KR20140043410A - Method of forming pattern and actinic-ray- or radiation-sensitive resin composition - Google Patents

Abstract

According to one embodiment, (i) at least one repeating unit (a) represented by at least one of the following general formulas (I) and (II) and the following general formulas (III), (IV) and general An inactivation comprising a resin (P) containing at least one repeating unit (b) represented by at least one of formula (V) and further comprising a compound (B) which generates an acid when exposed to actinic radiation or radiation Forming a film with a light- or radiation-sensitive resin composition,
(Ii) exposing the film with a KrF excimer laser, and
(Iii) Developing the said exposure film with the developing solution containing the organic solvent, The pattern formation method characterized by including the process of forming a negative pattern.

Description

Pattern forming method and actinic ray- or radiation-sensitive resin composition {METHOD OF FORMING PATTERN AND ACTINIC-RAY- OR RADIATION-SENSITIVE RESIN COMPOSITION}

The present invention provides a pattern forming method suitably used for semiconductor manufacturing processes such as ICs, the production of circuit boards such as liquid crystals and thermal heads, and other lithography processes used for photofabrication, actinic ray sensitivity used in such methods, or It relates to a radiation sensitive resin composition and an actinic ray sensitive or radiation sensitive film formed from the composition. Moreover, this invention relates to the manufacturing method of the electronic device using the said pattern formation method, and the electronic device manufactured using the said method. The pattern forming method according to the invention is particularly suitable for exposure using a KrF exposure apparatus.

After the appearance of the resist for KrF excimer laser (248 nm), it has been common practice to employ an image forming method using chemical amplification to compensate for any decrease in sensitivity caused by light absorption. First, as an image forming method in the positive chemical amplification method, for example, a photoacid generator contained in an exposed portion is decomposed by light irradiation using an excimer laser, an electron beam, extreme ultraviolet rays, and the like to generate an acid. Then, for example, in the post-exposure bake (post exposure bake: PEB) step, the generated acid is used as the reaction catalyst to convert the alkali insoluble groups contained in the photosensitive composition into alkali-soluble groups. Next, the said exposure part is removed using alkaline solution.

Various alkaline developing solutions have been proposed for use in the above method. For example, the water-soluble alkaline developing solution containing 2.38 mass% TMAH (tetramethylammonium hydroxide aqueous solution) is common.

On the other hand, not only the positive patterning method which is currently mainstream, but also the method using the negative developer, ie, the developer containing the organic solvent, is also developed (for example, refer patent document 1-patent document 3). In the manufacture of semiconductor devices and the like, they reflect a situation in which there is a demand for the formation of patterns having various shapes such as lines, trenches and holes, and there are patterns that are difficult to form using current positive resists.

Recently, the state-of-the-art patterning method under development in negative patterning as well as positive patterning can form high-resolution patterns, including exposure by ArF excimer lasers performed in an immersion method. However, there is a demand for not only miniaturization in semiconductor manufacturing but also promotion of efficient use of existing facilities and cost reduction. Therefore, a method of replacing part of the process previously performed by ArF exposure with KrF exposure is currently being investigated. However, ArF exposure technology now replaces the limitation of KrF exposure. In replacing part of the above-described ArF exposure process with KrF exposure, it is difficult not only to cope with the above miniaturization but also to solve technical problems related to the necessity of improvement of the material (resin, etc.) used, differences in exposure mechanisms, and the like. The current situation is to solve a variety of problems, such as.

Japanese Patent Application Publication (hereinafter, referred to as JP-A-) No. 2010-40849 JP-A-2008-292975 JP-A-2010-217884

An object of the present invention is to provide a pattern forming method which can be carried out at low cost and is excellent in pattern formability on a stepped substrate. Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition used in the above method.

An embodiment of the present invention is as follows.

[1] (i) at least one repeating unit (a) represented by at least one of the following general formulas (I) and (II) and the following general formulas (III), (IV) and (V) Actinic ray sensitivity or sensitivity comprising resin (P) containing at least one repeating unit (b) represented by at least one of and further comprising a compound (B) which generates an acid when exposed to actinic radiation or radiation Forming a film with a radioactive resin composition,

(Ii) exposing the film with a KrF excimer laser, and

(Iv) developing the said exposure film with the developing solution containing the organic solvent, and forming the negative pattern. The pattern formation method characterized by the above-mentioned.

Where R ₁₁ , R ₂₁ , R ₃₁ , and 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 of 1 to 4 carbon atoms,

m is O or 1,

n is 1 or 2.)

[2] The method of [1], wherein the repeating unit (a) includes at least one repeating unit represented by the general formula (I), and the repeating unit (b) is represented by the general formula (IV). Pattern forming method comprising at least one repeating unit.

[3] The organic solvent of [1] or [2], wherein the organic solvent contained in the developer is at least one solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents. The pattern formation method characterized by the above-mentioned.

[4] The pattern formation according to any one of [1] to [3], further comprising the step of (ii) washing the film with a cleaning solution containing an organic solvent after the step of developing the film with the developer. Way.

[5] any one of [1] to [4],

A negative pattern is formed on a stepped substrate.

[6] An actinic ray-sensitive or radiation-sensitive resin composition, which is used in the pattern forming method according to any one of [1] to [5].

[7] An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to [6].

[8] A method for 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 for producing an electronic device according to [8].

The present invention can be carried out at low cost and can be realized to provide a pattern forming method excellent in pattern formability on a stepped substrate. Another object of the present invention makes it possible to provide an actinic ray-sensitive or radiation-sensitive resin composition used in the above method.

1A to 1G are diagrams illustrating a method for producing a stepped substrate.

Hereinafter, the present invention will be described.

Here, with respect to the expression of a group (or atomic group) used in the present specification, an expression not explicitly mentioning whether the group is substituted or unsubstituted includes not only a group having no substituent but also a group having one or more substituents. For example, the expression “alkyl group” includes alkyl groups having no substituent (ie, unsubstituted alkyl groups) as well as alkyl groups having one or more substituents (ie, substituted alkyl groups).

≪ Pattern formation method >

The pattern forming method according to the present invention comprises (i) at least one repeating unit (a) represented by at least one of the following general formulas (I) and (II), the following general formulas (III), (IV) and Persimmon containing resin (P) containing at least one repeating unit (b) represented by at least one of general formula (V), and further including a compound (B) which produces an acid when exposed to actinic light or radiation Forming a film from an actinic ray- or radiation-sensitive resin composition; (ii) exposing the film with a KrF excimer laser; (iv) developing the exposed film with a developer containing an organic solvent to form a negative pattern. It includes.

(In the general 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, and R ₃₂ , R ₄₂ And R ₅₂ each independently represent an alkyl group of 1 to 4 carbon atoms, m is O or 1 and n is 1 or 2.

Here, the term "negative pattern" means a pattern obtained by negative development (a phenomenon in which the exposed portion remains in a pattern while the unexposed portion is dissolved away during exposure due to a decrease in solubility in a developing solution).

Usually, the actinic ray sensitive or radiation sensitive resin composition used for the pattern formation method which concerns on this invention is used for patterning by ArF exposure.

Therefore, not only the low-cost resin composition normally used in the pattern formation method which concerns on this invention can be used, but existing KrF exposure equipment can also be used, and cost reduction can be aimed at. Moreover, the pattern formation method which concerns on this invention can produce a preferable pattern also in the patterning on a stepped board | substrate.

In the pattern forming method according to the present invention, the step of forming a film of actinic ray-sensitive or radiation-sensitive resin composition on a substrate, the step of exposing the film and the step of developing the exposure film are usually carried out by a known method. Can be.

The developer used in the pattern formation method according to the present invention is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents (hereinafter also referred to as organic developer). Is preferred.

As the ketone solvent, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetylcarbinol, Acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate and the like can be enumerated.

As the ester solvent, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monoethyl 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, methyl formate, ethyl formate, butyl formate, Propyl formate, ethyl lactate, butyl lactate, propyl lactate and the like.

Examples of the alcohol solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, Alcohols such as alcohol, n-octyl alcohol or n-decanol; Glycol solvents such as ethylene glycol, diethylene glycol or triethylene glycol; Or glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol Can be.

As said ether solvent, dioxane, tetrahydrofuran, etc. can be mentioned in addition to the above-mentioned glycol ether solvent, for example.

As the amide solvent, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethyl phosphate triamide, 1,3-dimethyl-2-imida Zolidinones and the like can be enumerated.

As said hydrocarbon solvent, aromatic hydrocarbon solvents, such as toluene or xylene, or aliphatic hydrocarbon solvents, such as a pentane, hexane, an octane, or a decane, can be mentioned, for example.

Two or more kinds of these solvents may be mixed together before use. However, each of the solvents may be used for mixing with solvents or water other than those described above. It is preferable that the water content in all the developing solutions is less than 10 mass% from the viewpoint of the full effect of the effect of this invention. It is more preferable that the developer does not substantially contain moisture.

That is, it is preferable that content of the organic solvent in the said organic developing solution exists in the range of 90-100 mass% with respect to the total amount of a developing solution, and 95-100 mass% is more preferable.

5 kPa or less is preferable, as for the vapor pressure in 20 degreeC of the said organic developing solution, 3 kPa or less is more preferable, and 2 kPa or less is the most preferable.

When the vapor pressure of the organic developer is 5 kPa or less, evaporation of the developer on the substrate or the developing cup is suppressed, thereby improving in-plane temperature uniformity of the wafer, thereby improving in-plane dimensional uniformity of the wafer.

Specific examples of the organic developer 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 Ketone solvents such as hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone or methyl isobutyl ketone; Butyl acetate, pentyl acetate, isopentyl 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-ethoxypropio Ester solvents such as ethyl acetate, butyl acetate, butyl acetate, propyl lactate, butyl lactate or propyl lactate; organic solvents such as methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, solvent; Glycol solvents such as ethylene glycol, diethylene glycol or triethylene glycol; Glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethyl butanol; Ether solvents such as tetrahydrofuran; Amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide or N, N-dimethylformamide; Aromatic hydrocarbon solvents, such as toluene or xylene, and aliphatic hydrocarbon solvents, such as octane or decane, are mentioned.

As a specific example of the organic developer which shows the vapor pressure of 2 kPa or less which shows especially preferable range, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diiso Ketone solvents such as butyl ketone, cyclohexanone, methylcyclohexanone or 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-ethoxypropionate, 3-methoxybutyl Ester solvents such as acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate or propyl lactate; alcohol solvents such as n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol or n-decanol; Glycol solvents such as ethylene glycol, diethylene glycol or triethylene glycol; Glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethyl butanol; Amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide or N, N-dimethylformamide; Aromatic hydrocarbon solvents such as xylene; And aliphatic hydrocarbon solvents such as octane or decane.

If necessary, an appropriate amount of surfactant can be added to the organic developer.

The surfactant is not particularly limited. For example, any one of ionic and nonionic fluorine-based and / or silicon-based surfactants can be used. As such a fluorine type and / or silicon type surfactant, JP-A S62-36663, JP-A S61-226746, JP-A S61-226745, JP-A S62-170950, JP-A S63-34540, JP -A H7-230165, JP-A H8-62834, JP-A H9-54432 and JP-A H9-5988, and USP 5405720, USP 5360692, USP 5529881, USP 5296330, USP 5436098, USP 5576143, USP 5294511 and USP What is described in 5824451 can be listed. The said nonionic surfactant is preferable. Although the said nonionic surfactant is not specifically limited, It is more preferable to use a nonionic fluorine-type surfactant or a silicon type surfactant.

Usually, the addition amount of the said surfactant exists in the range of 0.001-5 mass% with respect to the total amount of a developing solution, 0.005-2 mass% is preferable, and its 0.01-0.5 mass% is more preferable.

As the developing method, for example, a method of immersing the substrate in a tank filled with a developer for a predetermined time (immersion method), a method of developing by puddle the developer by the surface tension on the surface of the substrate for a predetermined time (Puddle method), a method of spraying a developer onto the surface of the substrate (spray method), or a method of continuously discharging developer while scanning the developer discharge nozzle at a predetermined speed on a substrate which is rotated at a predetermined speed (dynamic dispensing) Law) can be used.

In the case of various development methods, in the case of including the step of discharging the developer toward the resist film through the developing nozzle of the developing apparatus, the discharge pressure (flow rate per unit area of the developer to be discharged) of the discharged developer is 2 ml / sec / mm 2 or less. Preferably, 1.5 ml / sec / mm 2 or less is more preferable, and 1 ml / sec / mm 2 or less is still more preferable. There is no minimum in particular of the said flow velocity. However, from the viewpoint of throughput, the flow rate is preferably 0.2 ml / sec / mm 2 or more.

By adjusting the discharge pressure of the developer to be discharged to fall within the above range, pattern defects resulting from any resist residue after development can be significantly reduced.

The mechanism is not clear in detail. However, it is estimated that unintentional shaving or collapse of the resist film / resist pattern is suppressed by reducing the pressure of the developer so that the discharge pressure on the resist film is included in the above range.

The discharge pressure (ml / sec / mm 2) of the developing solution means a value indicated at the outlet of the developing nozzle of the developing apparatus.

For adjusting the discharge pressure of the developing solution, for example, a method of adjusting the discharge pressure by a pump or the like or a method in which the discharge pressure is changed by pressure adjustment by supply from a pressure tank may be adopted.

The step of developing with a developer containing the organic solvent may be followed by a step of replacing with another solvent to stop the development.

The pattern formation method which concerns on this invention may further include carrying out the process of wash | cleaning the developed film | membrane with the washing | cleaning liquid containing the organic solvent (d) after the process of developing with the developing solution containing an organic solvent.

The cleaning liquid used in the cleaning step after the developing step is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a conventional organic solvent may be used in the same manner. It is preferable that the said washing | cleaning liquid contains at least 1 organic solvent chosen from the group which consists of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent.

Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are as described above with respect to the developer containing the organic solvent.

The step of developing with the developer containing the organic solvent is preferably a step of washing with a cleaning solution containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents and amide solvents, and alcohol solvents. Or a step of washing with a washing liquid containing an ester solvent is more preferable, a step of washing with a washing liquid containing a monovalent alcohol is more preferable, and a step of washing with a washing liquid containing a monovalent alcohol having five or more carbon atoms is most preferred. desirable.

As monohydric alcohol used for the said washing process, linear, branched, or cyclic monovalent alcohol can be mentioned. Specific examples thereof include 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol , 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol and 4-octanol May be listed. Specific examples of the monovalent alcohol having five or more carbon atoms each include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, and 3-methyl-1-butanol. desirable.

Among these components, two or more kinds may be mixed together before use. Moreover, you may mix with another organic solvent before use.

It is preferable that the moisture content of the said washing | cleaning liquid is 10 mass% or less, 5 mass% or less is more preferable, and 3 mass% or less is the most preferable. By adjusting the water content of the cleaning liquid to 10% by mass or less, desirable developing performance can be obtained.

The vapor pressure at 20 ° C is preferably in the range of 0.05 to 5 kPa, more preferably 0.1 to 5 kPa, and most preferably 0.12 to 3 kPa, with respect to the cleaning solution used after the step of developing with the developer containing the organic solvent. . When the vapor pressure of the cleaning liquid is in the range of 0.05 to 5 kPa, not only the in-plane temperature uniformity of the wafer can be improved, but also the swelling caused by the penetration of the cleaning liquid can be suppressed to improve the in-plane dimensional uniformity of the wafer.

Before use, an appropriate amount of surfactant may be added to the cleaning liquid.

In the cleaning step, the developing wafer is cleaned with the developer containing the organic solvent using the cleaning solution containing the organic solvent. The method of the said washing process is not specifically limited. For example, a method of continuously applying a cleaning liquid onto a substrate being rotated at a predetermined speed (spin coating method), a method of immersing the substrate in a tank filled with the cleaning liquid for a predetermined time (immersion method), and a surface of the substrate Any of the method (spray method) of spraying a washing | cleaning liquid can be used. It is preferable that the said washing process is performed according to the spin coating method, and then the said board | substrate is rotated at the rotational speed of 2000-4000 rpm, and the washing | cleaning liquid is removed from the upper end of a board | substrate. Moreover, it is preferable that a baking process (post baking) is performed after a washing process. All developer and cleaning solution remaining between and within the pattern are removed by the baking process. Usually, the post-baking process after the said washing process is performed at 40-160 degreeC, Preferably it is 70 to 95 degreeC for 10 second-3 minutes, Preferably it is 30 to 90 second.

In the pattern formation method which concerns on this invention, it is preferable that a prebaking (PB) process is performed after a film formation process and before an exposure process.

In addition, it is preferable that post exposure baking (PEB) is performed after an exposure process and before a image development process.

In both the PB and PEB processes, the baking step is preferably performed at 70 to 120 ° C, more preferably 80 to 110 ° C.

It is preferable that the said baking time exists in the range of 30-300 second, 30-180 second is more preferable, and 30-90 second is still more preferable.

In general, the baking process may be performed using a means provided in the exposure / development apparatus. In addition, the baking process may be performed using a hot plate or the like.

The baking process accelerates the reaction of the exposed portion to improve the sensitivity and pattern profile.

The pattern forming method of the present invention may include a plurality of baking processes.

The pattern formation method of this invention may further include the process of developing with alkaline developing solution.

When the pattern formation method according to the present invention further includes a step of developing with an alkaline developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate or ammonia water. Secondary amines such as primary amines such as inorganic alkalis such as inorganic alkali, ethylamine or n-propylamine, diethylamine or di-n-butylamine, tertiary amines such as triethylamine or methyldiethylamine, and dimethylethanol Any of aqueous alkali solutions, such as quaternary ammonium salts, such as alcohol amines, such as an amine or a triethanolamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide, and cycloamines, such as a pyrrole or piperidine, can be used.

Before use, an appropriate amount of alcohol and surfactant may be added to the aqueous alkali solution.

Usually, the alkali concentration of the said alkaline developing solution exists in the range of 0.1-20 mass%.

Usually, the pH value of the said alkaline developing solution exists in the range of 10.0-15.0.

In particular, 2.38 mass% tetramethylammonium hydroxide aqueous solution is preferable.

Pure water is used as a washing | cleaning liquid used for the washing | cleaning process after the said alkali image development.

Before use, an appropriate amount of surfactant may be added.

The developing step or cleaning step may be followed by a step of removing a part of the developing solution or cleaning solution adhered onto the pattern using a supercritical fluid.

The pattern forming method according to the present invention may include a plurality of exposure processes.

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

In this invention, the board | substrate for film formation is not specifically limited. Substrate that is commonly used in the semiconductor manufacturing process, manufacturing a circuit substrate such as a liquid crystal, thermal head step and other photo applications, lithography process, such as IC, for example, silicon, SiN, the coated inorganic such as inorganic substrate and SOG of SiO _2, etc. Substrates and the like can be used. In addition, an organic antireflection film may be formed between the film and the substrate as necessary.

For example, an anti-reflection film may be formed as a lower layer of the resist. As the anti-reflection film, both inorganic films such as titanium, titanium oxide, titanium nitride, chromium oxide, carbon, amorphous silicon, and organic films made of light absorbers and polymer materials can be used. In the film forming step, the former film requires equipment such as a vacuum deposition apparatus, a CVD apparatus, a sputtering apparatus, and the like. As said organic antireflection film, For example, what consists of condensates of the diphenylamine derivative of Unexamined-Japanese-Patent No. 7-69611, and formaldehyde modified melamine resin, alkali-soluble resin, and a light absorber; Consisting of a reactant between the maleic anhydride copolymer described in USP 5294680 and a diamine light absorber; Containing the resin binder according to JP-A-6-118631 and the methylolmelamine thermal crosslinking agent; Acrylic resin antireflection film which has a carboxylic acid group, an epoxy group, and a light absorber as described in JP-A-6-118656 simultaneously in a molecule | numerator; Consisting of methylolmelamine and benzophenone light absorber described in JP-A-8-87115; And those obtained by adding a low molecular light absorber to the polyvinyl alcohol resin described in JP-A-8-179509.

In addition, Brewer Science Inc. as the organic antireflection film. DUV30 series and DUV40 series, and Shipley Co., Ltd. Commercially available organic antireflective films, such as AR-2, AR-3, and AR-5, can be used.

In addition, an antireflection film may be provided as an upper layer of the resist as necessary.

As the anti-reflection film, AZ Electronic Materials Co., Ltd. And AQUATAR-II, AQUATAR-III, AQUATAR-III, and the like.

Moreover, this invention relates to the manufacturing method of the electronic device containing the pattern formation method of this invention, and the electronic device manufactured by the said method.

The electronic device of the present invention can be suitably mounted in electrical and electronic devices (home appliances, OA / media related devices, optical devices, and communication devices).

<Active ray sensitive or radiation sensitive resin composition>

Hereinafter, an actinic ray-sensitive or radiation-sensitive resin composition that can be used in the pattern forming method according to the present invention will be described.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is used for negative development (a phenomenon in which the exposed portion remains as a pattern while the unexposed portion dissolves away due to a decrease in the solubility in the developer during exposure). That is, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may be an actinic ray-sensitive or radiation-sensitive resin composition for organic solvent development used for development using a developer containing an organic solvent. Here, the expression "for developing an organic solvent" means a use including application to a step of developing with a developer containing at least an organic solvent.

Usually, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is a resist composition. In particular, the same thing as a negative resist composition (namely, the resist composition for organic solvent development) is preferable from a viewpoint which high efficiency can be achieved. In addition, the compositions according to the invention are typically chemically amplified resist compositions, in particular KrF exposure resist compositions.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is a resin (P) having a reduced solubility in a developer containing an organic solvent upon the action of an acid and a compound which generates an acid when exposed to actinic rays or radiation ( B). Moreover, the said resist composition may contain at least 1 sort (s) chosen from a solvent, a basic compound, surfactant, and other additives. Hereinafter, the components of these compositions will be described in order.

[1] Resin (P)

The resin (P) is a resin which reduces the solubility in a developing solution containing an organic solvent when acting with an acid, and includes at least one repeating unit represented by at least one of the following general formulas (I) and (II) ( a) and at least one repeating unit (b) represented by the following general formulas (III), (IV) and (V). The repeating unit (b) is a repeating unit containing a group (hereinafter also referred to as an acid decomposable group) that decomposes upon action by an acid to form a polar group. The acid-decomposable group may be located in the main chain or the side chain of the resin (P), or may be located in both the main chain and the side chain. The repeating unit (a) is a repeating unit having a lactone structure. When the repeating unit having the lactone group is contained in the resin (P), the dissolution contrast in the developer containing the organic solvent can be improved. In addition, desirable pattern formation can be realized on the stepped substrate by use of a specific lactone structure.

In the above general 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 -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.

As the alkyl group having 1 to 4 carbon atoms represented by R ₃₂ , R ₄₂ and R ₅₂ , respectively, a linear or branched alkyl group having 1 to 4 carbon atoms may be listed. In particular, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or tert-butyl group may be mentioned.

It is preferable that said R <_32> is a methyl group, an ethyl group, n-propyl group, or an isopropyl group, and it is more preferable that it is a methyl group, an ethyl group, or an isopropyl group.

It is preferable that R <_42> is a methyl group, an ethyl group, n-propyl group, or an isopropyl group, and it is more preferable that it is a methyl group, an ethyl group, or an isopropyl group. Most preferable are the methyl group and the ethyl group.

It is preferable that said R <_52> is a methyl group, an ethyl group, n-propyl group, or an isopropyl group, and it is more preferable that it is a methyl group, an ethyl group, or an isopropyl group. Most preferable are the methyl group and the ethyl group.

In the general formula, m is 0 or 1, n is 1 or 2.

The content of the repeating unit (a) in the resin (P) according to the present invention (in the case where a plurality of other repeating units (a) is contained) is not particularly limited. However, from the viewpoint of reliably achieving the effect of the present invention, the content is preferably 20 mol% or more, more preferably 25 mol% or more, and most preferably 30 mol% or more based on the total repeating units of the resin (P). Do. There is no particular upper limit of the content. However, from the viewpoint of forming a preferred pattern, the content is preferably 90 mol% or less, more preferably 85 mol% or less.

The content of the repeating unit (b) (or the sum thereof when a plurality of other repeating units (b) is contained) is not particularly limited. However, from the viewpoint of reliably achieving the effect of the present invention, the content is preferably 30 mol% or more, more preferably 35 mol% or more, and most preferably 40 mol% or more based on the total repeating units in the resin (P). Do. There is no particular upper limit of this content. However, from the viewpoint of forming a preferred pattern, the content is preferably 90 mol% or less, more preferably 85 mol% or less.

In addition, the content of the repeating unit (a) (the sum thereof when a plurality of other repeating units (a) is contained) and the content of the repeating unit (b) (a plurality of different repetitions) in view of reliably achieving the effect of the present invention. In the case where the unit (b) is contained, the sum thereof is preferably 50 mol% or more, more preferably 65 mol% or more, and most preferably 70 mol% or more with respect to all the repeating units of the resin (P). Do.

Specific examples of the repeating unit (a) of the general formulas (I) and (II) and specific examples of the repeating unit (b) of the general formulas (III) to (V) are shown below. It does not limit the scope of the invention.

[Specific example of general formula (I)]

Specific examples of general formula (II)

Specific examples of general formula (III)

[Specific example of general formula (IV)]

[Specific example of general formula (V)]

The repeating unit (a) includes at least one repeating unit represented by formula (I), and the repeating unit (b) includes at least one repeating unit represented by formula (IV).

In addition to the repeating unit (a) and the repeating unit (b), the resin (P) adjusts properties of commonly required resists such as dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance and sensitivity. It may contain various repeating structural units in order to do so. The said resin (P) may combine 2 or more types of other resin (P).

Hereinafter, the repeating unit which may be contained in the said resin (P) other than the said repeating unit (a) and repeating unit (b) is demonstrated.

[Repeating Unit Containing Acid Degradable Group]

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

When the resin (P) according to the present invention contains an acid decomposable group in addition to the repeating unit (b), the total content of these and the repeating unit (b) is 30 mol% or more based on the total repeating units of the resin (P). Preferably, 35 mol% or more is more preferable, and 40 mol% or more is the most preferable. There is no particular upper limit of this content. However, from the viewpoint of forming a preferred pattern, the content is preferably 90 mol% or less, more preferably 85 mol% or less.

[Repeating unit having a lactone structure]

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

When the resin (P) according to the present invention contains a repeating unit having a lactone structure in addition to the repeating unit (a), the content of the sum of these and the repeating unit (a) is in the total repeating units of the resin (P). 20 mol% or more is preferable, 25 mol% or more is more preferable, and 30 mol% or more is the most preferable. There is no particular upper limit of this content. However, from the viewpoint of forming a preferred pattern, the content is preferably 90 mol% or less, more preferably 85 mol% or less.

[Other repeating units]

The said resin (P) is a repeating unit containing a polar group (for example, a hydroxyl group, a cyano group, a carboxyl group, etc.), and an alicyclic hydrocarbon structure which does not have a polar group which does not show acid decomposability (for example, a cyclohexyl group, Compounds having repeating units having a norbornyl group, adamantyl group, tricyclodecanyl group and the like and unsaturated bonds capable of addition polymerization (e.g., acrylic esters, methacryl esters, acrylamides, methacrylamides, allyl compounds) , Vinyl ether, vinyl ester, etc.) may further contain a repeating unit obtained by polymerization. By containing these other repeating units, adhesiveness to a substrate and developer affinity are improved.

When the said resin (P) contains these other repeating units further, it is preferable that the content exists in the range of 1-30 mol% with respect to all the repeating units of resin (P), and 3-20 mol% is more preferable. 5-15 mol% is more preferable.

Resin (P) according to the present invention can be synthesized according to a conventional method (for example, radical polymerization). As a general synthesis method, for example, a batch polymerization method in which polymerization is performed by dissolving a monomer species and an initiator in a solvent and heating, and a dropwise polymerization method in which a solution of the monomer species and an initiator is added dropwise to a heating solvent over 1 to 10 hours, etc. May be listed. The dropwise polymerization method is preferred. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane or diisopropyl ether, ketones such as methyl ethyl ketone or methyl isobutyl ketone, ester solvents such as ethyl acetate, dimethylformamide or Amide solvents such as dimethylacetamide, or solvents capable of dissolving the composition of the present invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or cyclohexanone, described below. It is preferable to perform the said polymerization using the same solvent as the solvent used for the photosensitive composition which concerns on this invention. This suppresses the generation of particles during storage.

It is preferable that the said polymerization reaction is performed in the atmosphere which consists of inert gas, such as nitrogen or argon. The polymerization is initiated by the use of a commercially available radical initiator (azo initiator, peroxide, etc.) as the polymerization initiator. Among the radical initiators, azo initiators are preferred, and azo initiators having ester groups, cyano groups and carboxyl groups are particularly preferred. As particularly preferred initiators, there may be mentioned azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. As necessary, the initiator may be supplemented or added in fractions. After completion of the reaction, the reaction solution is poured into a solvent, and the target polymer is recovered by a method such as powder or solid content recovery. The said reaction concentration exists in the range of 5-50 mass%, and 10-30 mass% is preferable. Usually, the said reaction temperature exists in the range of 10-150 degreeC, 30-120 degreeC is preferable and 60-100 degreeC is more preferable.

It is preferable that the mass mean molecular weight of the said resin (P) exists in the range of 1,000-200,000 in polystyrene conversion value measured by GPC. It is more preferable to exist in the range of 2,000-70,000, 3,000-50,000 are still more preferable, 5,000-30,000 are the most preferable. By adjusting the mass average molecular weight so as to fall within the range of 1,000 to 200,000, not only the deterioration of heat resistance and dry etching resistance can be prevented, but also the deterioration of developability and an increase in viscosity leading to deterioration of film formation can be prevented.

Usually, the polydispersity (molecular weight distribution) of the said resin exists in the range of 1-3, 1-2.6 are preferable, 1-2 are more preferable, and 1.4-2.0 are the most preferable. The narrower the molecular weight distribution, the easier the pattern formation on the stepped substrate is.

In this invention, it is preferable that it is in the range of 30-99 mass% with respect to the total solid of a composition, and, as for the quantity of resin (P) contained in a whole composition, 60-95 mass% is more preferable.

Resin which concerns on this invention may be used individually by 1 type, and may be used in combination of 2 or more type. You may use combining resin other than the said resin (P) in the quantity which does not impair the effect of this invention.

Hereinafter, the specific example of the said resin (P) is shown.

[Compound (B) to generate acid when exposed to actinic light or radiation]

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may contain a compound (B) (hereinafter referred to as an acid generator (B)) that generates an acid when exposed to actinic light or radiation. As said acid generator (B), the well-known compound which produces | generates an acid when exposed to actinic light or radiation used for photocationic polymerization photoinitiator, photoradical polymerization photoinitiator, pigment | dye photochromic agent, photochromic agent, microresist, etc. And one kind appropriately selected from the mixtures thereof.

As the acid generator (B), diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imide sulfonate, oxime sulfonate, diazo sulfone, disulfone and o-nitrobenzyl sulfonate can be exemplified. . It is preferable that the said acid generator (B) contains a sulfonium salt or an iodonium salt.

In addition, compounds obtained by introducing any of the groups or compounds which generate acids when exposed to actinic radiation or radiation into the polymer backbone or side chain, for example USP 3,849,137, DE 3914407, JP-A-63-26653, JP- Compounds described in A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029 and the like can be used. Can be.

In addition, compounds which generate an acid when exposed to those described in USP 3,779,778, EP 126,712 and the like can be used.

As a compound which is preferable as an acid generator (B) among the compounds which generate | occur | produce an acid when exposed to the said actinic light or a radiation, what is represented by the following general formula (ZI), general formula (ZII), and general formula (ZIII) is illustrated. Can be.

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

Z ^- represents an acetonucleophilic anion.

As the non-nucleophilic anion represented by, sulfonate anion, a bis (alkylsulfonyl) amido anion, a tris (alkylsulfonyl) methyl anion, BF ₄ ^{- -} wherein Z can be exemplified by ^-, PF ₆ ^- and SbF ₆ . Z ⁻ is an organic anion containing one or more carbon atoms. As a preferable organic anion, any of what is shown by following ANl-AN3 can be illustrated.

In the general formulas ANl to AN3, Rc ₁ to Rc ₃ each independently represent an organic group. Examples of the organic group may include 1 to 30 carbon atoms. A substituted or unsubstituted alkyl group, a monocyclic or polycyclic cycloalkyl group, a hetero atom-containing cyclic group, an aryl group, or a group in which these groups are connected by a single bond or a linking group is preferable. As the linking group, for example, -0-, -CO _2- , -S-, -SO ₃ -and -S0 ₂ N (Rd ₁ )-can be exemplified. In addition, these groups may form a ring together with a bonding alkyl group or an aryl group.

Here, Rd ₁ may represent a hydrogen atom or an alkyl group, and may form a ring with a bonding alkyl group or an aryl group.

The organic group represented by Rc ₁ to Rc ₃ is an alkyl group in which the 1-position is substituted with a fluorine atom or a fluoroalkyl group; Or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. The presence of the fluorine atom or the fluoroalkyl group can further increase the acidity of the acid generated by light irradiation. This can improve the sensitivity of the composition. When Rc ₁ to Rc ₃ contain 5 or more carbon atoms, at least one of the carbon atoms is preferably substituted with a hydrogen atom (s), and the number of the hydrogen atoms is preferably larger than the number of fluorine atoms. . And any perfluoroalkyl group of at least 5 carbon atoms is present in Rc ₁ to Rc ₃ If not contained, toxicity to the living body can be reduced.

Usually, the number of carbon atoms in the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is in the range of 1 to 30, with 1 to 20 being preferred.

Two of R ₂₀₁ to R ₂₀₃ may combine with each other to form a ring. An oxygen atom, a sulfur atom, an ether bond, an amido bond, and a carbonyl group may be contained in the ring. As a group formed by two bonds of said R <_201> -R <_203> , alkylene groups, such as a butylene group and a pentylene group, can be illustrated, for example.

As specific examples of the organic groups as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , groups corresponding to the compound (ZI-1), the compound (ZI-2) or the compound (ZI-3) described below can be exemplified.

The compound which has two or more structures represented by the said general formula (ZI) can be used suitably. For example, R ₂₀₁ to R ₂₀₃ of the compound represented by General Formula (ZI). At least one of R ₂₀₁ to R ₂₀₃ represented by general formula (ZI) You may use the compound which has a structure couple | bonded with at least another of these.

As a preferable (ZI) component, the following compound (ZI-1) and compound (ZI-2) can be illustrated.

The compound (ZI-1) is an arylsulfonium compound of the general formula (ZI) in which at least one of R ₂₀₁ to R ₂₀₃ is an aryl group, that is, a compound containing arylsulfonium as a cation.

In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be aryl groups. In addition, it is preferable that R <_201> -R <_203> is a partially aryl group, and the remainder is an alkali group or a cycloalkyl group.

As said arylsulfonium compound, a triarylsulfonium compound, a diarylalkylsulfonium compound, and an aryldialkylsulfonium compound can be mentioned, for example.

The aryl group in the arylsulfonium compound is preferably an aryl group such as a phenyl group, a naphthyl group and a fluorene group or a heteroaryl group such as an indole group and a pyrrole group. Among these, a phenyl group or an indole group is especially preferable. When the arylsulfonium compound contains two or more aryl groups, these may be the same as or different from each other.

As needed, it is preferable that the alkyl group or cycloalkyl group contained in the said arylsulfonium compound is a C1-C15 linear or branched alkyl group, or a C3-C15 cycloalkyl group. For example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group, etc. can be mentioned.

The aryl group, alkyl group or cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ may have one or more substituents. As the substituent, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms), an alkoxy group (For example, 1-15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group can be illustrated.

The substituent is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms. As for the said substituent, it is more preferable that they are a C1-C4 alkyl group and a C1-C4 alkoxy group. The substituents may be contained in any one of three R ₂₀₁ ~ R _203, it may be contained in all of the three R ₂₀₁ ~ R _203. When R ₂₀₁ to R ₂₀₃ represent an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) is described.

The compound (ZI-2) is a compound of the formula (ZI) in which R ₂₀₁ to R ₂₀₃ each independently represent an organic group having no aromatic ring. The aromatic ring includes an aromatic ring having a hetero atom.

Usually, the organic group which does not have the aromatic ring represented by R <_201> -R <_203> is 1-30 carbon atoms, and 1-20 carbon atoms are preferable.

R ₂₀₁ to R ₂₀₃ each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group. The group is more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group and an alkoxycarbonylmethyl group. Particular preference is given to such linear or branched 2-oxoalkyl groups.

As a preferable alkyl group and cycloalkyl group represented by said R <_201> -R <_203> , a linear or branched alkyl group of 1-10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group) and a carbon atom 3- Ten cycloalkyl groups (cyclopentyl group, cyclohexyl group or norbornyl group) can be enumerated.

The 2-oxoalkyl group of R ₂₀₁ to R ₂₀₃ may be linear or branched. It is preferable that it is a group which has> C = 0 in the 2-position of the said alkyl group.

The 2-oxocycloalkyl group of R ₂₀₁ to R ₂₀₃ is preferably a group having> C = 0 at the 2-position of the cycloalkyl group.

Preferred alkoxy moieties in the alkoxycarbonylmethyl group include alkoxy groups having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group and pentoxy group).

R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group and / or a nitro group.

R ₂₀₁ to R ₂₀₃ 2 of It may combine with each other, and may form ring structure, and the ring in these may further contain an oxygen atom, a sulfur atom, an ester bond, an amido bond, or a carbonyl group. As a group formed by the said ring formation, alkylene groups, such as a butylene group and a pentylene group, can be illustrated.

Hereinafter, general formula (ZII) and general formula (ZIII) are demonstrated.

In the above general formula (ZII) and general formula (ZIII),

Each of R ₂₀₄ to R ₂₀₇ independently represents an aryl group, an alkyl group or a cycloalkyl group. These groups may contain one or more substituents.

As a preferable aryl group represented by said R <_204> -R <_207> , What was described about R <_201> -R <_203> in a compound (ZI-1) can be illustrated.

As preferred alkyl groups and cycloalkyl groups, those described for R ₂₀₁ to R ₂₀₃ in the compound (ZI-2) May be exemplified.

Z <^-> in the said general formula (ZII) and general formula (ZIII) is the same as that of general formula (ZI).

As another example of a compound which produces an acid when exposed to actinic light or radiation as the photoacid generator (B), a compound represented by the following general formula (ZIV), general formula (ZV) or general formula (ZVI) is exemplified. Can be.

In the said general formula (ZIV)-general formula (ZVI),

Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted aryl group.

R 2 _O8 is Independently of each other An alkyl group, a cycloalkyl group, or an aryl group is represented. These groups may be substituted or unsubstituted.

These groups are preferably substituted with one or more fluorine atoms. This makes the acidity of the acid produced by the photoacid generator even higher.

R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an alkylthio group or an electron withdrawing group. These groups may be substituted or unsubstituted. R ₂₀₉ and R ₂₁₀ may be bonded to each other to form a ring structure, and the ring therein may contain an oxygen atom, a sulfur atom, an alkylene group, an alkenylene group, or an arylene group.

As preferred R ₂₀₉ , substituted or unsubstituted aryl groups can be exemplified. As preferred R ₂₁₀ , electron withdrawing groups can be exemplified. Among these, a cyano group or a fluoroalkyl group is more preferable.

A represents an alkylene group, a cycloalkylene group, an alkenylene group or an arylene group. These groups may contain one or more substituents.

As specific examples of the aryl groups represented by Ar ₃ , Ar ₄ , R 2 _{O 8} , R ₂₀₉ and R ₂₁₀ , the same aryl groups as described for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ can be exemplified.

As specific examples of the alkyl group and cycloalkyl group represented by R _{2 O 8} , R ₂₀₉ and R ₂₁₀ , for example, R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in General Formula (ZI-2) may be described. The same alkyl and cycloalkyl groups as may be exemplified.

As specific examples of the alkyl moiety of the alkylthio group represented by R ₂₀₉ and R ₂₁₀ , for example, R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in General Formula (ZI-2) may be described. The same alkyl group as may be exemplified.

As an alkylene group represented by said A, the alkylene group of 1-12 carbon atoms, such as a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, can be illustrated, for example. As a cycloalkylene group represented by A, the monocyclic or polycyclic cycloalkylene group of 3-12 carbon atoms, such as a cyclohexylene group, a norbornylene group, an adamantylene group, can be illustrated, for example. As an alkenylene group represented by said A, the alkenylene group of 2-12 carbon atoms, such as an ethenylene group, a propenylene group, butenylene group, can be illustrated, for example. As an arylene group represented by said A, the arylene group of 6-10 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, can be illustrated, for example.

In addition, compounds having a plurality of structures represented by the general formula (ZVI) can be preferably used in the present invention, respectively. For example, R ₂₀₉ or R ₂₁₀ of the compound of general formula (ZVI). Whichever R ₂₀₉ or R ₂₁₀ of other compounds of formula (ZVI) Compounds having a structure bonded to any one of them can be preferably used.

As the acid generator (B), among the compounds which decompose when exposed to actinic radiation or radiation to generate an acid, the compounds of the above general formulas (ZIII) to (ZVI), that is, so-called nonionic compounds contain an organic solvent. The solubility of the unexposed part in a developing solution is high, and it is preferable from a viewpoint of suppressing generation | occurrence | production of a developing fault. In particular, the compound of the said general formula (ZV) and general formula (ZVI) is more preferable.

Moreover, it is preferable that an acid generator (B) has a structure which can produce the acid containing a fluorine atom from a viewpoint of improving the efficiency of acid generation and acid strength.

Hereinafter, although the specific example of a photo-acid generator (B) is shown, it does not limit the scope of the present invention.

The said acid generator (B) may be used individually by 1 type, and may be used in combination of 2 or more type. When using in combination of 2 or more types of said acid generators (B), it is preferable to use the combination of the compound which produces 2 types of organic acids in which 2 or more atoms differ with respect to all the atomic numbers except a hydrogen atom.

For example, a form in which a compound having a structure capable of generating an acid containing a fluorine atom in combination with a compound not having such a structure may be enumerated in view of improving the efficiency of acid generation and acid strength.

It is preferable that content of the said photo-acid generator (B) exists in the range of 0.1-20 mass% with respect to the total solid of an actinic-ray-sensitive or radiation-sensitive resin composition, 0.5-15 mass% is more preferable, 1- 10 mass% is more preferable.

[3] solvents

As a solvent that can be used to prepare the actinic ray- or radiation-sensitive resin composition according to the present invention, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate , Organic solvents such as cyclolactone (preferably 4 to 10 carbon atoms), cyclic monoketone compounds (preferably 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates and alkyl pyruvates Can be illustrated.

As specific examples of these solvents, for example, those described in paragraphs [0441] to [0445] of US Patent Application Publication No. 2008/0248425 can be enumerated.

In the present invention, a mixed solvent comprising a mixture of a solvent having a hydroxy group and a solvent having no hydroxy group in its structure can be used as the organic solvent.

As the solvent having a hydroxy group and the solvent having no hydroxy group, the compounds exemplified above can be suitably used. As the solvent having the hydroxy group, alkylene glycol monoalkyl ether and ethyl lactate can be exemplified. Among these, propylene glycol monomethyl ether (PGME, also called l-methoxy-2-propanol) and ethyl lactate are more preferable. Examples of the solvent having no hydroxy group include alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compounds which may have a ring structure, cyclic lactones and alkyl acetates. Among these, propylene glycol monomethyl ether acetate (also referred to as PGMEA, l-methoxy-2-acetoxy propane), ethyl ethoxy propionate, 2-heptanone, γ-butyl lactone, cyclohexanone or butyl acetate More preferred is propylene glycol monomethyl ether acetate, ethylethoxypropionate or 2-heptanone.

When using the mixed solvent which consists of a mixture of the solvent which has a hydroxyl group in a structure, and the solvent which does not have a hydroxyl group, it is preferable that the mass ratio between them exists in the range of 1/99-99/1, and 10/90-90/10 More preferably, 20/80-60/40 are still more preferable. From the viewpoint of uniform applicability, a mixed solvent containing 50% by mass or more of the solvent having no hydroxyl group is particularly preferable.

The solvent preferably contains propylene glycol monomethyl ether acetate. More preferred is a single solvent of propylene glycol monomethyl ether acetate or a mixture of two or more solvents containing propylene glycol monomethyl ether acetate.

[4] Basic compounds

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound in order to reduce any performance change with time from exposure to baking.

As said preferable basic compound, the compound which has a structure represented by the following general formula (A)-general formula (E) can be illustrated.

In the said general formula (A) and general formula (E),

R ^200, R ²⁰¹ and R ²⁰² are each independently a hydrogen atom, an alkyl group (preferably a carbon atom 1 to 20), a cycloalkyl group (preferably carbon atoms 3-20) or aryl group (the carbon atoms 6 to 20 ). R 2 ^{O 1} and R ²⁰² may be bonded to each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ each independently represent an alkyl group having 1 to 20 carbon atoms.

With respect to the alkyl group, preferable substituted alkyl groups may be exemplified by 1-20 carbon atoms, hydroxyalkyl groups of 1-20 carbon atoms and cyanoalkyl groups of 1-20 carbon atoms. It is more preferable that the alkyl group in the general formula (A) and the general formula (E) is amorphous.

As preferable basic compounds, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine and piperidine can be exemplified. As a more preferable compound, an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, a compound having an aniline structure or a pyridine structure, an alkyl having a hydroxy group and / or an ether bond Amine derivatives and aniline derivatives having hydroxyl groups and / or ether bonds can be exemplified.

As the compound having the imidazole structure, imidazole, 2,4,5-triphenylimidazole and benzimidazole can be exemplified. Examples of the compound having the 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 can be exemplified. Examples of the compound having an onium hydroxide structure include triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodine hydroxide, and phenacylthiophenium hydroxide Triarylsulfonium hydroxides, such as a roxide and 2-oxopropylthiophenium hydroxide, a phenacylsulfonium hydroxide, sulfonium hydroxide which has a 2-oxoalkyl group can be illustrated. As the compound having an onium carboxylate structure, a compound having a carboxylate at an anion site of a compound having an onium hydroxide structure such as acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate This can be illustrated. As the compound having the trialkylamine structure, tri (n-butyl) amine and tri (n-octyl) amine can be exemplified. As the aniline compound, 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline and N, N-dihexyl aniline can be exemplified. As the alkylamine derivative having the hydroxy group and / or the ether bond, ethanolamine, diethanolamine, triethanolamine and tris (methoxyethoxyethyl) amine can be exemplified. As the aniline derivative having the hydroxy group and / or the ether bond, N, N-bis (hydroxyethyl) aniline can be exemplified.

As preferable basic compounds, further exemplified are amine compounds having a phenoxy group, ammonium salt compounds having a phenoxy group, amine compounds having a sulfonic acid ester group, and ammonium salt compounds having a sulfonic acid ester group.

In the amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group, at least one alkyl group is preferably bonded to a nitrogen atom. More preferably, an oxygen atom is contained in the chain of the alkyl group to form an oxyalkylene group. One or more are preferable with respect to the number of oxyalkylene groups in each molecule, 3-9 are more preferable, and 4-6 are more preferable. Among these oxyalkylene groups, groups of the general formula -CH ₂ CH ₂ O-, the general formula -CH (CH ₃ ) CH ₂ 0- and the general formula -CH ₂ CH ₂ CH ₂ 0- are particularly preferable.

As specific examples of these compounds, compounds (C1-1) to (C3-3) illustrated in paragraph [0066] of US Patent Application Publication No. 2007/0224539 A may be listed.

The basic compound may be a compound in which the basicity is increased by the action of an acid. As specific examples of these compounds, for example, compounds described in JP-A-2007-298569 and JP-A-2009-199021 may be listed, but are not limited thereto.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may or may not contain a basic compound. When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a basic compound, the total amount of the basic compound is usually 0.001 to 10% by mass relative to the solids content of the actinic ray-sensitive or radiation-sensitive resin composition. , And 0.01-5 mass% is preferable.

It is preferable that the ratio (molar ratio) of an acid generator and a basic compound exists in the range of 2.5-300 with respect to the ratio between an acid generator and a basic compound used for the said composition. A molar ratio of 2.5 or more is preferable in view of sensitivity and resolution. The molar ratio of 300 or less is preferable from the viewpoint of suppressing a reduction in resolution due to pattern thickening with time after exposure and baking treatment. The ratio (molar ratio) of the acid generator and the basic compound is more preferably in the range of 5.0 to 200, and still more preferably 7.0 to 150.

[5] Surfactants

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may or may not contain a surfactant. In the case of containing a surfactant, any one of fluorine-based and / or silicon-based surfactants (fluorine-based surfactants, silicon-based surfactants or surfactants having both a fluorine atom and a silicon atom) or two or more of these surfactants may be added to the composition. It is preferable to contain.

When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains the above-mentioned surfactant, adhesion and development defects are realized by realizing desirable sensitivity and resolution in the use of an exposure light source of 250 nm or less, especially 220 nm or less. Less resist pattern can be produced.

As the fluorine-based and / or silicon-based surfactants, for example, those described in paragraph [0276] of US Patent Application Publication No. 2008/0248425 can be enumerated. Also useful as commercially available surfactants are Eftop EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florad FC 430, FC 431 and FC 4430 (manufactured by Sumitomo 3M Ltd.), Megafac F171, F173, F176, F189 , F113, F110, F177, F120 and R08 (manufactured by Dainippon Ink & Chemicals, Inc.), Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 and KH-20 (manufactured by Asahi Glass Co., Ltd.) ), Troy Sol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300 and GF-150 (manufactured by TOAGOSEI CO., LTD.), Sarfron S-393 (manufactured by SEIMI CHEMICAL CO., LTD.), Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 and EF601 (manufactured by JEMCO INC.), PF636, PF656, PF6320 and PF6520 (manufactured by OMNOVA), and FTX-204G, FTX-208G, Fluorine-type surfactants or silicon-based surfactants, such as FTX-218G, FTX-230G, FTX-204D, FTX-208D, FTX-212D, FTX-218D, and FTX-222D (made by NEOS), can be illustrated. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) may be used as the silicon-based surfactant.

As the surfactant, on the basis of a polymer having a fluorinated aliphatic group derived from a fluorinated aliphatic compound produced by a telomerization method (also called a telomer method) or an oligomerization method (also called an oligomer method) in addition to a known surfactant. Surfactant to be used can be used. In particular, a polymer having a fluoroaliphatic group derived from such a fluoroaliphatic compound may be used as the surfactant, respectively. The fluorine-based aliphatic compound can be synthesized by the method described in JP-A-2002-90991.

For example, Megafac F178, F-470, F-473, F-475, F-476 or F-472 (manufactured by Dainippon Ink & Chemicals, Inc.) may be cited as the above-mentioned surfactant. Also copolymers from acrylates (or methacrylates) with C ₆ F ₁₃ groups and poly (oxyalkylene) acrylates (or methacrylates), C ₆ F ₁₃ groups, poly (oxyethylene) acrylates And copolymers from acrylates (or methacrylates) with (or methacrylate) and poly (oxypropylene) acrylates (or methacrylates) and the like.

Moreover, you may use surfactant other than the fluorine type and / or silicon type surfactant described in Paragraph [0280] of US Patent application publication 2008/0248425.

These surfactants may be used alone or in combination.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may or may not contain a surfactant. When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a surfactant, the total amount used is preferably in the range of 0.0001 to 2% by mass, based on the total solids of the composition (excluding the solvent), and 0.0005 1 mass% is more preferable.

[6] other additives

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain or may not contain an onium carboxylate salt. As the carboxylic acid onium salt, those described in paragraphs [0605] to [0606] of US Patent Application Publication No. 2008/0187860 can be exemplified.

These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide or ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a carboxylic acid onium salt, the content ratio of the onium salt in the composition is usually in the range of 0.1 to 20% by mass based on the total solids of the composition. 0.5-10 mass% is preferable and 1-7 mass% is more preferable.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is a compound capable of increasing the solubility in a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, an anti-dissolution compound, and a developer, if necessary (eg, For example, a phenol compound or a carboxyl alicyclic or aliphatic compound having a molecular weight of 1,000 or less) may be further contained.

The phenolic compounds having a molecular weight of 1,000 or less can be readily synthesized by those skilled in the art with reference to the methods described in JP-A 4-122938 and JP-A 2-28531, USP 4,916,210 and EP 219294. .

As the carboxyl alicyclic or aliphatic compound, for example, a carboxylic acid derivative having a steroid structure such as cholic acid, deoxycholic acid or lysocolic acid, adamantanecarboxylic acid derivative, adamantanedicarboxylic acid, cyclohexane Carboxylic acid, cyclohexanedicarboxylic acid, and the like. However, the present invention is not limited to these.

From the viewpoint of improving the resolution, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used at a coating thickness of 30 to 250 nm. The actinic ray-sensitive or radiation-sensitive resin composition is more preferably used at a coating thickness of 30 to 200 nm. Such application thickness can be obtained by setting the solids content of the composition within an appropriate range so that the composition has an appropriate viscosity, thereby improving applicability and film formability.

Usually, solid content concentration of the actinic-ray-sensitive or radiation-sensitive resin composition which concerns on this invention exists in the range of 1.0-15 mass%, 2.5-13 mass% is preferable, and 3.0-12 mass% is more preferable. The resist solution can be uniformly applied onto the substrate by adjusting the solid concentration in this range. In addition, a resist pattern exhibiting high resolution and a rectangular profile and excellent in etching resistance can be formed. Although this reason is not necessarily clear, by adjusting the solid content concentration to 10% by mass or less, preferably 5.7% by mass or less, aggregation of materials, particularly photoacid generators, in the resist solution can be suppressed and a uniform resist film can be formed. It is assumed that this is very likely.

The term "solid content concentration" means the percentage of the weight of the resist component, not the solvent, relative to the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.

The resist film of the present invention is a film formed of the actinic ray-sensitive or radiation-sensitive resin composition. For example, it is a film | membrane formed by apply | coating the said actinic-ray-sensitive or radiation-sensitive resin composition on a board | substrate.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is used in such a manner that the above-mentioned components are dissolved in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtered, and applied onto a predetermined support (substrate). do. The filter medium used for the filtration is preferably made of any one of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 μm or less, preferably 0.05 μm or less, more preferably 0.03 μm or less. In the above filtration, for example, circulating filtration described in JP-A-2002-62667 may be performed, or two or more filters may be connected in series or in parallel. The composition may be filtered two or more times. The composition may also be degassed before or after filtration.

Example

The present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples.

&Lt; Synthesis Example (Synthesis of Resin P-1)

In nitrogen stream, 51.3 mass parts of cyclohexanone was heated at 80 degreeC. While stirring the liquid, 27.8 parts by mass of monomers of the following structural formula A, 21.0 parts by mass of monomers of the following structural formula B, 95.2 parts by mass of cyclohexanone, and 1.73 parts by mass of dimethyl 2,2'-azobisisobutyrate [V601, Wako Pure Chemical Industries, Ltd. The solution which consists of a mixture of] was dripped over 4 hours. After completion of dropping, the mixture was further stirred at 80 ° C. for 2 hours. The reaction solution thus obtained was allowed to cool, reprecipitated in a large amount of hexane / ethyl acetate (mass ratio: 8/2) and filtered. By drying the obtained solid content in vacuo, 45.2 mass parts of resin P-1 which concerns on this invention was obtained.

With respect to the obtained resin, it was found by GPC (carrier: tetrahydrofuran (THF)) that the mass average molecular weight (Mw: polystyrene equivalent) was 15,000 and the polydispersity (Mw / Mn) was 1.72. The composition ratio measured by ¹³ C-NMR was 50/50.

Resins P-2 to Resin P-31 were synthesized in the same manner as in the synthesis of Resin P-1. Hereinafter, the structure of the said synthetic resin P-1-synthetic resin P-31 is shown.

About each said synthetic resin, a repeating unit ratio, a weight average molecular weight (Mw), and polydispersity (Mw / Mn) are shown in Table 1, respectively. The left-to-right order of the list numerically showing the repeating unit ratios of Table 1 correspond to the arrangement of the repeating unit structures of the resins P-1 to P-31, respectively.

(Table 1)

<Acid Generator>

As the acid generator, the following compounds (PAG-1) to (PAG-8) were used.

&Lt; Basic compound >

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

<Surfactant>

Surfactant was suitably selected from the following surfactant (W-1)-surfactant (W-6), and was used.

W-1: Megafac F176 (Dainippon Ink & Chemicals, Inc., Fluorine)

W-2: Megafac R08 (manufactured by Dainippon Ink & Chemicals, Inc., fluorine-based and silicon-based)

W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd., silicon system)

W-4: Troy Sol S-366 (manufactured by Troy Chemical Co., Ltd.)

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

W-6: PolyFox PF-6320 (OMNOVA SOLUTIONS, INC., Fluorine)

<Solvent>

The solvent was suitably selected and used from the following solvent SL-1-solvent SL-8.

(group a)

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

(group c)

SL-7:? -Butyrolactone

SL-8: Propylene Carbonate

<Production of Resist>

The actinic ray sensitivity used in Examples 1 to 32 was dissolved by dissolving the components shown in Table 2 in a solvent having a solid content of 5.10% by mass in the same table and passing the solution through a polyethylene filter having a pore size of 0.1 μm. A radiation sensitive resin composition (resist composition) was produced.

(Table 2)

A substrate having a step was prepared for evaluation of the prepared resist composition. The characteristics of the pattern formation of the resist composition with respect to the stepped substrate were respectively evaluated. Hereinafter, the evaluation method will be described with reference to Table 1.

<Production of Substrate with Steps>

Referring to FIG. 1B, a positive resist composition 3 (FAiRS-G104: FUJIFILM Electronic Materials Co., Ltd.) on a Si substrate 1 having a 500 nm thick SiO ₂ film ₂ shown in FIG. Ltd.) was applied at a thickness of 200 nm and baked at 100 ° C. for 60 seconds. The baking positive resist film was exposed by an ArF excimer laser (PAS5500 / 1100, manufactured by ASML) through a mask having a width of 220 nm and a line pattern of 180 nm, and baked at 95 ° C. for 60 seconds. The wafer thus exposed was developed for 30 seconds with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, washed with pure water, and spin dried. As a result, a resist pattern having a line portion 220 nm and a space portion 180 nm was obtained (Fig. 1C).

A SiO ₂ film 2 is performed for 30 seconds to an etching treatment by the etching apparatus (NLD-800, manufactured by ULVAC ) using CF ₄ gas on the wafer that the pattern formed was etched to a depth 100㎚ (Fig. 1d). The wafer after the etching was immersed in an alkaline developer (TMAH: 2.38%) for 60 seconds to remove the resist composition. Subsequently, a substrate having a step shown in FIG. 1E was obtained.

<Evaluation of Pattern Formation Characteristics for Substrate with Steps>

On the substrate having the obtained step, the prepared resist compositions 4 of Examples 1 to 32 were each applied with a thickness of 150 nm on the protrusions (FIG. 1F) and prebaked at 100 ° C. for 60 seconds. . The prebaking resist film was exposed by a KrF excimer laser (PAS5500 / 850, manufactured by ASML) through a mask having a width of 400 nm line pattern and a 400 nm space, and post exposure baking (PEB) at 110 ° C. for 60 seconds. The exposure wafer thus obtained was developed for 30 seconds with an organic solvent (butyl acetate), and rotated for 30 seconds at a rotation speed of 4000 rpm. In this way the patterning shown in FIG. 1G was tested.

As a result, it was found that when the composition according to the present invention is used in any one of Examples 1 to 32, preferred patterning is realized on a substrate having a step by KrF exposure.

Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention is not limited to the specific details and representative embodiments described and described herein in its broader aspects. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.

1: Si substrate 2: SiO ₂ film
3: positive resist composition 4: resist composition of Examples

Claims (9)

(i) at least one repeating unit (a) represented by at least one of the following general formulas (I) and (II) and at least one of the following general formulas (III), (IV) and (V) Actinic ray-sensitive or radiation-sensitive resin comprising a resin (P) containing at least one repeating unit (b) represented and further comprising a compound (B) which generates an acid when exposed to actinic radiation or radiation Forming a film from the composition,
(Ii) exposing the film with a KrF excimer laser, and
(Iv) developing the said exposure film with the developing solution containing the organic solvent, and forming the negative pattern. The pattern formation method characterized by the above-mentioned.

Where R ₁₁ , R ₂₁ , R ₃₁ , and 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 of 1 to 4 carbon atoms,
m is O or 1,
n is 1 or 2.) The method according to claim 1,
The repeating unit (a) includes at least one repeating unit represented by the general formula (I), and the repeating unit (b) includes at least one repeating unit represented by the general formula (IV). The pattern formation method characterized by the above-mentioned. 3. The method according to claim 1 or 2,
The organic solvent contained in the developer is at least one solvent selected from the group consisting of ketone solvent, ester solvent, alcohol solvent, amide solvent, ether solvent and hydrocarbon solvent. 4. The method according to any one of claims 1 to 3,
And (i) washing the film with a cleaning solution containing an organic solvent after the step of developing the film with the developer. 5. The method according to any one of claims 1 to 4,
A negative pattern is formed on a stepped substrate. It is used for the pattern formation method in any one of Claims 1-5, The actinic-ray-sensitive or radiation-sensitive resin composition characterized by the above-mentioned. An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to claim 6. The manufacturing method of the electronic device containing the pattern formation method in any one of Claims 1-5. It is manufactured by the manufacturing method of the electronic device of Claim 8, The electronic device characterized by the above-mentioned.

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