TW201303506A - Method of forming pattern and actinic-ray-sensitive or radiation-sensitive resin composition used in thereof - Google Patents

Abstract

The method of forming the pattern could be executed inexpensively and a property of a formed pattern is excellent on a substrate of level difference. A characteristic of the method of forming the pattern of the invention includes steps below: (i) a step of forming a film by using the actinic-ray-sensitive or radiation-sensitive resin composition, wherein the actinic-ray-sensitive or radiation-sensitive resin composition include a resin (P) containing at least one repeating unit (a) represented by at least one of a general formula (I) and a general formula (II) as shown below and at least one repeating unit (b) represented by at least one of a general formula (III), a general formula (IV) and a general formula (V) as shown below, and a compound (B) that generates an acid by exposing to actinic rays or radiation; (ii) a step of exposing the film by KrF excimer laser; and (iii) a step of forming a negative pattern by using a developing solution containing an organic solvent to develop the film.

Description

Pattern forming method and sensitized ray- or radiation-sensitive resin composition used in the method

The present invention relates to a pattern which can be suitably used in a semiconductor manufacturing step of an IC or the like, a circuit substrate such as a liquid crystal or a thermal head, and another lithography step of photofabrication. A forming method, a sensitizing ray-sensitive or radiation-sensitive resin composition used in the method, and a sensitizing ray-sensitive or radiation-sensitive film using the composition. Moreover, the present invention also relates to a method of manufacturing an electronic device including the pattern forming method and an electronic device manufactured by the method. The pattern forming method of the present invention is particularly suitable for exposure using a KrF exposure apparatus.

After the appearance of the resist for the KrF excimer laser (248 nm), in order to compensate for the decrease in sensitivity due to light absorption, an image forming method using a so-called chemically amplified image forming method as a resist is used. If an image forming method for positive chemical amplification is exemplified, the image forming method is as follows: by exposure of an excimer laser, an electron beam, an extreme ultraviolet light, or the like, the acid generator of the exposed portion is decomposed to generate an acid for exposure. In the post-baking (PEB: Post Exposure Bake), the generated acid is used as a reaction catalyst to change the alkali-insoluble group to an alkali-soluble group, and the exposed portion is removed by an alkaline developing solution.

In the above method, various alkaline developing solutions have been proposed as the alkaline developing solution, and a water-based alkaline developing solution of 2.38 mass% of TMAH (tetramethylammonium hydroxide aqueous solution) has been used in general.

In addition, it is not only the mainstream positive type, but also developed and used. A pattern forming method of a negative developing solution, that is, a developing solution containing an organic solvent (for example, refer to Patent Document 1 to Patent Document 3). The reason for this is that when a semiconductor element or the like is manufactured, there is a demand for forming a pattern having various shapes such as lines, grooves, and holes, and on the other hand, there is a pattern which is difficult to form by a conventional positive resist.

In recent years, the pattern forming method at the forefront of development has been more than a positive type. In the negative type, an ArF excimer laser can be used to further perform immersion exposure to form a pattern having high resolution. However, in semiconductor manufacturing, not only the miniaturization of the limit is required, but also the effective use and low cost of existing equipment are required. Therefore, it is also studied to replace part of the process performed in the previous ArF exposure by KrF exposure, but it exceeds the limit of KrF exposure, thus retrograde the historical allusion of the development of ArF exposure technology. The current situation is that the operation of using KrF exposure instead of one part of the ArF exposure process is not only subject to the above-mentioned miniaturization, but also has various problems such as the necessity of improvement of the materials (resin, etc.) used, and the difference in exposure mechanism. Problems that are technically difficult to solve, etc.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-40849

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-292975

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-217884

An object of the present invention is to provide a pattern forming method which can be inexpensively implemented and which is excellent in pattern formation property on a step substrate, and sensitization for the method A ray- or radiation-sensitive linear resin composition.

The present invention is as follows, for example.

[1] A pattern forming method comprising the steps of: (1) forming a film by using a sensitizing ray-sensitive or radiation-sensitive resin composition, wherein the sensitized ray-sensitive or radiation-sensitive resin composition contains At least one repeating unit (a) represented by at least one of the following general formula (I) and formula (II), and the following general formula (III), general formula (IV) and general formula (V) At least one resin (P) of at least one repeating unit (b) and a compound (B) which generates an acid by irradiation with actinic rays or radiation; (b) a film by a KrF excimer laser a step of performing exposure; and (c) a step of developing the film using a developer containing an organic solvent to form a negative pattern,

Wherein R ₁₁ , R ₂₁ , R ₃₁ , R ₄₁ and R ₅₁ each independently represent a hydrogen atom or a methyl group; R ₁₂ represents a hydrogen atom or a -COOCH ₃ group; X represents a methylene group or an oxygen atom; R ₃₂ , R ₄₂ and R ₅₂ each independently represent an alkyl group having 1 to 4 carbon atoms; m represents 0 or 1; and n represents 1 or 2.

[2] The pattern forming method according to [1], wherein the repeating unit (a) comprises at least one repeating unit represented by the above formula (I), and the repeating unit (b) comprises at least 1 a repeating unit represented by the above formula (IV).

[3] The pattern forming method according to [1], wherein the organic solvent contained in the developer is selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. At least one solvent of the group formed.

[4] The pattern forming method according to [1], wherein after the step of developing the film using the developer, the method further comprises: (d) using the rinsing liquid containing an organic solvent to the film The step of cleaning.

[5] The pattern forming method according to [1], wherein the negative pattern is formed on a step substrate.

[6] A photosensitive ray-sensitive or radiation-sensitive resin composition, The pattern forming method according to any one of [1] to [5].

[7] A photosensitive ray-sensitive or radiation-sensitive linear film formed by the photosensitive ray-sensitive or radiation-sensitive resin composition as described in [6].

[8] A method of producing an electronic device, comprising the pattern forming method according to any one of [1] to [5].

[9] An electronic device manufactured by the method of manufacturing an electronic device according to [8].

According to the present invention, it is possible to provide a pattern forming method which can be inexpensively implemented and which is excellent in pattern formation property on a step substrate, and a sensitizing ray-sensitive or radiation-sensitive resin composition used in the method.

Hereinafter, embodiments of the present invention will be described in detail.

Further, here, it is not indicated that the substituted or unsubstituted group and the atomic group include both a non-substituent group and a substituent group. For example, it is not expressly stated that the substituted or unsubstituted "alkyl group" is not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group).

<pattern forming method>

The pattern forming method of the present invention comprises the steps of: (1) forming a film by using a sensitizing ray-sensitive or radiation-sensitive resin composition, the sensitizing ray-sensitive or radiation-sensitive resin composition having the following At least one repeating unit (a) represented by at least one of the formula (I) and the formula (II), and at least one of the following formula (III), formula (IV) and formula (V) a resin (P) representing at least one repeating unit (b) and a compound (B) which generates an acid by irradiation with actinic rays or radiation; (2) exposing the film by a KrF excimer laser And; (iii) developing the film using a developer containing an organic solvent to form a negative pattern,

(wherein R ₁₁ , R ₂₁ , R ₃₁ , R ₄₁ and R ₅₁ each independently represent a hydrogen atom or a methyl group; R ₁₂ represents a hydrogen atom or a -COOCH ₃ group; X represents a methylene group or an oxygen atom; R ₃₂ And R ₄₂ and R ₅₂ each independently represent an alkyl group having a carbon number of 1 to 4; m represents 0 or 1; and n represents 1 or 2).

Here, the negative pattern is a pattern obtained by negative development (developing when the exposure is reduced with respect to the developer, and the exposed portion remains as a pattern, and the unexposed portion is removed).

The sensitizing ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of the present invention is a usual user in pattern formation using ArF exposure. Therefore, in the pattern forming method of the present invention, an inexpensive resin composition which is generally used can be used, and the conventional KrF exposure apparatus can be used, so that cost reduction can be achieved. Further, according to the pattern forming method of the present invention, when a pattern is formed on the step substrate, a good pattern can be obtained.

In the pattern forming method of the present invention, the step of forming a film of a sensitizing ray-sensitive or radiation-sensitive resin composition on a substrate, the step of exposing the film, and the developing step can be carried out by a generally known method.

The developer used in the pattern forming method of the present invention preferably contains a group selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, an ether solvent, and a hydrocarbon solvent. A developer of at least one organic solvent (hereinafter also referred to as an organic developer).

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, and 1-hexanone. 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetamidine acetone, acetone acetone, ionone, diacetone alcohol , Ethyl mercapto methanol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate and the like.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether. Acid ester, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, acetic acid -3-methoxybutyl ester, acetic acid-3-methyl-3-methoxybutyl ester, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, lactate Ester and the like.

Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, and n-nonanol. Alcohol or glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol single A glycol ether solvent such as methyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol.

The ether solvent may, for example, be dioxane or tetrahydrofuran in addition to the above glycol ether solvent.

As the amide-based solvent, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphonium triamine, 1, 3-dimethyl-2-imidazolidinone and the like.

Examples of the hydrocarbon-based solvent include an aromatic hydrocarbon solvent such as toluene or xylene, and an aliphatic hydrocarbon solvent such as pentane, hexane, octane or decane.

The above solvents may be used in a plurality of types, or may be used in combination with a solvent or water other than the above. In order to fully exhibit the effects of the present invention, it is preferred that the water content of the entire developer is less than 10% by mass, and more preferably, it does not substantially contain moisture.

In other words, the amount of the organic solvent to be used in the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more, based on the total amount of the developer. Below mass%.

The vapor pressure of the organic developer is preferably 5 kPa at 20 ° C. Next, it is more preferably 3 kPa or less, and particularly preferably 2 kPa or less. When the vapor pressure of the organic developing solution is 5 kPa or less, the evaporation of the developing solution on the substrate or in the developing tank is suppressed, and the temperature uniformity in the wafer surface is improved, and as a result, the dimensional uniformity in the wafer surface is changed. good.

Specific examples of the vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, and 2 a ketone solvent such as ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone or methyl isobutyl ketone, butyl acetate, amyl acetate, isoamyl acetate, pentane acetate Ester, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, An ester solvent such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate or propyl lactate. Alcohol solvent such as propanol, isopropanol, n-butanol, second butanol, third butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, ethylene glycol, diethyl a glycol solvent such as a diol or a triethylene glycol, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, or triethylene glycol monoethyl ether. , glycol ether solvent such as methoxymethylbutanol, tetrahydrogen Oral ether solvent, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide amine solvent, toluene, xylene, etc. A hydrocarbon solvent, an aliphatic hydrocarbon solvent such as octane or decane.

Specific examples of the vapor pressure of 2 kPa or less which is a particularly preferable range include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, and diisobutylene. Ketone solvents such as ketone, 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, 3-ethoxy Ester ester of ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, n-butanol , an alcohol solvent such as a second butanol, a third butanol, an isobutanol, a n-hexanol, an n-heptanol, an n-octanol or a n-nonanol, or a glycol such as ethylene glycol, diethylene glycol or triethylene glycol. a solvent, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxy methyl butanol, etc. Alcohol ether solvent, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, amide solvent of N,N-dimethylformamide, aromatic hydrocarbon system such as xylene A solvent, an aliphatic hydrocarbon solvent such as octane or decane.

An appropriate amount of a surfactant may be added to the organic developer as needed.

The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or a lanthanoid surfactant can be used. Examples of the fluorine and/or lanthanum-based surfactants include, for example, Japanese Patent Laid-Open No. Sho 62-36663, Japanese Patent Laid-Open Publication No. SHO 61-226746, Japanese Patent Laid-Open No. 61-226745, and Japanese Patent No. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Publication No. 9-5988, U.S. Patent No. 5,405, 720, U.S. Patent No. 5,360,692, U.S. Patent No. 5,529,881, U.S. Patent No. 5,296,330 The surfactant described in the specification, U.S. Patent No. 5, 460, 998, U.S. Patent No. 5,576, 143, U.S. Patent No. 5,294, 511, and U.S. Patent No. 5,824,451 is preferably a nonionic surfactant. The nonionic surfactant is not particularly limited, and a fluorine-based surfactant or a quinone-based surfactant is more preferably used.

The amount of the surfactant to be used is usually 0.001% by mass to 5% by mass, preferably 0.005% by mass to 2% by mass, and more preferably 0.01% by mass to 0.5% by mass based on the total amount of the developer.

For the development method, for example, a method in which a substrate is immersed in a tank filled with a developing solution for a certain period of time (dipping method), a developing solution is accumulated on the surface of the substrate by surface tension, and development is performed for a certain period of time (liquid coating method). A method of spraying a developing solution on a surface of a substrate (spraying method), a method of discharging a developing solution while scanning a developing solution discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method), or the like.

In the case where the above various development methods include the step of ejecting the developing solution from the developing nozzle of the developing device to the resist film, the ejection pressure of the developing solution to be ejected (the flow rate per unit area of the ejected developing solution) is preferably 2 mL/sec/mm ² or less, more preferably 1.5 mL/sec/mm ² or less, still more preferably 1 mL/sec/mm ² or less. There is no lower limit of the specific flow rate, and in consideration of the treatment amount, it is preferably 0.2 mL/sec/mm ² or more.

By setting the discharge pressure of the developer to be discharged to the above range, pattern defects derived from the resist residue after development can be remarkably reduced.

The detailed mechanism is not certain, and it is likely that the pressure of the developer applied to the resist film is reduced by making the discharge pressure within the above range, thereby suppressing The resist film and the resist pattern are inadvertently cut or broken.

Further, the discharge pressure (mL/sec/mm ² ) of the developer is the value of the developing nozzle outlet in the developing device.

The method of adjusting the discharge pressure of the developer may, for example, be a method of adjusting the discharge pressure by a pump or the like, or a method of adjusting the pressure by supplying the pressure from the pressurized storage tank.

Further, after the step of performing development using a developing solution containing an organic solvent, a step of stopping development while replacing the solvent with another solvent may be employed.

The pattern forming method of the present invention may further comprise the step of: (4) washing the developed film with a rinsing liquid containing an organic solvent, after the step of performing development using a developing solution containing an organic solvent.

The rinse liquid used in the rinsing step after the development step is not particularly limited as long as the resist pattern is not dissolved, and a general solution containing an organic solvent can be used. It is preferable to use a rinse liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. .

Specific examples of the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, and the ether solvent are the same as those described for the developer containing the organic solvent.

Examples of the hydrocarbon-based solvent include an aromatic hydrocarbon solvent such as toluene or xylene, and an aliphatic hydrocarbon solvent such as pentane, hexane, octane or decane.

After the step of developing using a developing solution containing an organic solvent, it is more preferred to use a solvent selected from the group consisting of a ketone solvent, an ester solvent, and an alcohol. a step of washing a rinse liquid of at least one organic solvent of a group consisting of a solvent and a guanamine solvent, and more preferably, a step of washing with a rinse liquid containing an alcohol solvent or an ester solvent. It is particularly preferable to carry out the step of washing with a rinse liquid containing a monohydric alcohol, and it is preferable to carry out a step of washing with a rinse liquid containing a monohydric alcohol having 5 or more carbon atoms.

Here, the monohydric alcohol used in the rinsing step may, for example, be a linear, branched or cyclic monohydric alcohol, and specifically, 1-butanol, 2-butanol or 3-methyl-1- can be used. Butanol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentane Alcohol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, etc., particularly preferably a monohydric alcohol having a carbon number of 5 or more. Alcohol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and the like.

The components may be mixed in a plurality of types or may be used in combination with an organic solvent other than the above.

The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly 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 rinse liquid used after the step of developing using the developer containing the organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, preferably at 20 ° C. It is 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface can be improved, and the swelling due to the penetration of the rinse liquid can be further suppressed. The uniformity of the inch is better.

It is also possible to use an appropriate amount of a surfactant in the rinse solution.

In the rinsing step, the wafer subjected to development using the developer containing the organic solvent is subjected to a cleaning treatment using the rinsing liquid containing the organic solvent. The method of the cleaning treatment is not particularly limited, and for example, it can be applied to a method of continuously discharging a rinse liquid on a substrate rotating at a constant speed (spin coating method), and immersing the substrate in a tank filled with a rinse liquid for a certain period of time (dipping method) a method of spraying a rinsing liquid on a surface of a substrate (spraying method), etc., wherein it is preferred to perform a cleaning treatment by a spin coating method, and after the cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm, and the rinsing liquid is self-cleaned. Removed on the substrate. Moreover, it is also preferred to include a heating step (Post Bake) after the rinsing step. The developer and the rinse liquid remaining between the patterns and the inside of the pattern are removed by baking. The heating step after the rinsing step is usually carried out at 40 ° C to 160 ° C, preferably at 70 ° C to 95 ° C, usually for 10 seconds to 3 minutes, preferably for 30 seconds to 90 seconds.

It is also preferred that the pattern forming method of the present invention comprises a pre-heating step (PB; Prebake, pre-bake) after film formation and before the exposure step.

Moreover, it is also preferred to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.

As the heating temperature, both PB and PEB are preferably carried out at 70 ° C to 130 ° C, more preferably at 80 ° C to 120 ° C.

The heating time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 180 seconds, and even more preferably from 30 seconds to 90 seconds.

Heating can be carried out by the usual exposure and the device on the developing machine. The line can also be carried out using a hot plate or the like.

The reaction of the exposed portion is promoted by baking to improve the sensitivity or pattern outline.

The pattern forming method of the present invention may comprise multiple heating steps.

The pattern forming method of the present invention may further comprise a step of developing using an alkaline developing solution.

In the case where the pattern forming method of the present invention further includes a step of developing using an alkaline developing solution, for example, an alkaline aqueous solution of the following compounds may be used: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, Inorganic bases such as sodium metasilicate, ammonia, etc.; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; triethylamine and methyldiethyl Tertiary amines such as amines, alcohol amines such as dimethylethanolamine and triethanolamine, tetra-ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, pyrrole, Such as cyclic amines and the like.

Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution to be used.

The alkali concentration of the alkaline developer is usually from 0.1% by mass to 20% by mass.

The pH of the alkaline developer is usually from 10.0 to 15.0.

Particularly preferred is a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

As the rinsing liquid in the rinsing treatment performed after the alkaline development, pure water may be used, and an appropriate amount of the surfactant may be added and used.

Further, after the development treatment or the rinsing treatment, the treatment for removing the developer or the rinsing liquid adhering to the pattern by the supercritical fluid can be performed.

The pattern forming method of the present invention may comprise a multiple exposure step.

The wavelength of the light source used in the exposure apparatus of the present invention is preferably a KrF excimer laser (248 nm).

The substrate on which the film is formed in the present invention is not particularly limited, and a semiconductor substrate manufacturing step such as IC, a manufacturing process of a circuit substrate such as a liquid crystal or a thermal induction head, and a lithography step of another photosensitive etching process can be used. The substrate to be used is, for example, an inorganic substrate such as ruthenium, SiN or SiO ₂ , or a coated inorganic substrate such as SOG. Further, an organic anti-reflection film may be formed between the film and the substrate as needed.

For example, an anti-reflection film may be provided under the resist. As the antireflection film, any of an inorganic film type of titanium, titanium oxide, titanium nitride, chromium oxide, carbon, amorphous germanium, or the like, and an organic film type containing a light absorbing agent and a polymer material can be used. The former requires a vacuum vapor deposition apparatus, a CVD (chemical vapor deposition) apparatus, a sputtering apparatus, and the like in film formation. Examples of the organic anti-reflection film include an organic anti-reflection film containing a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin, an alkali-soluble resin, and a light absorbing agent described in Japanese Patent Publication No. Hei 7-69611. And a reaction of a maleic anhydride copolymer and a diamine type light absorbing agent described in U.S. Patent No. 5,294,680, a resin binder and a methylol melamine-based thermal crosslinking agent as described in Japanese Patent Laid-Open No. Hei. An organic anti-reflection film of the agent, an acrylic resin type antireflection film having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule, as described in Japanese Patent Laid-Open No. Hei 6-118656, Japanese Patent Application Laid-Open No. Hei 8-87115 An organic anti-reflection film comprising a methylol melamine and a benzophenone-based light absorbing agent, as described in Japanese Patent Application An organic antireflection film or the like in which a low molecular weight light absorbing agent is added to a polyvinyl alcohol resin as described in JP-A No. 8-179509.

Further, the organic anti-reflection film may be a commercially available organic anti-reflection film such as DUV30 series or DUV-40 series manufactured by Brewer Science, Inc., AR-2, AR-3, AR-5 manufactured by Shipley Company, LLC. .

Moreover, it is possible to use an anti-reflection film on the upper layer of the resist as needed.

Examples of the antireflection film include AQUATAR-II, AQUATAR-III, AQUATAR-VII, and the like manufactured by AZ Electronic Materials Co., Ltd.

Furthermore, the present invention also relates to a method of manufacturing an electronic device including the above-described pattern forming method of the present invention, and an electronic device manufactured by the method.

The electronic device of the present invention can be suitably mounted in an electric and electronic device (a home appliance, an OA, a media-related device, an optical device, a communication device, or the like).

<Photosensitized ray-sensitive or radiation-sensitive resin composition>

Hereinafter, a sensitizing ray-sensitive or radiation-sensitive resin composition which can be used in the pattern forming method of the present invention will be described.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention is used for negative development (in the case where exposure is performed, the solubility is reduced with respect to the developer, and the exposed portion remains as a pattern, and the unexposed portion is removed). In other words, the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention can be used as a sensitizing ray-sensitive or radiation-sensitive resin composition for developing an organic solvent used for development using a developing solution containing an organic solvent. Here, the term "organic solvent development" means at least the use of an organic solvent-containing display. The purpose of the step of developing the liquid solution.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is typically a resist composition, and a negative resist composition (i.e., an organic solvent) is preferred from the viewpoint of obtaining a particularly high effect. Resist composition for development). Further, the composition of the present invention is typically a chemically amplified resist composition, particularly a resist composition for KrF exposure.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin (P) which reduces the solubility of a developing solution containing an organic solvent by an action of an acid, and generates an acid by irradiation with actinic rays or radiation. Compound (B). Further, the resist composition may further contain at least one of a solvent, a basic compound, a surfactant, and other additives. Hereinafter, each component will be described in order.

[1] Resin (P)

The resin (P) is a resin having a reduced solubility in a developer containing an organic solvent due to the action of an acid, and has at least one repeating unit represented by at least one of the following general formula (I) and formula (II). (a) and at least one repeating unit (b) represented by at least one of the following general formula (III), general formula (IV) and general formula (V). The repeating unit (b) is a repeating unit having a group which is decomposed by an action of an acid to generate a polar group (hereinafter also referred to as an acid-decomposable group), and the acid-decomposable group may be located in a main chain or a side chain of the resin (P). Or both the main chain and the side chain. The repeating unit (a) is a repeating unit having a lactone structure. When the resin (P) contains a repeating unit having a lactone group, the dissolution contrast with respect to the developer containing the organic solvent can be further improved. Moreover, by using a specific lactone structure, The pattern formation property on the step substrate becomes good.

In the above formula, R ₁₁ , R ₂₁ , R ₃₁ , R ₄₁ and R ₅₁ each independently represent a hydrogen atom or a methyl group.

R ₁₂ represents a hydrogen atom or a -COOCH ₃ group.

X represents a methylene group or an oxygen atom.

R ₃₂ , R ₄₂ and R ₅₂ each independently represent an alkyl group having 1 to 4 carbon atoms.

The alkyl group having 1 to 4 carbon atoms of R ₃₂ , R ₄₂ and R ₅₂ may, for example, be a linear or branched alkyl group having 1 to 4 carbon atoms, and specific examples thereof include a methyl group and an ethyl group. N-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.

R _{32 is} preferably a methyl group, an ethyl group, a n-propyl group or an isopropyl group, more preferably a methyl group, an ethyl group or an isopropyl group.

R _{42 is} preferably a methyl group, an ethyl group, a n-propyl group or an isopropyl group, more preferably a methyl group, an ethyl group or an isopropyl group, and particularly preferably a methyl group or an ethyl group.

R _{52 is} preferably a methyl group, an ethyl group, a n-propyl group or an isopropyl group, more preferably a methyl group, an ethyl group or an isopropyl group, and particularly preferably a methyl group or an ethyl group.

m represents 0 or 1. n represents 1 or 2.

In the resin (P) of the present invention, the content of the repeating unit (a) (in the case where it is contained in a plurality of cases) is not particularly limited, and from the viewpoint of more reliably achieving the effects of the present invention, it is preferred. It is 20 mol% or more, more preferably 25 mol% or more, and particularly preferably 30 mol% or more with respect to all the repeating units in the resin (P). Further, the upper limit is not particularly limited, and from the viewpoint of forming a good pattern, it is preferably 90 mol% or less, more preferably 85 mol% or less.

Further, the content of the repeating unit (b) (in total, when it is contained in a plurality of cases) is not particularly limited, and from the viewpoint of more reliably achieving the effect of the present invention, it is preferably relative to the resin (P). All repeating units are 30 mol% or more, more preferably 35 mol% or more, and particularly preferably 40 mol% or more. Further, the upper limit is not particularly limited, and from the viewpoint of forming a good pattern, it is preferably 90 mol% or less, more preferably 85 mol% or less.

In addition, as for the total content of the content of the repeating unit (a) (the total of the contents in the case of containing a plurality of cases) and the content of the repeating unit (b) (in the case of containing a plurality of cases), the present invention is more reliably achieved. From the viewpoint of the effects of the invention, it is preferably 50 mol% or more, more preferably 65 mol% or more, and particularly preferably 70 mol% or more, based on all the repeating units in the resin (P).

Hereinafter, the repetition represented by the above formula (I) and formula (II) is exemplified Specific examples of the unit (a) and specific examples of the repeating unit (b) represented by the above formula (III) to formula (V), but the present invention is not limited thereto.

[Specific example of the general formula (I)]

[Specific example of the general formula (II)]

[Specific example of the general formula (III)]

[Specific example of the general formula (IV)]

[Specific example of the general formula (V)]

More preferably, the repeating unit (a) comprises at least one repeating unit represented by the formula (I), and the repeating unit (b) comprises at least one repeating unit represented by the formula (IV).

In addition to the above repeating unit (a) and repeating unit (b), the resin (P) can also be used as a resist for adjusting dry etching resistance or standard developer suitability, substrate adhesion, resist profile, and further The resolving power, heat resistance, sensitivity, and the like of the usual essential characteristics have various repeating structural units. Further, the resin (P) may be a resin obtained by mixing two or more kinds of resins.

Hereinafter, a repeating unit which may be included in the resin (P) in addition to the repeating unit (a) and the repeating unit (b) will be described.

[Repeating unit having acid-decomposable group]

The resin (P) may further contain, in addition to the repeating unit (b), a repeating unit having a repeating unit which is decomposed by an action of an acid to generate a polar group (that is, an acid-decomposable group).

In the case where the resin (P) of the present invention contains a repeating unit having an acid-decomposable group in addition to the repeating unit (b), the total content of the resin (P) and the repeating unit (b) is preferably relative to the resin (P). In all of the repeating units, it is 30 mol% or more, more preferably 35 mol% or more, and particularly preferably 40 mol% or more. Further, the upper limit is not particularly limited, and from the viewpoint of forming a good pattern, it is preferably 90 mol% or less, more preferably 85 mol% or less.

[repeating unit having a lactone structure]

The resin (P) may further contain a repeating unit having a lactone structure in addition to the repeating unit (a).

When the resin (P) of the present invention contains a repeating unit having a lactone structure in addition to the repeating unit (a), it is the total of the repeating unit (a) with respect to all the repeating units in the resin (P). The content ratio is preferably 20 mol% or more, more preferably 25 mol% or more, and particularly preferably 30 mol% or more. Further, the upper limit is not particularly limited, and from the viewpoint of forming a good pattern, it is preferably 90 mol% or less, more preferably 85 mol% or less.

[other repeating units]

The resin (P) may further comprise a repeating unit having a polar group (for example, a hydroxyl group, a cyano group, a carboxyl group, etc.), and an alicyclic hydrocarbon structure having a nonpolar group (for example, a cyclohexyl group, a decyl group, an adamantyl group, a repeating unit which does not exhibit acid decomposition property, and a compound having one addition polymerizable unsaturated bond (for example, acrylates, methacrylates, acrylamides, methacrylamides, olefins) A repeating unit obtained by polymerization of a propyl compound, a vinyl ether, a vinyl ester or the like. Thereby, the substrate adhesion and the developer affinity are improved.

In the case where the resin (P) further contains a repeating unit having the above group, the content of the repeating unit is preferably from 1 mol% to 30 mol%, more preferably 3, based on all the repeating units of the resin (P). Mol%~20 mol%, further preferably 5 mol%~15 mol%.

The resin (P) of the present invention can be synthesized in accordance with a usual method (e.g., radical polymerization). For example, a general synthesis method includes a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent and polymerization is carried out by heating; and a monomer species is added dropwise to the heating solvent for 1 hour to 10 hours. The dropwise addition polymerization method or the like of the solution with the initiator is preferably a dropwise addition polymerization method. The reaction solvent may, for example, be a solvent which dissolves the composition of the present invention: an ether such as tetrahydrofuran, 1,4-dioxane or diisopropyl ether or a ketone such as methyl ketone or methyl isobutyl ketone, such as An ester solvent such as ethyl acetate, a guanamine-based solvent such as dimethylformamide or dimethylacetamide, or propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or cyclohexanone to be described later. More preferably, it is polymerized using the same solvent as the solvent used in the photosensitive composition of the present invention. Thereby, the generation of particles during storage can be suppressed.

It is preferred to carry out the polymerization in an inert gas atmosphere such as nitrogen or argon. The polymerization initiation can be carried out by using a commercially available radical initiator (azo initiator, peroxide, etc.) as a polymerization initiator. The radical initiator is preferably an azo initiator, and preferably an azo initiator having an ester group, a cyano group or a carboxyl group. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, 2,2'-azobis(2-methylpropionic acid) dimethyl ester and the like. Add as needed or The initiator is added separately, and after completion of the reaction, the solvent is introduced and the desired polymer is recovered by a method such as powder or solid recovery. The reaction concentration is 5 mass% to 50 mass%, preferably 10 mass% to 30 mass%. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, and more preferably from 60 ° C to 100 ° C.

The weight average molecular weight of the resin (P) is preferably from 1,000 to 200,000, more preferably from 2,000 to 70,000, still more preferably from 3,000 to 50,000, particularly preferably in terms of polystyrene equivalent value by GPC method. It is 5,000~30,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance or dry etching resistance can be prevented, and deterioration of developability or viscosity can be prevented to cause deterioration of film formability.

The degree of dispersion (molecular weight distribution) is usually from 1 to 3, preferably from 1 to 2.6, more preferably from 1 to 2, and particularly preferably from 1.4 to 2.0. The smaller the molecular weight distribution, the more excellent the pattern formation property on the step substrate.

In the present invention, the blending ratio of the resin (P) in the entire composition is preferably from 30% by mass to 99% by mass, more preferably from 60% by mass to 95% by mass, based on all the solids.

Further, the resin of the present invention may be used alone or in combination of two or more. Further, other resins than the above resin (P) may be used in combination within a range that does not impair the effects of the present invention.

Specific examples of the resin (P) are shown below.

[2] A compound which produces an acid by irradiation with actinic rays or radiation (B)

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention contains a compound (B) (hereinafter also referred to as "acid generator (B)") which generates an acid by irradiation with actinic rays or radiation. The acid generator (B) can be suitably selected from the following compounds: photocationic polymerization photoinitiator, photoradical A known compound which produces an acid by irradiation with actinic rays or radiation used in a photoinitiator of a polymerization, a photodegradant of a dye, a photochromic agent, or a micro-resist, and the like, and a mixture thereof.

For example, a diazonium salt, a phosphonium salt, a phosphonium salt, a phosphonium salt, a sulfonium imide sulfonate, an anthraquinone sulfonate, a diazodiazine, a diterpene, an o-nitrobenzene methanesulfonate, preferably an acid The generating agent (B) contains a phosphonium salt or a phosphonium salt.

Further, the compound which generates an acid group or a compound by irradiation with actinic rays or radiation, and which is introduced into the main chain or the side chain of the polymer, for example, can be used in the specification of U.S. Patent No. 3,849,137 and the specification of German Patent No. 3914407. Japanese Patent Laid-Open No. Sho 63-63653, Japanese Patent Laid-Open No. Sho 55-164824, Japanese Patent Laid-Open No. SHO-62-69263, Japanese Patent Laid-Open No. SHO63-146038, Japanese Patent Laid-Open No. 63 The compound described in Japanese Laid-Open Patent Publication No. SHO-63-153029, and the like.

Further, a compound which generates an acid due to light described in the specification of the U.S. Patent No. 3,779,778 and the specification of European Patent No. 126,712 can also be used.

Preferred examples of the compound which is decomposed by irradiation with actinic rays or radiation to generate an acid as the acid generator (B) include the following general formula (ZI), general formula (ZII), and general formula (ZIII). Expressed as a compound.

In the above formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

Z ^- represents a non-nucleophilic anion, preferably a sulfonate anion, a bis(alkylsulfonyl)guanamine anion, a tris(alkylsulfonyl)methide anion, BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- and the like, preferred is the organic anion containing a carbon atom. Preferred organic anions include organic anions represented by the following formulas AN1 to AN3.

In the formula AN1 to the formula AN3, Rc ₁ to Rc ₃ each independently represent an organic group. The organic group in Rc ₁ to Rc ₃ may, for example, be a carbon number of 1 to 30, preferably a substituted alkyl group, a monocyclic or polycyclic cycloalkyl group, a hetero atom-containing cyclic group, or an aromatic group. a group or a plurality of such groups having a single bond, a linking group such as -O-, -CO ₂ -, -S-, -SO ₃ -, -SO ₂ N(Rd ₁ )- or the like. Further, it may form a cyclic structure with other bonded alkyl groups and aryl groups.

Rd ₁ represents a hydrogen atom or an alkyl group, and may form a cyclic structure with the bonded alkyl group or aryl group.

The organic group of Rc ₁ to Rc ₃ may also be an alkyl group substituted with a fluorine atom or a fluoroalkyl group at one position, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. Since the fluorine atom or the fluoroalkyl group has a fluorine acid, the acidity of the acid generated by light irradiation increases, and the sensitivity is improved. When Rc ₁ to Rc ₃ have 5 or more carbon atoms, it is preferred that at least one carbon atom is substituted by a hydrogen atom, and more preferably, the number of hydrogen atoms is more than that of a fluorine atom. Ecological toxicity can be alleviated by the absence of a perfluoroalkyl group having a carbon number of 5 or more.

The carbon number of the organic groups of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is usually from 1 to 30, preferably from 1 to 20.

Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a cyclic structure, and may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group in the ring.

Examples of the group formed by bonding two of R ₂₀₁ to R ₂₀₃ include an alkyl group (for example, a butyl group and a pentyl group).

Specific examples of the organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the compound (ZI-1) and the compound (ZI-2) which will be described later.

Further, it may be a compound having a plurality of structures represented by the general formula (ZI). For example, R can also be a compound having the general formula (ZI) represents the sum of at least ₂₀₁ ~ R ₂₀₃ represented by a general formula (ZI) of the other R ₂₀₁ ~ R ₂₀₃ of a compound of at least one bonding formed Structure of the compound.

More preferably, the (Z1) component is exemplified by the compound (ZI-1) and the compound (ZI-2) described below.

The compound (ZI-1) is at least one of R ₂₀₁ to R ₂₀₃ of the above formula (ZI), which is an aryl group. A compound, that is, a compound having an aryl ruthenium as a cation.

Aryl sulfonium compound may be of the R ₂₀₁ ~ R ₂₀₃ are all aryl groups, may also be R ₂₀₁ ~ R ₂₀₃ is part of an aryl group, an alkyl rest.

Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, and an aryldialkylsulfonium compound.

The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group, a naphthyl group or a fluorenyl group, a heteroaryl group such as an anthracene residue or a pyrrole residue, and more preferably a phenyl group or a hydrazine residue. to When the compound has two or more aryl groups, the two or more aryl groups may be the same or different.

The alkyl group as desired in the aryl hydrazine compound is preferably a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, and a second group. Butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclohexyl and the like.

The aryl group and the alkyl group of R ₂₀₁ to R ₂₀₃ may have an alkyl group (for example, a carbon number of 1 to 15), an aryl group (for example, a carbon number of 6 to 14), or an alkoxy group (for example, a carbon number of 1 to 15). ), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent. Preferred substituents are straight-chain, branched or cyclic alkyl groups having a carbon number of 1 to 12, linear, branched or cyclic alkoxy groups having a carbon number of 1 to 12, and most preferably having a carbon number of 1 ~4 alkyl group, alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted for any of the three R ₂₀₁ to R ₂₀₃ , or all of the three may be substituted. Further, in the case where R ₂₀₁ to R ₂₀₃ are an aryl group, it is preferred that the substituent is substituted for the para position of the aryl group.

Next, the compound (ZI-2) will be described.

The compound (ZI-2) is a compound in the case where R ₂₀₁ to R ₂₀₃ in the formula (ZI) each independently represent an organic group which does not contain an aromatic ring. The aromatic ring herein also includes an aromatic ring containing a hetero atom.

The organic group containing no aromatic ring of R ₂₀₁ to R ₂₀₃ usually has a carbon number of 1 to 30, preferably a carbon number of 1 to 20.

R ₂₀₁ to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, a 2-sided oxyalkyl group, a 2-sided oxycycloalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group. More preferred are linear or branched 2-sided oxyalkyl groups, 2-sided oxycycloalkyl groups, alkoxycarbonylmethyl groups, and most preferably linear or branched 2-sided oxyalkyl groups.

The alkyl group and the cycloalkyl group of R ₂₀₁ to R _{203 are} preferably a linear or branched alkyl group having a carbon number of 1 to 10 (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), A cycloalkyl group having a carbon number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

The 2-sided oxyalkyl group as R ₂₀₁ to R ₂₀₃ may be either a straight chain or a branched one, and preferably a group having a C=O at the 2-position of the above alkyl group.

The 2-sided oxycycloalkyl group of R ₂₀₁ to R ₂₀₃ is preferably a group having >C=O at the 2-position of the above cycloalkyl group.

The alkoxy group in the alkoxycarbonylmethyl group of R ₂₀₁ to R ₂₀₃ is preferably an alkoxy group having a carbon number of 1 to 5 (methoxy group, ethoxy group, propoxy group, butoxy group). Base, pentyloxy).

R ₂₀₁ to R ₂₀₃ may be further substituted by a halogen atom, an alkoxy group (for example, a carbon number of 1 to 5), a hydroxyl group, a cyano group or a nitro group.

Two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a cyclic structure, and may further contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group in the ring. The group formed by bonding two of R ₂₀₁ to R ₂₀₃ may be an alkyl group (for example, a butyl group or a pentyl group).

Next, the general formula (ZII) and the general formula (ZIII) will be described.

In the formula (ZII) and the formula (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group which may have a substituent, an alkyl group which may have a substituent, or a cycloalkyl group which may have a substituent .

Specific examples and preferred examples of the aryl group of R ₂₀₄ to R ₂₀₇ are the same as those described for the aryl group of R ₂₀₁ to R ₂₀₃ in the compound (ZI-1).

Specific examples and preferred examples of the alkyl group and the cycloalkyl group of R ₂₀₄ to R ₂₀₇ and the linear, branched or cyclic alkyl group as R ₂₀₁ to R ₂₀₃ in the compound (ZI-2) The same.

Z ^- in general formula (ZI) in the Z ^- synonymous.

Preferred compounds among the compounds which generate an acid by irradiation with actinic rays or radiation as the acid generator (B) can be further represented by the following formula (ZIV), formula (ZV) and formula (ZVI). Compound.

In the general formula (ZIV) to the general formula (ZVI), Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted aryl group.

R ₂₀₈ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group or a substituted or unsubstituted aryl group in the formula (ZV) and the formula (ZVI). In terms of increasing the strength of the acid generated, it is preferred that R ₂₀₈ is substituted by a fluorine atom.

R ₂₀₉ and R ₂₁₀ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, an alkylthio group or an electron withdrawing group.

Further, R ₂₀₉ and R ₂₁₀ may be bonded to form a cyclic structure. The cyclic structures may also contain an oxygen atom, a sulfur atom, an alkylene group, an alkenyl group, an extended aryl group and the like.

R _{209 is} preferably a substituted or unsubstituted aryl group. R _{210 is} preferably an electron withdrawing group, more preferably a cyano group or a fluoroalkyl group.

A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted extended alkenyl group or a substituted or unsubstituted extended aryl group.

Specific examples of the aryl group of Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R _{210 are} the same as those of the specific examples of the aryl group as R ₂₀₁ to R _{203 in} the above formula (ZI-1).

Specific examples of the alkyl group and the cycloalkyl group of R ₂₀₈ , R ₂₀₉ and R ₂₁₀ may be the same as the specific examples of the alkyl group and the cycloalkyl group as R ₂₀₁ to R _{203 in} the above formula (ZI-2). .

The alkyl moiety of the alkylthio group of R ₂₀₉ and R ₂₁₀ may be the same as the specific example of the alkyl group as R ₂₀₁ to R _{203 in} the above formula (ZI-2).

The alkyl group of A may, for example, be an alkylene group having a carbon number of 1 to 12 (e.g., a methylene group, an exoethyl group, a propyl group, an exo-propyl group, a butyl group, an isobutylene group, etc.), and the elongation of A The cycloalkyl group may be a monocyclic or polycyclic cycloalkyl group having a carbon number of 3 to 12 (e.g., a cyclohexylene group, a decyl group, an adamantyl group, etc.), and an alkenyl group of A may be a carbon number of 2 to 12 alkenyl group (for example, vinyl group, propylene group, butyl group, etc.), and the aryl group of A may be an extended aryl group having a carbon number of 6 to 10 (for example, a phenyl group, a phenylene group) Base, naphthyl, etc.).

Further, a compound having a plurality of structures represented by the formula (ZVI) is also preferred in the present invention. For example, any one of R ₂₀₉ or R ₂₁₀ having a compound represented by the general formula (ZVI) may be bonded to any of R ₂₀₉ or R ₂₁₀ of another compound represented by the general formula (ZVI). Structure of the compound.

As for the compound which is decomposed by irradiation with actinic rays or radiation to generate an acid as the acid generator (B), the solubility of the developer containing the organic solvent from the unexposed portion is good, and development defects are hard to occur. From the viewpoint of the above, a compound represented by the above formula (ZIII) to (ZVI), which is a so-called nonionic compound, is preferred. Among them, a compound represented by the above formula (ZV) or formula (ZVI) is more preferred.

Further, from the viewpoint of improving the acid generation efficiency and the acid strength, the acid generator (B) preferably has a structure in which an acid containing a fluorine atom is generated.

Specific examples of the acid generator (B) are shown below, but are not limited to these specific examples.

The acid generator (B) may be used alone or in combination of two or more. When two or more types are used in combination, it is preferred to combine a compound having two or more different organic acids having two or more atoms other than a hydrogen atom.

For example, from the viewpoint of improving the acid production efficiency and the acid strength, a compound having a structure which generates an acid containing a fluorine atom and a compound having no such structure can be used.

The content of the acid generator (B) in the composition is preferably from 0.1% by mass to 20% by mass based on the total mass of the photosensitive ray-sensitive or radiation-sensitive resin composition, and more preferably 0.5% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass.

[3] Solvent

The solvent which can be used for modulating the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may, for example, be an alkylene glycol monoalkyl ether carboxylate, an alkylene glycol monoalkyl ether or an alkyl lactate. , alkoxypropionic acid alkyl ester, cyclic lactone (preferably having a carbon number of 4 to 10), or a monoketone compound having a ring (preferably having a carbon number of 4 to 10), and a carbonic acid An organic solvent such as an alkyl ester, an alkyl alkoxyacetate or an alkyl pyruvate.

Specific examples of such solvents include those described in [0441] to [0455] of the specification of U.S. Patent Application Publication No. 2008/0187860.

In the present invention, the organic solvent may be used in a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent containing no hydroxyl group are mixed.

As the solvent containing a hydroxyl group and a solvent containing no hydroxyl group, the above-exemplified compounds can be suitably selected, and the solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether or an alkyl lactate, and more preferably a propylene glycol monomethyl ether. (PGME, alias 1-methoxy-2-propanol), ethyl lactate. Further, the solvent containing no hydroxyl group is preferably an alkylene glycol monoalkyl ether acetate, an alkyl alkoxypropionate, a monoketone compound which may also contain a ring, a cyclic lactone, an alkyl acetate, or the like. Particularly preferred among these are propylene glycol monomethyl ether acetate (PGMEA, alias 1-methoxy-2-ethoxypropane propane), ethyl ethoxypropionate, 2-heptanone, γ-butyl The lactone, cyclohexanone, and butyl acetate are most preferably propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, and 2-heptanone.

The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent containing no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. A mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is particularly preferable in terms of coating uniformity.

Preferably, the solvent contains propylene glycol monomethyl ether acetate, preferably propylene glycol monomethyl ether acetate alone solvent or a mixed solvent of two or more kinds of propylene glycol monomethyl ether acetate.

[4] Basic compounds

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may contain a basic compound in order to reduce the change in performance due to the passage of time from exposure to heating.

The basic compound is preferably a compound having a structure represented by the following formula (A) to formula (E).

In the formula (A) and the formula (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each represents a hydrogen atom, an alkyl group (preferably, a carbon number of 1 to 20), a cycloalkyl group. (preferably, the carbon number is 3 to 20) or the aryl group (carbon number is 6 to 20), and here, R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring. 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.

With respect to the above alkyl group, 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.

More preferably, the alkyl groups of the formula (A) and the formula (E) are unsubstituted.

Preferred examples of the compound include anthracene, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc., and more preferred compounds include imidazole structure and dinitrogen. a compound having a heterobicyclic structure, a hydrazine hydroxide structure, a hydrazine carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, having a hydroxyl group and/or an ether An aniline derivative such as a bond.

Examples of the compound having an imidazole structure include imidazole, 2, 4, 5-triphenylimidazole, benzimidazole and the like. 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. The compound having a ruthenium hydroxide structure may, for example, be a triarylsulfonium hydroxide, benzamidine methylhydrazine hydroxide, a phosphonium hydroxide having a 2-sided oxyalkyl group, specifically, triphenylphosphonium hydrogen Oxide, tris(t-butylphenyl)phosphonium hydroxide, bis(t-butylphenyl)phosphonium hydroxide, benzamidine methylthiophene hydroxide, 2-sided oxypropylthiophene鎓 hydroxide and the like. The compound having an oxime carboxylate structure is one in which the anion portion of the compound having a ruthenium hydroxide structure is a carboxylic acid ester, and examples thereof include acetate, adamantane-1-carboxylate, perfluoroalkyl carboxylate, and the like. . Examples of the compound having a trialkylamine structure include tri(n-butyl)amine, tris(n-octyl)amine and the like. Examples of the compound having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, tris(methoxyethoxyethyl)amine, and the like. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

The preferred basic compound may further be an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group.

The amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group are preferably at least one alkyl group bonded to nitrogen. On the atom. Further, it is preferred to have an oxygen atom in the alkyl chain to form an alkyloxy group. The number of alkyloxy groups is one or more in the molecule, preferably from 3 to 9, more preferably from 4 to 6. Preferred among the oxyalkylene groups are structures of -CH ₂ CH ₂ O-, -CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-.

Specific examples of the phenoxy group-containing amine compound, the phenoxy group-containing ammonium salt compound, the sulfonate group-containing amine compound, and the sulfonate group-containing ammonium salt compound include U.S. Patent Application Publication No. 2007/0224539. The compound (C1-1) to the compound (C3-3) exemplified in the specification [0066] are not limited to these compounds.

Further, the above basic compound may be a compound which increases alkalinity due to the action of an acid. Specific examples thereof include the compounds described in JP-A-2007-298569 and JP-A-2009-199021, but are not limited thereto.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention may contain a basic compound or may not be contained. When it is contained, it may be used as a basic compound, and may be composed of a photosensitive ray-sensitive or radiation-sensitive resin. The solid content of the material is usually 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass.

The ratio of the acid generator to the basic compound to be used in the composition is preferably an acid generator/basic compound (mole ratio) = 2.5 to 300. That is, from the viewpoint of sensitivity and resolution, it is preferable that the molar is 2.5 or more, and it is preferable from the viewpoint of suppressing the decrease in resolution due to the coarse resist pattern which passes through the heat treatment after the exposure. It is below 300. The acid generator/basic compound (mole ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

[5] surfactants

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a surfactant or may not be contained. More preferably, it contains a fluorine and/or a lanthanide surfactant (fluorine-based interface). Any one or two or more kinds of the active agent, the lanthanoid surfactant, and the surfactant having both a fluorine atom and a ruthenium atom.

The photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention contains a surfactant, so that when an exposure light source of 250 nm or less, particularly 220 nm or less is used, it is possible to provide adhesion with good sensitivity and resolution. Resist pattern with less defects and development defects.

Examples of the fluorine-based and/or lanthanide-based surfactants include the surfactants described in [0276] of the specification of the US Patent Application Publication No. 2008/0248425, for example, Eftop EF301, EF303, (manufactured by New Akita Chemical Co., Ltd.), Fluorad FC430, FC431, FC4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106, KH-20 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Corporation, Inc.), GF-300, GF-150 (manufactured by Toagosei Synthetic Chemical Co., Ltd.), Surflon S-393 ( SEIMI CHEMICAL Co., Ltd., Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Jemco Co., Ltd.), PF636, PF656, PF6320, PF6520 (OMNOVA) Manufactured by the company, FTX-204G, FTX-208G, FTX-218G, FTX-230G, FTX-204D, FTX-208D, FTX-212D, FTX-218D, FTX-222D (manufactured by Neos Co., Ltd.), etc. Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a lanthanoid surfactant.

Further, in addition to the well-known surfactants as shown above, the surfactant may also be a surfactant which is used by a short-chain polymerization method (also referred to as a short-chain polymer method). Or a fluoroaliphatic polymer derived from a fluoroaliphatic compound produced by a low polymerization method (also referred to as an oligomer method). The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

The surfactants corresponding to the above are exemplified by Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), and having a C ₆ F ₁₃ group. Copolymer of acrylate (or methacrylate) with (poly(oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate) with C ₃ F ₇ group and (poly( Oxyethylene) a copolymer of acrylate (or methacrylate) and (poly(oxypropylene)) acrylate (or methacrylate).

Further, in the present invention, other surfactants other than the fluorine-based and/or lanthanoid surfactants described in [0280] of the specification of U.S. Patent Application Publication No. 2008/0248425 may be used.

These surfactants may be used singly or in combination of several kinds.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a surfactant, and the amount of the surfactant used when the sensitizing ray-sensitive or radiation-sensitive resin composition contains a surfactant The amount of the photosensitive ray-sensitive or radiation-sensitive resin composition (excluding the solvent) is preferably 0.0001% by mass to 2% by mass, more preferably 0.0005% by mass to 1% by mass.

[6] Other additives

The sensitizing ray-sensitive or radiation-sensitive resin composition in the present invention may or may not contain a cerium carboxylate salt. Such a carboxylic acid sulfonium salt can be exemplified in [0605] to [0606] of the specification of US Patent Application Publication No. 2008/0187860.

The cerium carboxylate salts can be synthesized by reacting cerium hydroxide, cerium hydroxide, ammonium hydroxide and a carboxylic acid with silver oxide in a suitable solvent.

When the sensitizing ray-sensitive or radiation-sensitive resin composition contains a cerium carboxylate salt, the content thereof is usually 0.1% by mass to 20% by mass, preferably 0.5% by mass based on the total solid content of the composition. ~10% by mass, more preferably 1% by mass to 7% by mass.

The sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a dye, a plasticizer, a photosensitizer, a light absorbing agent, as needed, An alkali-soluble resin, a dissolution inhibitor, and a compound which promotes solubility in a developing solution (for example, a phenol compound having a molecular weight of 1,000 or less, an alicyclic group having a carboxyl group or an aliphatic compound).

Such a phenolic compound having a molecular weight of 1,000 or less can be referred to, for example, by the method described in Japanese Patent Laid-Open No. Hei 4-122938, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei. The technicians easily synthesize.

Specific examples of the alicyclic or aliphatic compound having a carboxyl group include a carboxylic acid derivative having a steroid structure such as cholic acid, deoxycholic acid, and lithocholic acid, an adamantanecarboxylic acid derivative, an adamantane dicarboxylic acid, and a ring. Hexacarboxylic acid, cyclohexanedicarboxylic acid, etc., but not limited to these compounds.

The photosensitive ray-sensitive or radiation-sensitive resin composition in the present invention is preferably used in a film thickness of 30 nm to 250 nm from the viewpoint of improving the resolution, and more preferably 30 nm to 200 nm. The film thickness is used. By setting the solid content in the composition to a suitable range to have an appropriate viscosity, the coatability and film formability are improved, and the film thickness can be made.

The solid content of the photosensitive ray-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0% by mass to 15% by mass, preferably 2.5% by mass to 13% by mass, more preferably 3.0% by mass to 12% by mass. quality%. By setting the solid content concentration to the above range, the resist solution can be uniformly applied onto the substrate, and a resist pattern having high resolution and a rectangular outline and excellent in etching resistance can be formed. The reason for this is not clear, and it may be that the solid content concentration is 10% by mass or less, preferably 5.7% by mass. Hereinafter, aggregation of the material in the resist solution, particularly the photoacid generator, can be suppressed, and as a result, a uniform resist film can be formed.

The solid content concentration is a weight percentage of the weight of the other resist component excluding the solvent with respect to the total weight of the sensitizing ray-sensitive or radiation-sensitive resin composition.

The resist film of the present invention is a film formed of the above-described sensitized ray-sensitive or radiation-sensitive resin composition, and is formed, for example, by coating a sensitizing ray-sensitive or radiation-sensitive resin composition on a substrate.

In the sensitizing ray-sensitive or radiation-sensitive resin composition of the present invention, the above-mentioned components may be dissolved in a predetermined organic solvent, preferably in the mixed solvent, filtered, and applied to a predetermined support ( Used on the substrate). Preferably, the filter used in the filter filtration has a pore diameter of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less of polytetrafluoroethylene, polyethylene or nylon. Device. In the filter filtration, for example, filtration may be carried out as in the case of JP-A-2002-62667, or a plurality of filters may be connected in series or in parallel to perform filtration. Moreover, the composition can be filtered multiple times. Further, after the filter is filtered, the composition may be subjected to a degassing treatment or the like.

[Example]

Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited thereto.

<Synthesis Example (Synthesis of Resin P-1)>

51.3 parts by mass of cyclohexanone was heated to 80 ° C under a nitrogen stream. While stirring the liquid, the following structural formula A was added dropwise over 4 hours. 27.8 parts by mass of the monomer shown, 21.0 parts by mass of the monomer represented by the following structural formula B, 95.2 parts by mass of cyclohexanone, dimethyl 2,2'-azobisisobutyrate [V-601, and pure light Manufactured by Pharmaceutical Industry Co., Ltd.] 1.73 parts by mass of a mixed solution. After the completion of the dropwise addition, the mixture was further stirred at 80 ° C for 2 hours. After the reaction solution was allowed to stand for cooling, it was reprecipitated by a large amount of hexane/ethyl acetate (mass ratio: 8/2), filtered, and the obtained solid was vacuum dried, whereby the resin of the present invention (P-1) was obtained. ) 45.2 parts by mass.

The weight average molecular weight (Mw: polystyrene conversion) obtained by GPC (carrier: tetrahydrofuran (THF)) of the obtained resin was Mw=15000, and the degree of dispersion was Mw/Mn=1.72. The composition ratio measured by ¹³ C-NMR was 50/50.

The resin P-2 to the resin P-31 were also synthesized in the same manner as the resin P-1. The structure of the synthesized resin P-1 to resin P31 is shown as follows.

The composition ratio, the weight average molecular weight (Mw), and the degree of dispersion (Mw/Mn) of each repeating unit of the above-described synthesized resin are shown in Table 1 below. In Table 1, the order of the numerical values indicating the composition ratio of each repeating unit corresponds to the order of arrangement of the respective repeating units in the structural formula of the resin P-1 to the resin P-31 shown in the above from left to right.

<acid generator>

As the acid generator, the following compound (PAG-1)~ compound (PAG-8) was used.

<alkaline compound>

As the basic compound, the following compound (N-1) to the compound (N-4) was used.

<Surfactant>

The surfactant can be suitably selected from the following (W-1) to (W-6).

W-1: Megafac F176 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.; fluorine system)

W-2: Megafac R08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.; fluorine and lanthanide) W-3: polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.;

W-4: Troysol S-366 (manufactured by Troy Chemical Corporation, Inc.)

W-5: KH-20 (made by Asahi Glass Co., Ltd.)

W-6: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine system)

<solvent>

The solvent can be suitably selected from the following SL-1 to SL-8.

(a group)

SL-1: Propylene glycol monomethyl ether acetate (PGMEA)

SL-2: Propylene glycol monomethyl ether propionate

SL-3: 2-heptanone

(group b)

SL-4: ethyl lactate

SL-5: Propylene Glycol Monomethyl Ether (PGME)

SL-6: cyclohexanone

(c group)

SL-7: γ-butyrolactone

SL-8: propylene carbonate

<Refraction Modification>

The components shown in the following Table 2 were dissolved in the solvent shown in Table 2 at a solid content of 5.10% by mass, and respectively filtered with a polyethylene filter having a pore diameter of 0.1 μm to prepare Examples 1 to 32. A sensitizing ray-sensitive or radiation-sensitive resin composition (resist composition).

In order to evaluate the resist composition prepared as described above, a substrate having a step was prepared, and the pattern formation property of the resist composition on the step substrate was evaluated. This method will be described with reference to Fig. 1 .

<Manufacture of substrate with step difference>

On the Si substrate 1 having a SiO ₂ film 2 having a surface of 500 nm as shown in Fig. 1(a), a positive resist composition 3 (FAiRS-G104; FUJIFILM) was applied as shown in Fig. 1(b). Electronic materials Co., Ltd.) was baked at 100 ° C for 60 seconds with a film thickness of 200 nm. Thereafter, a mask having a line pattern of 220 nm wide at intervals of 180 nm was used, and exposure was performed using an ArF excimer laser (PAS5500/1100 manufactured by ASML), and baking was performed at 95 ° C for 60 seconds. grilled. The exposed wafer was developed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 30 seconds, and then rinsed with pure water and spin-dried to obtain a line portion of 220 nm and a gap portion of 180. Resist pattern of nm (Fig. 1(c)).

With respect to such a patterned wafer, etching treatment was performed for 30 seconds by CF ₄ gas using an etching apparatus (NLD-800 manufactured by ULVAC Co., Ltd.), thereby etching the SiO ₂ film 2 at 100 nm (Fig. 1(d)). The etched wafer was immersed in an alkaline developing solution (TMAH: 2.38%) for 60 seconds to remove the resist composition, thereby producing a substrate having a step as shown in FIG. 1(e). .

<Evaluation of pattern formation on a substrate having a step difference>

On the substrate having the step prepared as described above, the above-described Example 1 to Example 32 were applied so that the film thickness on the convex portion became 150 nm. The resist composition 4 (Fig. 1 (f)) was subjected to a heating step (PB) at 100 ° C for 60 seconds. Thereafter, a mask having a line pattern of 400 nm wide at intervals of 400 nm was used, and exposure was performed using a KrF excimer laser (PAS-5500/850 manufactured by ASML), and subjected to exposure at 110 ° C for 60 seconds. Post-exposure bake (PEB). The exposed wafer was developed using an organic solvent (butyl acetate) for 30 seconds, and then the wafer was rotated at 4000 rpm for 30 seconds, thereby attempting to form a pattern as shown in FIG. 1(g). Show the pattern.

As a result, in the case of using the composition of the present invention, in any of the cases of Examples 1 to 32, the target pattern can be formed on the substrate having the step by KrF exposure.

1‧‧‧Si substrate

2‧‧‧SiO ₂ film

3‧‧‧Positive resist composition

4‧‧‧resist composition

1(a) to 1(g) are views showing a method of fabricating a substrate having a step.

1‧‧‧Si substrate

2‧‧‧SiO ₂ film

3‧‧‧Positive resist composition

4‧‧‧resist composition

Claims (9)

A pattern forming method comprising the steps of: (1) forming a film by using a sensitizing ray-sensitive or radiation-sensitive resin composition, wherein the sensitized ray-sensitive or radiation-sensitive resin composition has a pass At least one repeating unit (a) represented by at least one of the formula (I) and the formula (II), and at least one of the following formula (III), formula (IV) and formula (V) a resin (P) representing at least one repeating unit (b) and a compound (B) which generates an acid by irradiation with actinic rays or radiation; (2) exposing the film by a KrF excimer laser And; (iii) developing the film using a developer containing an organic solvent to form a negative pattern, Wherein R ₁₁ , R ₂₁ , R ₃₁ , R ₄₁ and R ₅₁ each independently represent a hydrogen atom or a methyl group; R ₁₂ represents a hydrogen atom or a -COOCH ₃ group; X represents a methylene group or an oxygen atom; R ₃₂ , R ₄₂ and R ₅₂ each independently represent an alkyl group having 1 to 4 carbon atoms; m represents 0 or 1; and n represents 1 or 2. The pattern forming method according to claim 1, wherein the repeating unit (a) comprises at least one repeating unit represented by the above formula (I), and the repeating unit (b) comprises at least one The repeating unit represented by the above formula (IV). The pattern forming method according to claim 1, wherein the organic solvent contained in the developer is selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. At least one solvent of the group. The pattern forming method according to claim 1, wherein after the step of developing the film by using the developer, the method further comprises: (4) performing the film on the film using a rinsing liquid containing an organic solvent. The steps of cleaning. The pattern forming method according to claim 1, wherein the negative pattern is formed on a step substrate. A sensitizing ray-sensitive or radiation-sensitive resin composition for use in a pattern forming method according to any one of claims 1 to 5. A photosensitive ray-sensitive or radiation-sensitive linear film formed by the sensitizing ray-sensitive or radiation-sensitive resin composition as described in claim 6 of the patent application. A method of manufacturing an electronic device, comprising the pattern forming method according to any one of claims 1 to 5. An electronic device manufactured by the method of manufacturing an electronic device according to claim 8 of the patent application.