JP2013045086A - Pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a fine resist pattern free of defects such as line edge roughness, scum and a microbridge, which is favorably used for processes of manufacturing semiconductors such as an IC, for manufacturing a circuit board such as a thermal head, and for lithographic processes of other photo-applications, in particular, in negative development technology.SOLUTION: The pattern forming method includes the steps of: forming a resist film by applying the following composition on a substrate; exposing the resist film; and developing the film by using a developing solution containing an organic solvent. The composition is prepared by passing a radiation-sensitive composition the solubility of which with an organic solvent is decreased by an action of an acid that generates by exposure, through a filter satisfying conditions (1) that the filter has a critical surface tension of 70 dyne/cm or more and that the filter is not modified with charges.

Description

  The present invention relates to a method for forming a pattern of a radiation-sensitive composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and a lithography process for other photo applications.

With the miniaturization of semiconductor elements, the wavelength of an exposure light source has been shortened and the projection lens has a high numerical aperture (high NA). Currently, an exposure machine using an ArF excimer laser having a 193 nm wavelength as a light source has been developed.
As a technique for increasing the resolving power, an immersion method is proposed in which a high refractive index liquid (hereinafter also referred to as “immersion liquid”) is filled between the projection lens and the sample.

  Further, as a technique for further improving the resolution, a double exposure technique and a double patterning technique have been proposed.

  An example in which the effect of the double exposure method is studied for transferring a fine image pattern of a semiconductor element is introduced in Patent Document 1 and the like. Recent progress in double exposure technology is also reported in Non-Patent Document 1, Non-Patent Document 2, Non-Patent Document 3, and the like.

Currently, 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous alkaline developer is widely used as a developer for lithography such as g-line, i-line, KrF, ArF, EB, EUV. Yes.
However, in a positive system (combination of a radiation-sensitive composition and a positive developer), a pattern is formed by selectively dissolving / removing areas with high light irradiation intensity in the optical aerial image (light intensity distribution). Only the material to do is provided. On the other hand, in the case of a combination of a negative type system (a radiation sensitive composition and a negative type developer), a material system is provided that selectively dissolves and removes a region with low light irradiation intensity to form a pattern. Only.
Here, the positive developer is a developer that selectively dissolves / removes the exposed portion above a predetermined threshold, and the negative developer selectively dissolves the exposed portion below the predetermined threshold. -Developer to be removed. The development process using a positive developer is referred to as positive development (also referred to as a positive development process), and the development process using a negative developer is referred to as a negative development (also referred to as a negative development process). Call.

JP 2006-156422 A

SPIE Proc 5754, 1508 (2005) SPIE Proc 5377, 1315 (2004) SPIE Proc 61561K-1 (2006)

  In recent years, the size of resist patterns has become increasingly fine due to the techniques described above, but as they become finer, it becomes difficult to obtain a good resist pattern due to foreign substances in the composition that had not had a significant effect until then. It is coming.

  The present invention has been made in view of the above circumstances, and in the radiation-sensitive composition, it is possible to suppress defects in the resist pattern after development, particularly generation of fine scum and microbridge (hereinafter referred to as “defects”). It is an object to provide a resist pattern forming technique.

The present invention has the following configuration, whereby the above object of the present invention is achieved.
A step of forming a resist film by applying a radiation-sensitive composition whose solubility in an organic solvent is reduced by the action of an acid generated by exposure on a substrate through a composition that passes a filter that satisfies the following condition (1): And a step of exposing the resist film and developing using a developer containing an organic solvent.
Condition (1): The critical surface tension of the filter is not less than 70 dyne / cm and is not charge-modified.
[2] The pattern forming method according to [1], wherein the filter has a zeta potential of more than −25 mV and 15 mV or less in distilled water having a pH of 7.0.
[3] The pattern forming method according to [1] or [2], wherein a pattern including a hole pattern is formed by the pattern forming method.
[4] The pattern forming method as described in [1] to [3], wherein the radiation-sensitive composition contains a polymer having a monocyclic or polycyclic alicyclic hydrocarbon structure.
[5] The pattern forming method as described in [4] above, wherein the polymer further has a lactone structure.
[6] The pattern forming method as described in [1] to [5], wherein the filtration is performed after the radiation-sensitive composition is prepared and before the composition is filled in a container. .
[7] The [1] to [1], wherein the filtration is performed after the radiation-sensitive composition is prepared and after the container containing the composition is attached to a device for applying to a substrate. [6] The pattern forming method according to [6].
[8] The pattern forming method as described in [4] to [7] above, wherein the lactone structure is at least one selected from groups of the following general formulas (LC1-1 to LC1-16).

n ₂ represents an integer of 0-4. Rb ₂ represents a substituent, when n ₂ is 2 or more, Rb ₂ existing in plural numbers may be the same or different or may be bonded to form a ring Rb ₂ between the plurality of .
[9] The lactone structure is represented by the general formula (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), or (LC1-14). The pattern forming method according to any one of [4] to [8], wherein the pattern forming method is a group.
[10] The above [7] to [9], wherein the lactone structure is a group represented by the general formula (LC1-4) wherein Rb ₂ is a cyano group and n ₂ is 1. The pattern forming method according to 1.
[11] The pattern formation according to any one of [3] to [10], wherein the polymer has at least one of groups represented by the following general formula (pI) or (pII): Method.

In the general formula (pI) or (pII), R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a sec-butyl group, and Z together with a carbon atom It represents an atomic group necessary for forming a cycloalkyl group.
R _{12 to} R ₁₄ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms. However, at least one of R _{12 to} R ₁₄ represents a cycloalkyl group.
[12] The pattern forming method as described in any one of [1] to [11], wherein development is further performed using an alkaline developer.
[13] The pattern forming method as described in any one of [1] to [11], wherein the exposure is performed a plurality of times before development.
[14] The pattern forming method as described in any one of [1] to [13], wherein the resist film after exposure and before development is heated.
[15]
The pattern forming method according to [14], wherein the heating after the exposure and before the development is performed a plurality of times.
[16] The developer is at least one organic solvent selected from the group consisting of ketone solvents, alcohol solvents, amide solvents, ether solvents, the following general formula (1) and the following general formula (2). The pattern formation method in any one of said [1]-[15] containing.

In the general formula (1), R and R ′ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group, or a halogen atom. R and R ′ may be bonded to each other to form a ring.

(In the general formula (2), R ″ and R ″ ″ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, or a cyano group. Or represents a halogen atom. R ″ and R ″ ″ may combine with each other to form a ring. R ′ ″ represents an alkylene group or a cycloalkylene group.)
[17] The pattern forming method according to any one of [1] to [16], wherein the developer contains alkyl acetate.
[18] The pattern forming method according to any one of [1] to [16], wherein the developer contains butyl acetate.
[19] The pattern forming method according to any one of [1] to [18], wherein the content of the organic solvent not containing a halogen atom in the total mass of all the solvents in the developer is 60% by mass or more. .
[20] The pattern forming method according to any one of [1] to [19], wherein the development using the developer is followed by washing with a rinse solution containing an organic solvent.
[21] The rinsing liquid contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. 20].
[22] The pattern forming method according to [20] or [21], wherein the rinse liquid contains an alcohol solvent.
[23] The pattern forming method according to any one of [20] to [22], wherein the rinse liquid contains a linear, branched or cyclic monovalent alcohol solvent having 6 to 8 carbon atoms.
[24]
The pattern formation method according to any one of [20] to [23], wherein the water content of the rinse liquid is 30% by mass or less.

  According to the present invention, it is possible to provide a resist pattern forming technique capable of suppressing resist pattern defects, particularly generation of fine scum and microbridges.

  First, terms used in this specification will be described. There are two types of pattern formation methods: positive and negative. Both use the fact that the solubility of the resist film in the developer changes due to a chemical reaction triggered by light irradiation. The case where the part is dissolved in the developer is called a positive type, and the case where the non-irradiated part is dissolved in the developer is called a negative type. There are two types of developers used in this case, a positive developer and a negative developer.

  In the present invention, as a technique for increasing the resolving power, a polymer whose polarity is increased by the action of an acid is contained, and the solubility in a positive developer (preferably an alkali developer) is increased by irradiation with actinic rays or radiation. A pattern forming method for forming a film with reduced solubility in a mold developer (preferably an organic developer) is presented.

As used in the present invention, the term “filtration” includes the commonly used chemical “filtration” (“permeate only the fluid phase [gas or liquid] using a porous membrane or phase, In addition to the meaning of “separating a semi-solid or solid from a fluid phase”, published on July 31, 1937, Kyoritsu Shuppan Co., Ltd. This includes cases where the semi-solid or solid trapped by the membrane cannot be visually confirmed by passing through.
In the present invention, the radiation-sensitive composition that passes through the filter may be a radiation-sensitive composition having the same concentration as that of the product, or includes a so-called stock solution having a solid content concentration of about 8 to 15% by mass before dilution. Let it be a concept. Moreover, in this specification, when the stock solution and the thing of the density | concentration similar to a product are not distinguished, it shall be described as a concept containing stock solution.
Further, in the present invention, the coating apparatus is a comprehensive concept including not only a radiation-sensitive composition coating apparatus but also a coating apparatus integrated with another apparatus such as a developing apparatus, such as a coating and developing apparatus. And
In addition, in this specification, the term “zeta potential” simply means “zeta potential in distilled water at pH 7.0”. The numerical value in the present invention is the nominal value of the filter manufacturer.

A pattern forming method necessary for carrying out the present invention includes the following steps.
(A) the process of adjusting the radiation sensitive composition mentioned later,
(B) a step of passing through a filter that satisfies the following condition (1):
(A) a step of applying the radiation-sensitive composition on a substrate;
(A) an exposure step; and (d) a step of developing using a negative developer.
Condition (1): The critical surface tension of the filter is not less than 70 dyne / cm and is not charge-modified.

  Further, the filter preferably has a zeta potential of more than −25 mV and 15 mV or less in distilled water having a pH of 7.0.

  The above-mentioned step (B) is a step (B1) of filtering after adjusting the radiation-sensitive composition and before filling the composition into a container, and after adjusting the radiation-sensitive composition And at least one step (B2) of filtering after the container containing the composition is attached to a device for applying to the substrate.

Here, the filter includes, for example, a film that allows at least the radiation-sensitive composition to pass therethrough and a support member that supports the film. Specifically, various materials and pore sizes are used for filtering ultrapure water, high-purity chemicals, fine chemicals, etc. from filter manufacturers such as Nippon Pole Co., Ltd., Advantech Toyo Co., Microlith Co., Ltd. or Kitz Co. Things are manufactured or sold.
In the present embodiment, the form of the filter is not particularly limited. For example, a so-called disk type or cartridge type is generally used.

The filter is provided with a membrane having a critical surface tension of 70 dyne / cm or more and is not subjected to charge modification, thereby reducing defects, particularly suppressing fine scum and microbridge, improving foreign matter characteristics, foreign matter The effect of improving the aging characteristics can be obtained.
The upper limit of the critical surface tension is 95 dyne / cm or less because the effect of reducing defects is inferior. A more preferable range is 75 dyne / cm or more and 90 dyne / cm or less, and a further preferable range is 75 dyne / cm or more and 80 dyne / cm or less.

  Although it is easy to use the nominal value of the critical surface tension of the filter manufacturer, specifically, prepare multiple liquids of known surface tension, drop them onto the target film, and soak into the film with its own weight. It can also be easily determined by identifying the boundaries between things and imperfections.

  Charge modification is synonymous with the expression of forced potential modification.

  A “non-charge modified” membrane has a zeta potential in the range above −25 mV and below 15 mV. From the viewpoint of the effect of the present invention, it is preferably in the range of more than −20 mV and 10 mV or less; more preferably in the range of more than −20 mV and less than 10 mV; most preferably a negative zeta potential (however, more than −20 mV).

  In the present invention, the negative zeta potential is preferably −5 mV or less (however, over −20 mV), preferably −10 to −18 mV, and more preferably −12 to −16 mV.

In the present embodiment, a nylon (polyamide) film that is not charge-modified is preferable from the viewpoint of satisfying the value of critical surface tension.
In addition, as a filter that satisfies the value of critical surface tension and is not charge-modified, nylon 66 (registered trademark) Ultipleat (registered trademark: P-Nylon Filter) (product name: manufactured by Nippon Pole Co., Ltd.) Zeta potential is about −12 to −16 mV, pore diameter 0.04 μm, critical surface tension 77 dyne / cm).

  The pattern forming method of the present invention preferably forms a pattern including a hole pattern.

  The pattern forming method of the present invention preferably further includes (f) a step of washing using a negative developing rinse solution.

  The pattern forming method of the present invention preferably includes (e) a heating step after (b) the exposure step.

  The pattern formation method of this invention can have (b) exposure process in multiple times.

  The pattern formation method of this invention can have (e) a heating process in multiple times.

  In carrying out the present invention, a radiation-sensitive composition containing a polymer whose polarity is increased by the action of an acid and whose solubility in a negative developer is reduced by irradiation with actinic rays or radiation, and (b) a negative type A developer (preferably an organic developer) is required.

  Conventionally, there are two types of resist pattern forming methods, positive type and negative type, both of which utilize the fact that the solubility of the resist film in the developer changes due to a chemical reaction triggered by light irradiation. In general, the case where the light irradiation part is dissolved in the developer is called a positive type, and the case where the non-irradiation part is dissolved in the developer is called a negative type. The positive radiation sensitive composition uses a chemical reaction such as polarity conversion in order to enhance the solubility in the developer. In the negative radiation sensitive composition, there is an intermolecular reaction such as a crosslinking reaction or a polymerization reaction. It uses bond generation.

However, in the present invention, one radiation-sensitive composition (a) simultaneously acts as a positive type for a positive developer and as a negative type for a negative developer.
The radiation-sensitive composition (a) is “a polymer composition that forms a film with increased polarity as a result of a chemical reaction triggered by exposure to radiation”.
In the present invention, the radiation-sensitive composition (a) not only reduces the solubility in the negative developer by the polarity conversion reaction of the polymer side chain, but also has a specific chemical reaction (of the polymer side chain). The polarity conversion reaction) simultaneously increases the solubility in an alkali developer and decreases the solubility in an organic developer.

When performing negative development, it is preferable to use an organic developer containing an organic solvent.
Organic developers that can be used for negative development are represented by ketone solvents, alcohol solvents, amide solvents, ether solvents, the following general formula (1), and the following general formula (2). At least one kind of solvent can be used.

In general formula (1),
R and R ′ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R and R ′ may be bonded to each other to form a ring.

In general formula (2),
R ″ and R ″ ″ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R ″ and R ″ ″ may be bonded to each other to form a ring.
R ′ ″ represents an alkylene group or a cycloalkylene group.

For example, ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone. Etc.

Examples of alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n- Alcohols such as octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether and triethylene glycol mono List glycol ether solvents such as ethyl ether and methoxymethylbutanol. Can.
Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.
As the general formula (1) or the general formula (2), methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol Monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Etc.

A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water.

  As a development method, a method of developing by raising the developer on the surface of the substrate by surface tension and allowing it to stand for a certain time (paddle method), a method of spraying the developer on the surface of the substrate (spray method), and rotating at a constant speed There are methods such as a method of continuously applying the developer while scanning the developer application nozzle on the substrate at a constant speed (dynamic dispensing method). When these development methods are used, the vapor pressure of the negative developer is used. Is high, the developer surface evaporates, the substrate surface is cooled, the temperature of the developer solution is lowered, the dissolution rate of the film of the radiation-sensitive composition formed on the substrate is not constant, and the dimensional uniformity Gets worse. For this reason, the preferable range of the vapor pressure of the developer that can be used when performing negative development is 5 kPa or less, more preferably 3 kPa or less, and most preferably 2 kPa or less at 20 ° C.

  Specific examples having a vapor pressure of 5 kPa or less at 20 ° C. include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenyl Acetone, ketone solvents such as methyl isobutyl ketone, 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 acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Ester solvents, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, etc. Alcohol solvents, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and glycol ethers such as propylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, etc. Solvents, ether solvents such as tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylacetate Amide, N, N-dimethylformamide amide solvents, toluene, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.

  Specific examples having a vapor pressure of 2 kPa or less at 20 ° C., which is the most preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, and cyclohexanone. , Ketone solvents such as methylcyclohexanone and phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate Ester solvents such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate, n-butyl Alcohol solvents such as alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol and n-decanol, glycols such as ethylene glycol, diethylene glycol and triethylene glycol Solvents, glycol ether solvents such as propylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, N-methyl-2-pyrrolidone, N, N-dimethylacetamide Amide solvents of N, N-dimethylformamide, aromatic hydrocarbon solvents such as xylene, aliphatics such as octane and decane It includes hydrocarbon solvents.

An appropriate amount of a surfactant can be added to the developer that can be used for negative development, if necessary.
Although it does not specifically limit as surfactant, For example, an ionic and nonionic fluorine type and / or silicon type surfactant etc. can be used, Preferably it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

  Further, after the step of performing the negative development, a step of stopping the development may be performed while substituting with another solvent.

  After the negative development, it is preferable to include a step of washing with a rinsing liquid containing an organic solvent.

  In the rinsing step after negative development, a rinsing solution containing at least one organic solvent selected from alkane solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. It is preferable to wash. More preferably, after the negative development, a step of washing with a rinsing solution containing at least one organic solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent is performed. is there. Even more preferably, after negative development, a step of washing with a rinse solution containing an alcohol solvent or an ester solvent is performed. Particularly preferably, after the negative development, a step of washing with a rinse solution containing a monohydric alcohol having 6 to 8 carbon atoms is performed. Here, examples of the monohydric alcohol having 6 to 8 carbon atoms used in the rinsing step after the negative development include linear, branched, and cyclic monohydric alcohols, specifically, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, benzyl alcohol, and the like can be used. Hexanol, 2-hexanol, and 2-heptanol.

  A plurality of these components may be mixed, or may be used by mixing 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.

  An appropriate amount of a surfactant can be added to the rinse solution.

  As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously applying the developer while scanning the developer application nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method) ) Etc. can be applied.

  Although there is no restriction | limiting in the light source wavelength used for the exposure apparatus in this invention, KrF excimer laser wavelength (248 nm), ArF excimer laser wavelength (193 nm), F2 excimer laser wavelength (157 nm), etc. are applicable.

Moreover, the immersion exposure method can be applied in the step of performing exposure according to the present invention.
The immersion exposure method is a technology for filling and exposing a projection lens and a sample with a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”) as a technique for increasing the resolving power.

  In the present invention, the substrate on which the film is formed is not particularly limited, and silicon, SiN, inorganic substrates such as SiO2 and SiN, coated inorganic substrates such as SOG, semiconductor manufacturing processes such as IC, liquid crystal, thermal head, etc. A substrate generally used in the manufacturing process of the circuit board, and also in the lithography process of other photo applications can be used. Further, if necessary, an organic antireflection film may be formed between the film and the substrate.

  Hereinafter, adjustment of the radiation-sensitive composition that can be used in the present invention will be described.

Polymer (A) contained in a radiation-sensitive composition whose solubility in an organic solvent is reduced by the action of an acid generated by exposure
The polymer used in the radiation-sensitive composition of the present invention decomposes into the main chain or side chain of the polymer, or both of the main chain and side chain by the action of an acid, increases its polarity, A polymer (also referred to as “acid-decomposable polymer”, “acid-decomposable polymer (A)” or “polymer (A)”) having a generated group (hereinafter also referred to as “acid-decomposable group”) Preferably, the solubility in a positive developer is increased, the monocyclic or polycyclic alicyclic hydrocarbon structure is increased, the polarity is increased by the action of an acid, the solubility in an alkali developer is increased, and the solubility in an organic solvent is increased. Is a polymer (hereinafter also referred to as “alicyclic hydrocarbon-based acid-decomposable polymer”). The reason is that the polarity of the polymer changes greatly before and after irradiation with actinic rays or radiation, and a positive developer (preferably an alkali developer) and a negative developer (preferably an organic solvent) are used. This is because the dissolution contrast when developed is improved. Furthermore, a polymer having a monocyclic or polycyclic alicyclic hydrocarbon structure is generally highly hydrophobic, and a negative developing solution (preferably an organic solvent) is used to develop a region of a resist film with low light irradiation intensity. The developing speed is high, and the developability when using a negative developer is improved.
Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) Imido group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group A group having
Preferred alkali-soluble groups include carboxylic acid groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.
A preferred group as an acid-decomposable group (acid-decomposable group) is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.
As the acid eliminable group, there can be, for _{example, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R _{01 to} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

  The radiation-sensitive composition of the present invention containing a polymer (a1) having a monocyclic or polycyclic alicyclic hydrocarbon structure and increasing in polarity by the action of an acid is used when irradiating ArF excimer laser light. It can be preferably used.

  As a polymer having a monocyclic or polycyclic alicyclic hydrocarbon structure and increasing in polarity by the action of an acid (hereinafter also referred to as “alicyclic hydrocarbon-based acid-decomposable polymer”), the following general formula ( A polymer containing at least one selected from the group of repeating units represented by repeating units having a partial structure containing an alicyclic hydrocarbon represented by pI) to general formula (pV) is preferable.

In general formulas (pI) to (pV),
R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a sec-butyl group, and Z is an atom necessary for forming a cycloalkyl group together with a carbon atom. Represents a group.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms. However, at least one of R _{12 to} R ₁₄ , or any of R ₁₅ and R ₁₆ represents a cycloalkyl group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{17 to} R ₂₁ represents a cycloalkyl group. Further, any one of R ₁₉ and R ₂₁ represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{22 to} R ₂₅ represents a cycloalkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In the general formulas (pI) to (pV), the alkyl group in R _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms.

The cycloalkyl group in R _{11 to} R ₂₅ or the cycloalkyl group formed by Z and the carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. These cycloalkyl groups may have a substituent.

  The alicyclic hydrocarbon-based acid-decomposable polymer of the present invention preferably has a lactone group. As the lactone group, any group can be used as long as it contains a lactone structure, but it is preferably a group containing a 5- to 7-membered ring lactone structure, and a bicyclo structure in the 5- to 7-membered ring lactone structure, Those in which other ring structures are condensed to form a spiro structure are preferred. It is more preferable to have a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16). Further, a group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are groups represented by general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), By using a specific lactone structure, line edge roughness and development defects are improved.

  The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.

The alicyclic hydrocarbon-based acid-decomposable polymer of the present invention has a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Is preferred. This improves the substrate adhesion and developer compatibility. The alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diamantyl group, or a norbornane group. The polar group is preferably a hydroxyl group or a cyano group.
As the alicyclic hydrocarbon structure substituted with a polar group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferable.

In general formulas (VIIa) to (VIIc),
R _{2C to} R _4C each independently represent a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R _{2C to} R _4C represents a hydroxyl group or a cyano group. Preferably, one or two of R _{2C to} R _4C are a hydroxyl group and the remainder is a hydrogen atom.
In general formula (VIIa), it is more preferable that two of R2c to R4c are a hydroxyl group and the remaining is a hydrogen atom.

The following are mentioned as a preferable aspect of the alicyclic hydrocarbon type acid-decomposable polymer of this invention.
(1) What contains the repeating unit which has a partial structure containing the alicyclic hydrocarbon represented by said general formula (pI)-(pV) (side chain type).
Preferably those containing (meth) acrylate repeating units having a structure of (pI) to (pV).
(2) One containing a repeating unit represented by the general formula (II-AB) (main chain type).
However, in (2), for example, the following can be further mentioned.
(3) A repeating unit represented by the general formula (II-AB), a maleic anhydride derivative and a (meth) acrylate structure (hybrid type).

  In the alicyclic hydrocarbon-based acid-decomposable polymer, the content of the repeating unit having an acid-decomposable group is preferably from 10 to 60 mol%, more preferably from 20 to 50 mol%, still more preferably from all repeating structural units. 30 to 50 mol%.

  In the alicyclic hydrocarbon-based acid-decomposable polymer, the content of the repeating unit having a partial structure containing the alicyclic hydrocarbon represented by the general formulas (pI) to (pV) is 20 to 20 in all the repeating structural units. 70 mol% is preferable, More preferably, it is 20-50 mol%, More preferably, it is 30-50 mol%.

  In the alicyclic hydrocarbon-based acid-decomposable polymer, the content of the repeating unit represented by the general formula (II-AB) is preferably 10 to 60 mol%, more preferably 15 to 55 mol in all repeating structural units. %, More preferably 20 to 50 mol%.

In the acid-decomposable polymer, the content of the repeating unit having a lactone ring is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, still more preferably 25 to 50 mol% in all repeating structural units. .
In the acid-decomposable polymer, the content of the repeating unit having an organic group having a polar group is preferably 1 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 5 to 20 in all repeating structural units. Mol%.

  Further, the content of the repeating structural unit in the polymer based on the monomer of the further copolymer component can be appropriately set according to the performance of the desired radiation-sensitive composition. The total number of moles of the repeating structural unit having a partial structure containing the alicyclic hydrocarbon represented by the general formulas (pI) to (pV) and the repeating unit represented by the general formula (II-AB) On the other hand, 99 mol% or less is preferable, More preferably, it is 90 mol% or less, More preferably, it is 80 mol% or less.

The weight average molecular weight of the polymer according to the present invention is preferably 6000 or less, more preferably 1000 to 5000, and particularly preferably 2000 to 3500 in terms of polystyrene by GPC method. By setting the weight average molecular weight of the polymer to 6000 or less, the line edge roughness of the resist pattern is reduced.
The dispersity (molecular weight distribution, Mw / Mn) is preferably 1.7 or less, more preferably 1.5 or less, and particularly preferably 1.3 or less. The smaller the degree of dispersion, the smaller the line edge roughness of the resist pattern.

In the radiation-sensitive composition of the present invention, the blending amount of all the polymers according to the present invention in the entire composition is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass in the total solid content. %.
In the present invention, the polymers may be used alone or in combination.

(B) Compound that generates acid upon irradiation with actinic ray or radiation The radiation-sensitive composition of the present invention is a compound that generates acid upon irradiation with actinic ray or radiation ("photoacid generator" or "component (B)") (Also called).

Acid generator (B):
The acid generator (B) is a compound represented by the following formula (6).

In the formula (6), R ₅₅ represents a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxyl group having 1 to 10 carbon atoms, Or a C2-C11 linear or branched alkoxycarbonyl group is represented. R ₅₆ is a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxyl group having 1 to 10 carbon atoms, or a linear or branched group having 1 to 10 carbon atoms. Represents a cyclic or cyclic alkanesulfonyl group. Further, R ₅₅ represents each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a phenyl group, or a naphthyl group, or two R ¹⁵ are bonded to each other. A divalent group having 2 to 10 carbon atoms containing a sulfur cation. However, the phenyl group, the naphthyl group, and the divalent group having 2 to 10 carbon atoms may have a substituent. k represents an integer of 0 to 2, and r represents an integer of 0 to 10 (preferably an integer of 0 to 2). X ⁻ represents an anion represented by the following formulas (7-1) to (7-4).

In formulas (7-1) and (7-2), R ₅₈ represents a fluorine atom or an optionally substituted hydrocarbon group having 1 to 12 carbon atoms. In Formula (7-1), t represents an integer of 1 to 10. In the formulas (7-3) and (7-4), R ₅₉ independently represents a linear or branched alkyl group having 1 to 10 carbon atoms substituted with a fluorine atom, or 2 R 2 represents a divalent organic group having 2 to 10 carbon atoms substituted with a fluorine atom, which is formed by bonding R ₅₉ to each other. However, the C2-C10 divalent organic group substituted with a fluorine atom may have a substituent other than a fluorine atom.

The acid generator (B) may contain the acid generator represented by the above formula (6) alone or in combination of two or more.
Further, it may contain a radiation sensitive acid generator other than the acid generator (hereinafter also referred to as “other acid generator”).
Examples of other acid generators include onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, and sulfonic acid compounds. In addition, an acid generator (B) may contain another acid generator individually by 1 type, and may contain 2 or more types.

The usage-amount of an acid generator (B) is 20 mass% or less with respect to 100 mass% of radiation sensitive compositions, Preferably it is 1-15 mass%.
Moreover, when using another acid generator, the use ratio is 80 mass% or less normally with respect to 100 mass% of acid generators (B), Preferably it is 60 mass% or less.

Solvent (C):
Examples of the solvent (C) include 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, and 3,3-dimethyl. Linear or branched ketones such as 2-butanone, 2-heptanone, 2-octanone; cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, isophorone Cyclic ketones such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether Propylene glycol monoalkyl ether acetates such as acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-butyl ether acetate; methyl 2-hydroxypropionate, 2-hydroxypropionic acid Ethyl, 2-hydroxypropionate n-propyl, 2-hydroxypropionate i-propyl, 2-hydroxypropionate n-butyl, 2-hydroxypropionate i-butyl, 2-hydroxypropionate sec-butyl, 2-hydroxy Alkyl 2-hydroxypropionates such as t-butyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate Methyl propionic acid, other 3-alkoxy propionic acid alkyl such as ethyl 3-ethoxypropionate,

  n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether , Propylene glycol monoethyl Ether, propylene glycol mono-n-propyl ether, toluene, xylene, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, Ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol Cole monoethyl ether, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, etc. .

  Among these, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionate, alkyl 3-alkoxypropionate, γ-butyrolactone and the like are preferable.

The radiation sensitive composition may contain 1 type of solvent (C), and may contain 2 or more types.
The amount of the solvent (C) used is such that the total solid concentration of the radiation-sensitive composition is usually 1 to 50% by mass, preferably 1 to 25% by mass.
Additive:
The radiation-sensitive composition may be an acid diffusion controller, an alicyclic additive, a surfactant, if necessary.
You may contain various additives, such as a sensitizer.
(I) Acid diffusion controller (D):
The acid diffusion control agent is a component having an action of controlling a diffusion phenomenon of an acid generated from the acid generator (B) by exposure in the resist layer and suppressing an undesirable chemical reaction in a non-exposed region. By containing such an acid diffusion controller, the storage stability of the radiation-sensitive composition is improved. In addition, the resolution as a resist is further improved, and it is possible to suppress changes in the line width of the resist pattern due to fluctuations in the holding time (PED) from exposure to post-exposure heat treatment, and an extremely excellent process stability. Things are obtained.

(Iii) Surfactant:
A surfactant is a component that exhibits an effect of improving coating properties, striation, developability, and the like.
Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol In addition to nonionic surfactants such as distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), Megafax F171, F173 (above, manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 ( As mentioned above, manufactured by Asahi Glass Co., Ltd. In addition, these surfactants may be used individually by 1 type, and 2 or more types may be mixed and used for them.

(Iv) Sensitizer:
The sensitizer absorbs radiation energy and transmits the energy to the acid generator (B), thereby increasing the amount of acid produced. The apparent sensitivity of the radiation-sensitive composition. Has the effect of improving.
Examples of the sensitizer include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines, and the like. In addition, these sensitizers may be used individually by 1 type, and 2 or more types may be mixed and used for them.

(V) Other additives:
The radiation-sensitive composition may contain additives other than the additives described above (hereinafter also referred to as “other additives”). Other additives include alkali-soluble polymers, low-molecular alkali solubility control agents having acid-dissociable protecting groups, antihalation agents, storage stabilizers, antifoaming agents, and the like. In addition, by including a dye or a pigment, the latent image of the exposed portion can be visualized, and the influence of halation during exposure can be reduced. Furthermore, the adhesiveness with a board | substrate can be improved by containing an adhesion assistant.

(Vi) Adjustment of Radiation Sensitive Composition The radiation sensitive composition is, for example, the polymer (A), the acid generator (B) added as necessary, and an acid diffusion controller in the solvent (C). It can be prepared by mixing (D) and other optional components at a predetermined ratio. The radiation-sensitive composition is usually dissolved in the solvent (C) so that the total solid content is 1% by mass to 50% by mass, preferably 2% by mass to 25% by mass, and then the filter is used. It is prepared by filtering with.

  The radiation-sensitive composition only needs to pass through the filter at least once, and may be circulated a plurality of times. Further, the filtration may be performed at least one of before being put in the transport bottle and during application from the transport bottle onto the substrate.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

Synthesis Example 1 (Synthesis of polymer (A1))
Under a nitrogen stream, 100 g of methyl isobutyl ketone was placed in a three-necked flask and heated to 80 ° C. To this, monomer 1: 39.71 g of a monomer represented by the following formula (1-1), monomer 2: 23.55 g of a monomer represented by the following formula (2-2), A monomer 3: 36.74 g of the monomer represented by the following (3-2) and 6 mol% (4.60 g) of azobisisobutyronitrile in 200 g of methyl isobutyl ketone are dissolved in the total amount of monomers. The solution was added dropwise over 6 hours. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then poured into a mixture of 1350 ml of heptane / 150 ml of ethyl acetate, and the precipitated powder was collected by filtration and dried, yielding 77.9 g of polymer (A1). The obtained polymer had a weight average molecular weight of 5,500 and a dispersity (Mw / Mn) of 1.50.

Synthesis Examples 2 to 4 (Synthesis of polymers (A2) to (A4))
In the same manner as in Synthesis Example 1, the polymers (A2) to (A4) listed in Table 1 below were synthesized.

The abbreviations used in Table 1 above are as follows.

Radiation sensitive composition (A1)
The following components were dissolved in a mixed solvent of polyethylene glycol monomethyl ether acetate / polyethylene glycol monomethyl ether (60:40) to obtain a solid content concentration of 5.8% by weight of nylon 66 (polyamide 66) having a pore size of 0.1 μm. It filtered with the filter and prepared the radiation sensitive composition (A1).
1.83 g of polymer (A1), 69.6 mg of triphenylsulfonium nonaflate, 8.7 mg of diphenylaniline, 1.7 mg of PF6320 (fluorine surfactant manufactured by OMNOVA).

Radiation sensitive composition (A2) to (A4)
Radiation sensitive compositions (A2) to (A4) were prepared in the same manner except that the polymers (A2) to (A4) were used instead of the polymer (A1).

Radiation sensitive composition (A1 ′)
Except having filtered with the polyethylene filter, it adjusted similarly to the above-mentioned radiation sensitive composition (A1).

Examples 1-4, Comparative Example 1
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on an 8-inch silicon wafer, and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. On top of this, the radiation-sensitive composition (A1) described above was applied and baked at 120 ° C. for 60 seconds to form a 150 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75). Thereafter, the film was heated at 120 ° C. for 60 seconds and then developed with butyl acetate (negative developer) for 30 seconds (negative development). Next, after rinsing with 1-hexanol (negative developing rinse) for 30 seconds, the wafer was rotated at 3000 rpm for 30 seconds to obtain a 45 nm (1: 1) line and space resist pattern.
Examples 2 to 4 and Comparative Example 1 were 45 nm (1: 1) in the same manner as in Example 1 except that the radiation-sensitive compositions (A2) to (A5) and the composition (A1 ′) were used, respectively. ) A resist pattern was obtained.

Evaluation of Line Edge Roughness (LER) The 45 nm (1: 1) line and space resist pattern obtained in Examples 1 to 4 and Comparative Example 1 was observed with a scanning microscope (S9260 manufactured by Hitachi, Ltd.). In the range of the edge of 2 μm in the longitudinal direction, the distance from the reference line where the edge should be was measured at 50 points, the standard deviation was obtained, and 3σ (unit: nm) was calculated. A smaller value indicates better performance. The results are shown in Table 2.

Defect Evaluation The scum and bridges of the substrates obtained in Examples 1 to 4 and Comparative Example 1 were evaluated using KLA-Tencor and KLA2810. The case where there was a scum or bridge was evaluated as x, and the case where there was no scum or bridge was evaluated as o. The results are shown in Table 2.

  The abbreviations used in the examples are the above specific examples and the following.

DIA: 2,6-diisopropylaniline TPA: tripentylamine PEA: N-phenyldiethanolamine TOA: trioctylamine PBI: 2-phenylbenzimidazole

W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-5: PF656 (manufactured by OMNOVA, fluorine-based)
W-6: PF6320 (manufactured by OMNOVA, fluorine-based)

A1: Propylene glycol monomethyl ether acetate A2: Cyclohexanone B1: Propylene glycol monomethyl ether B2: Ethyl lactate B3: γ-Butyrolactone

  From the above examples, it is clear that the generation of fine scum and microbridge could be suppressed by the combination of the radiation sensitive composition of the present invention and the negative developer.

Claims (24)

A step of forming a resist film by applying a radiation-sensitive composition whose solubility in an organic solvent is reduced by the action of an acid generated by exposure on a substrate through a composition that passes a filter that satisfies the following condition (1): And a step of exposing the resist film and developing using a developer containing an organic solvent.
Condition (1): The critical surface tension of the filter is not less than 70 dyne / cm and is not charge-modified.   The pattern forming method according to claim 1, wherein the filter has a zeta potential of more than −25 mV and 15 mV or less in distilled water having a pH of 7.0.   The pattern forming method according to claim 1, wherein a pattern including a hole pattern is formed by the pattern forming method.   The pattern forming method according to claim 1, wherein the radiation-sensitive composition includes a polymer having a monocyclic or polycyclic alicyclic hydrocarbon structure.   The pattern forming method according to claim 4, wherein the polymer further has a lactone structure.   The pattern formation method according to claim 1, wherein the filtration is performed after the radiation-sensitive composition is prepared and before the composition is filled in a container.   7. The filtration according to claim 1, wherein the filtration is performed after the radiation-sensitive composition is prepared and after the container containing the composition is attached to a device for applying to a substrate. Pattern forming method. The pattern forming method according to claim 4, wherein the lactone structure is at least one selected from groups of the following general formulas (LC1-1 to LC1-16).
_{(N 2} are .rb ₂ represents an integer of 0 to 4 represents a substituent, when n ₂ is 2 or more, Rb ₂ existing in plural numbers may be the same or different, also, there are a plurality Rb ₂ may be bonded to form a ring.)   The lactone structure is a group represented by the general formula (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), or (LC1-14). The pattern forming method according to claim 4, wherein: The pattern formation method according to claim 7, wherein the lactone structure is a group represented by the general formula (LC1-4) in which Rb ₂ is a cyano group and n ₂ is 1. . The pattern forming method according to claim 3, wherein the polymer has at least one of groups represented by the following general formula (pI) or (pII).
(In the general formula (pI) or (pII), R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents a carbon atom. And represents an atomic group necessary for forming a cycloalkyl group.
R _{12 to} R ₁₄ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms. However, at least one of R _{12 to} R ₁₄ represents a cycloalkyl group. ) Furthermore, it develops using an alkaline developing solution, The pattern formation method in any one of Claims 1-11 characterized by the above-mentioned.   The pattern forming method according to claim 1, wherein exposure is performed a plurality of times before development.   The pattern forming method according to claim 1, wherein the resist film after exposure and before development is heated.   The pattern forming method according to claim 14, wherein the heating after the exposure and before the development is performed a plurality of times. The developer contains at least one organic solvent selected from the group consisting of ketone solvents, alcohol solvents, amide solvents, ether solvents, the following general formula (1) and the following general formula (2). The pattern formation method in any one of Claims 1-15.
(In the general formula (1), R and R ′ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom. R and R ′ may combine with each other to form a ring.)
(In the general formula (2), R ″ and R ″ ″ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, or a cyano group. Or represents a halogen atom. R ″ and R ″ ″ may combine with each other to form a ring. R ′ ″ represents an alkylene group or a cycloalkylene group.) The pattern forming method according to claim 1, wherein the developer contains alkyl acetate.   The pattern forming method according to claim 1, wherein the developer contains butyl acetate.   The pattern forming method according to claim 1, wherein the content of the organic solvent not containing a halogen atom in the total mass of all the solvents in the developer is 60% by mass or more.   The pattern formation method in any one of Claims 1-19 wash | cleaned using the rinse liquid containing an organic solvent after the image development using the said developing solution.   21. The rinsing liquid contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Pattern forming method.   The pattern forming method according to claim 20 or 21, wherein the rinse liquid contains an alcohol solvent.   The pattern formation method according to any one of claims 20 to 22, wherein the rinse liquid contains a linear, branched or cyclic monovalent alcohol solvent having 6 to 8 carbon atoms.   The pattern formation method according to any one of claims 20 to 23, wherein a moisture content of the rinse liquid is 30% by mass or less.