.
  • the residual monomer and oligomer components are preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass.
  • the molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.
  • hydrophobic resin (D) various commercially available products can be used, and the hydrophobic resin (D) can be synthesized according to a conventional method (for example, radical polymerization).
  • the resist composition used in the present invention may further contain a surfactant.
  • a surfactant By containing a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.
  • the surfactant it is particularly preferable to use a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425.
  • F top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); 01 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or
  • the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). You may synthesize. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991. Further, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may be used.
  • surfactants may be used alone or in combination of two or more.
  • the content thereof is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and still more preferably based on the total solid content of the composition. 0.0005 to 1% by mass.
  • the resist composition used in the present invention comprises a crosslinking agent, a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a molecular weight of 1000 or less).
  • the resist composition used in the present invention may further contain a dissolution inhibiting compound.
  • the “dissolution inhibiting compound” is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce the solubility in an organic developer.
  • the resist composition used in the present invention may further contain an organic acid (for example, an organic carboxylic acid).
  • the organic acid neutralizes the basic compound in the resist composition, prevents alkali decomposition with time of the resin (A) and the hydrophobic resin (D), and improves stability with time.
  • the amount of the organic acid is preferably large from the viewpoint of stability over time, and is preferably added so that the content of the organic acid in the resist composition exceeds 5% by mass with respect to the total solid content.
  • the content of the organic acid in the resist composition is more preferably more than 5% by mass and less than 15% by mass based on the total solid content in the resist composition, and more preferably more than 5% by mass and less than 10% by mass. Further preferred.
  • the organic acid preferably has a pKa in the range of 0 to 10, more preferably in the range of 2 to 8, still more preferably in the range of 3 to 7, from the viewpoint of stability over time.
  • pKa represents pKa in an aqueous solution.
  • Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
  • a lower value indicates a higher acid strength.
  • pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution.
  • the pKa of the organic acid is preferably lower than the pKa of the resin, and moreover than the pKa of the acid generated from the photoacid generator. High is preferred.
  • the pKa of the organic acid is preferably 3 or more lower than the pKa of the resin (A), more preferably 5 or more.
  • the pKa of the organic acid (A) is preferably 2 or more, more preferably 3 or more, higher than the pKa of the acid generated from the photoacid generator.
  • organic acids include organic carboxylic acids and organic sulfonic acids, and organic carboxylic acids are preferred.
  • organic carboxylic acids include aromatic organic carboxylic acids, aliphatic carboxylic acids, alicyclic carboxylic acids, unsaturated aliphatic carboxylic acids, oxycarboxylic acids, and alkoxycarboxylic acids.
  • the organic acid is preferably an aromatic organic carboxylic acid, more preferably benzoic acid, 2-hydroxy-3-naphthoic acid, or 2-naphthoic acid.
  • organic acids particularly organic carboxylic acids
  • examples of organic acids include the following.
  • resin (A) As the resin (A), a resin represented by the following structural formula was used.
  • the acid generator was selected from z1 to z36 exemplified above.
  • hydrophobic resin As the hydrophobic resin, a resin represented by the following structural formula was used.
  • W-1 Megafuck R08 (Dainippon Ink & Chemicals, Inc .; fluorine and silicon)
  • W-2 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
  • W-3 Troisol S-366 (manufactured by Troy Chemical Co., Ltd .; fluorine-based)
  • W-4 PF6320 (manufactured by OMNOVA; fluorine-based)
  • solvent the following solvents were used.
  • Example 1 [Preparation of support]
  • a support a 6-inch silicon wafer on which Cr oxide deposition was performed (prepared with a shielding film used for ordinary photomask blanks) was prepared. One inch is 25.4 mm.
  • resist film The resist composition was coated on a support using a spin coater Mark8 manufactured by Tokyo Electron, and then the support was dried on a hot plate at 140 ° C. for 90 seconds to obtain a resist film having a thickness of 80 nm. It was. That is, resist-coated mask blanks were obtained.
  • the exposure dose X1 was calculated by the following procedure. Using an electron beam lithography system (manufactured by Elionix Co., Ltd .; ELS-7500, acceleration voltage 50 keV), the exposure dose is increased from 1 ⁇ C / cm 2 to 1 ⁇ C / cm 2 with respect to the resist film at different positions on the resist film. 99-point exposure was performed. Thereafter, the exposed resist film was baked at 110 ° C. for 90 seconds (Post Exposure Bake; PEB), developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 60 seconds, and rinsed with water for 30 seconds. , Dried.
  • PEB Post Exposure Bake
  • the film thickness of 99 exposed areas corresponds to the film thickness and exposure dose at each exposure location in the orthogonal coordinates with the thickness (nm) as the vertical axis and the exposure dose ( ⁇ C / cm 2 ) as the horizontal axis.
  • the points to be plotted were plotted to produce a plot (see FIG. 7).
  • the exposure amount at the point where the exposure amount was the largest among the points where the film thickness was 0 was calculated as the exposure amount X1.
  • a resist pattern was prepared using the other support having the resist film prepared above.
  • Table 1 shows the exposure amount at the time of pattern irradiation. After the irradiation, the resist film subjected to pattern irradiation was heated on a hot plate at 110 ° C. for 90 seconds.
  • Example 2 Instead of the tetramethylammonium hydroxide aqueous solution (2.38% by mass), the developer described in Table 2 was used, and instead of the pure water used for rinsing, the rinse liquid described in Table 2 was used. A pattern was formed and various evaluations were performed according to the same procedure as in Example 1 except that the following “Calculation of Exposure X2” was performed instead of [Calculation of Exposure X1]. The results are shown in Table 2. In the above process, when the pattern as shown in FIG.
  • pattern formation The evaluation of the “patternability” was “A”, and the evaluation of the “patternability” was “B” when the pattern was not formed (when the film remained in the high exposure region 18).
  • the exposure dose X2 was calculated according to the following procedure. Using an electron beam lithography system (manufactured by Elionix Co., Ltd .; ELS-7500, acceleration voltage 50 keV), the exposure dose is increased from 1 ⁇ C / cm 2 to 1 ⁇ C / cm 2 with respect to the resist film at different positions on the resist film. 99-point exposure was performed. After that, the exposed resist film was baked at 110 ° C. for 90 seconds (Post Exposure Bake; PEB), and then developed for 60 seconds with a developer containing an organic solvent used in each example and comparative example.
  • PEB Post Exposure Bake
  • the film thickness of 99 exposed areas After rinsing with a rinsing solution used for 30 seconds, it was dried. Measures the film thickness of 99 exposed areas, and corresponds to the film thickness and exposure dose at each exposure location in the orthogonal coordinates with the thickness (nm) as the vertical axis and the exposure dose ( ⁇ C / cm 2 ) as the horizontal axis. The points to be plotted were plotted to produce a plot (see FIG. 11). Next, from the obtained plot, the exposure amount at the point where the exposure amount was the largest among the points where the film thickness was maximum was calculated as the exposure amount X2.
  • Example 3 [Preparation of resist composition] A composition having the composition shown in Table 3 below (the concentration (% by mass) of each component represents the concentration in the total solid content concentration) is dissolved in a solvent, and the coating liquid composition has a solid content concentration of 1.5% by mass. Was prepared. Next, the coating liquid composition was filtered through a polytetrafluoroethylene filter having a pore size of 0.05 ⁇ m to prepare a resist composition.
  • the exposure dose X1 was calculated by the following procedure. Using an EUV exposure apparatus (Microexposure Tool, manufactured by Exitech, NA 0.3, X-dipole, outer sigma 0.68, inner sigma 0.36), the exposure amount can be applied to the resist film without using an exposure mask. 99-point exposure was performed at different positions on the resist film while increasing from 1 mJ / cm 2 to 1 mJ / cm 2 . Thereafter, the exposed resist film was baked at 100 ° C.
  • EUV exposure apparatus Microexposure Tool, manufactured by Exitech, NA 0.3, X-dipole, outer sigma 0.68, inner sigma 0.36
  • a resist pattern was prepared using the other support having the resist film prepared above. Pattern exposure is performed on the obtained resist film through an exposure mask using an EUV exposure apparatus (Microexposure Tool, manufactured by Exitech, NA 0.3, X-dipole, outer sigma 0.68, inner sigma 0.36). Went.
  • the silicon wafer having the resist film subjected to the exposure treatment was heated on a hot plate at 100 ° C. for 60 seconds.
  • development was performed by immersing the resist film in an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 60 seconds.
  • the obtained resist pattern was rinsed with pure water for 30 seconds, and then the obtained resist pattern was dried.
  • Example 4 Instead of the tetramethylammonium hydroxide aqueous solution (2.38% by mass), the developer described in Table 4 is used, and the rinse liquid described in Table 4 is used instead of the pure water used for rinsing. A pattern was formed and various evaluations were performed according to the same procedure as in Example 3 except that the following “calculation of exposure amount X2” was performed instead of [calculation of exposure amount X1]. The results are shown in Table 4. In the above process, when the pattern as shown in FIG.
  • pattern formation The evaluation of the “patternability” was “A”, and the evaluation of the “patternability” was “B” when the pattern was not formed (when the film remained in the high exposure region 18).
  • the exposure dose X2 was calculated according to the following procedure. Using an EUV exposure apparatus (Microexposure Tool, manufactured by Exitech, NA 0.3, X-dipole, outer sigma 0.68, inner sigma 0.36), the exposure amount can be applied to the resist film without using an exposure mask. 99-point exposure was performed at different positions on the resist film while increasing from 1 mJ / cm 2 to 1 mJ / cm 2 . Thereafter, the exposed resist film was baked at 100 ° C. for 60 seconds (Post Exposure Bake; PEB), and then developed with a developer containing an organic solvent used in each example and comparative example for 60 seconds.
  • PEB Post Exposure Bake
  • each example and comparative example After rinsing with a rinsing solution used for 30 seconds, it was dried. Measures the film thickness of 99 exposed areas, and corresponds to the film thickness and exposure dose at each exposure location on the orthogonal coordinates with the film thickness (nm) as the vertical axis and the exposure dose (mJ / cm 2 ) as the horizontal axis. The points to be plotted were plotted to produce a plot (see FIG. 11). Next, from the obtained plot, the exposure amount at the point where the exposure amount was the largest among the points where the film thickness was maximum was calculated as the exposure amount X2.
  • Example 5 [Preparation of resist composition] A composition having the composition shown in Table 5 below (the concentration (% by mass) of each component represents the concentration in the total solid content concentration) is dissolved in a solvent, and the coating liquid composition has a solid content concentration of 5.0% by mass. Was prepared. Next, the coating liquid composition was filtered through a polyethylene filter having a pore size of 0.03 ⁇ m to prepare a resist composition.
  • the exposure dose X1 was calculated by the following procedure. Using an ArF excimer laser immersion scanner (manufactured by ASML, XT1700i, NA 1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection) on the resist film without using an exposure mask 99 points of exposure were performed at different positions on the resist film while increasing the exposure amount from 1 mJ / cm 2 to 1 mJ / cm 2 . Thereafter, the exposed resist film was baked at 100 ° C.
  • an ArF excimer laser immersion scanner manufactured by ASML, XT1700i, NA 1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection
  • a resist pattern was prepared using the other support having the resist film prepared above.
  • Resist film obtained through exposure mask using ArF excimer laser immersion scanner (manufactured by ASML, XT1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection)
  • a pattern exposure was carried out.
  • Ultra pure water was used as the immersion liquid.
  • the silicon wafer having the resist film subjected to the exposure treatment was heated on a hot plate at 100 ° C. for 60 seconds.
  • development was performed by immersing the resist film in an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 60 seconds.
  • the obtained resist pattern was rinsed with pure water for 30 seconds, and then the obtained resist pattern was dried.
  • Example 6 Instead of the tetramethylammonium hydroxide aqueous solution (2.38% by mass), the developer described in Table 6 is used, and the rinse liquid described in Table 6 is used instead of the pure water used in the rinse. A pattern was formed and various evaluations were performed according to the same procedure as in Example 5 except that the following “calculation of exposure amount X2” was performed instead of [calculation of exposure amount X1]. The results are shown in Table 6. In the above process, when the pattern as shown in FIG.
  • pattern formation The evaluation of the “patternability” was “A”, and the evaluation of the “patternability” was “B” when the pattern was not formed (when the film remained in the high exposure region 18).
  • the exposure dose X2 was calculated according to the following procedure. Using an ArF excimer laser immersion scanner (manufactured by ASML, XT1700i, NA 1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection) on the resist film without using an exposure mask 99 points of exposure were performed at different positions on the resist film while increasing the exposure amount from 1 mJ / cm 2 to 1 mJ / cm 2 . Thereafter, the exposed resist film was baked at 100 ° C.
  • an ArF excimer laser immersion scanner manufactured by ASML, XT1700i, NA 1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection
  • each example and comparative example After rinsing with a rinsing solution used for 30 seconds, it was dried. Measures the film thickness of 99 exposed areas, and corresponds to the film thickness and exposure dose at each exposure location in the orthogonal coordinates with the thickness (nm) as the vertical axis and the exposure dose ( ⁇ C / cm 2 ) as the horizontal axis. The points to be plotted were plotted to produce a plot (see FIG. 11). Next, from the obtained plot, the exposure amount at the point where the exposure amount was the largest among the points where the film thickness was maximum was calculated as the exposure amount X2.

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Abstract

L'invention concerne un nouveau procédé de formation de motif, capable de former des motifs fins avec une procédure plus simple, et un procédé de fabrication de dispositif électronique. Ce procédé de formation de motif comprend une étape A pour former un film d'épaisseur T sur un substrat en utilisant une composition de résine sensible à un rayonnement ou sensible aux rayons actiniques contenant une résine et un générateur de photoacide, une étape B pour exposer le film aux rayons actiniques ou à un rayonnement, et une étape C pour développer le film exposé à l'aide d'un agent de développement pour former un motif, dans l'étape B, l'exposition étant réalisée avec une quantité de lumière d'exposition supérieure à la quantité de lumière d'exposition calculée par un procédé prescrit.
PCT/JP2017/002242 2016-01-27 2017-01-24 Procédé de formation de motif, procédé de fabrication de dispositif électronique WO2017130932A1 (fr)

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CN112289681A (zh) * 2020-10-28 2021-01-29 上海华力集成电路制造有限公司 去除沟槽内非晶硅层的方法

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KR20200060264A (ko) 2018-11-22 2020-05-29 도오꾜오까고오교 가부시끼가이샤 레지스트 조성물 및 레지스트 패턴 형성 방법
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CN112289681A (zh) * 2020-10-28 2021-01-29 上海华力集成电路制造有限公司 去除沟槽内非晶硅层的方法

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