JP2016075920A - Production method of organic process liquid for patterning chemically amplified resist film, pattern forming method, and method for manufacturing electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of an organic process liquid for patterning a chemically amplified resist film, the organic process liquid capable of reducing generation of particles, particularly in negative pattern forming technology for forming a fine pattern by use of an organic developer, an organic process liquid for patterning a chemically amplified resist film by using the above method, a pattern forming method, a method for manufacturing an electronic device, and an electronic device.SOLUTION: The production method of an organic process liquid for patterning includes a step of allowing a liquid comprising an organic solvent to pass through a filtration device that includes a liquid inlet, a liquid outlet, and a filtration membrane disposed in a flow passage connecting the liquid inlet and the liquid outlet. An absolute value of a difference between a temperature of the liquid at the liquid inlet and a temperature of the liquid at the liquid outlet is 3°C or less; a filtration speed of the liquid in the filtration device is 0.5 L/min/mor more; and a filtration pressure of the liquid in the filtration device is 0.1 MPa or less.SELECTED DRAWING: None

Description

  The present invention relates to a method for manufacturing an organic processing liquid for patterning a chemically amplified resist film, an organic processing liquid for patterning a chemically amplified resist film, a pattern forming method, an electronic device manufacturing method, and an electronic device. More specifically, the present invention relates to an organic layer for patterning a chemically amplified resist film suitable for a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal and a thermal head, and a photolithographic lithography process. The present invention relates to a method for producing a system treatment liquid, an organic treatment liquid for patterning a chemically amplified resist film, a pattern formation method, a method for producing an electronic device, and an electronic device. In particular, the present invention relates to an organic processing liquid for patterning a chemically amplified resist film suitable for exposure in an ArF exposure apparatus and an ArF immersion projection exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source. The present invention relates to a manufacturing method, an organic processing liquid for patterning a chemically amplified resist film, a pattern forming method, a manufacturing method of an electronic device, and an electronic device.

  Conventionally, various configurations have been proposed as a positive pattern forming method using an alkali developer and a positive resist composition used therefor (see, for example, Patent Documents 1 to 3). In addition to this, in recent years, the negative pattern forming method using an organic developer and the negative resist composition used therefor mainly form fine contact holes and trench patterns that cannot be achieved with a positive resist composition. It is being developed as a use (see, for example, Patent Documents 4 to 7).

  The resist composition or developer used in the positive or negative pattern forming method is usually used after fine particles in the resist composition or developer are removed by a filter (for example, Patent Documents). 8 and 9).

JP 2006-257078 A JP 2005-266766 A JP 2006-330098 A JP 2007-325915 A International Publication No. 2008-153110 Pamphlet JP 2010-039146 A JP 2010-164958 A JP 2000-005546 A JP 2004-195427 A

  By the way, in recent years, the need for further miniaturization (for example, 30 nm node or less) is rapidly increasing in the formation of contact holes and trench patterns. In response to this, it is required to further suppress the generation of particles that are likely to affect the performance of the miniaturized pattern.

  The present invention has been made in view of the above problems, and the object thereof is, in particular, in a negative pattern forming technique for forming a fine pattern (for example, a node of 30 nm or less) using an organic developer. Method of manufacturing chemical processing liquid for patterning chemical amplification resist film capable of reducing generation, organic processing liquid for patterning of chemical amplification resist film using the same, pattern formation method, and manufacturing method of electronic device And providing an electronic device.

  As a result of intensive studies, the inventors have made contact with the organic solvent and the filter to elute a small amount of low-molecular-weight organic matter into the organic solvent from the filter. In the case where a fine pattern is formed by using as an organic developer in the above, it has been found that the low molecular weight organic matter causes generation of particles that are difficult to ignore on the fine pattern or the substrate. And in the manufacture of organic processing liquids such as organic developers and organic rinsing liquids using a filtering device, the present inventors specify specific filtering conditions, so that in the organic processing liquid It has been found that while removing fine particles with a filter, elution of low-molecular-weight organic substances from the filter can be suppressed, and by using this organic processing liquid, the generation of particles that are likely to be problematic in the formation of miniaturized patterns can be reduced. The present invention has been completed.

That is, the present invention has the following configuration, whereby the above object of the present invention is achieved. <1>
A step of allowing a liquid containing an organic solvent to pass through a filtration device having a liquid inlet part, a liquid outlet part, and a filtration filter membrane provided in a flow path connecting the liquid inlet part and the liquid outlet part. And the absolute value (| T _I −T _o |) of the difference between the temperature (T _I ) of the liquid at the liquid inlet and the temperature (T _o ) of the liquid at the liquid outlet is 3 Or less, the filtration rate of the liquid in the filtration device is 0.5 L / min / m ² or more, the filtration pressure by the liquid in the filtration device is 0.10 MPa or less, and the filtration device is For patterning a chemically amplified resist film, including a filtration filter film made of a fluororesin as the filtration filter film, and the liquid containing the organic solvent is an ester solvent, a ketone solvent, or an alcohol solvent Organic processing A manufacturing method for patterning organic processing liquid prepared chemically amplified resist film by,
An organic processing solution for patterning a chemically amplified resist film, wherein the number of wet particles (N) obtained by the following (1) to (3) is 120 or less.
(1) The number of particles (N1) on an 8-inch silicon wafer is inspected by an AMAT wafer defect evaluation apparatus ComPLUS 3T (inspection mode 30T) installed in a class 1000 clean room;
(2) 5 mL of the organic processing solution for patterning is discharged onto the silicon wafer, and the silicon wafer is rotated at 1000 rpm for 1.6 seconds, whereby the organic processing solution for patterning is transferred to the silicon wafer. Diffused above, allowed to stand for 20 seconds, then spin dried at 2000 rpm for 20 seconds;
(3) After 24 hours, the number of particles (N2) on the silicon wafer is inspected by a wafer defect evaluation apparatus ComPLUS3T (inspection mode 30T) manufactured by AMAT, and N2-N1 is set as the number of wet particles (N).
<2>
The organic processing solution for patterning a chemically amplified resist film according to <1>, wherein the organic processing solution is an organic developer.
<3>
The organic treatment liquid for patterning a chemically amplified resist film according to <2>, wherein the liquid containing the organic solvent is butyl acetate or methyl amyl ketone.
<4>
The organic processing liquid for patterning a chemically amplified resist film according to <1>, wherein the organic processing liquid is an organic rinsing liquid.
<5>
The organic treatment liquid for patterning a chemically amplified resist film according to <4>, wherein the liquid containing the organic solvent is 4-methyl-2-pentanol or butyl acetate.
<6>
The organic processing solution for patterning of the chemically amplified resist film according to any one of the above <1> to <5>, wherein a pore size of the filtration filter film made of the fluororesin is 50 nm or less.
<7>
The organic system for patterning a chemically amplified resist film according to any one of <1> to <6>, wherein the temperature (T _I ) of the liquid at the liquid inlet is 20 ° C. or higher and 30 ° C. or lower. Treatment liquid.
<8>
The organic system for patterning a chemically amplified resist film according to any one of <1> to <7>, wherein the filtration device includes only a filtration filter membrane made of a fluororesin as the filtration filter membrane. Treatment liquid.
In addition, although this invention is invention which concerns on said <1>-<8>, below, it described for reference also.

[1]
A step of allowing a liquid containing an organic solvent to pass through a filtration device having a liquid inlet part, a liquid outlet part, and a filtration filter membrane provided in a flow path connecting the liquid inlet part and the liquid outlet part. A method for producing an organic processing liquid for patterning a chemically amplified resist film,
The absolute value (| T _I −T _o |) of the difference between the temperature (T _I ) of the liquid at the liquid inlet and the temperature (T _o ) of the liquid at the liquid outlet is 3 ° C. or less. The organic solvent for patterning a chemically amplified resist film, wherein the filtration speed of the liquid in the filtration device is 0.5 L / min / m ² or more, and the filtration pressure by the liquid in the filtration device is 0.10 MPa or less. A method for producing a system treatment liquid.
[2]
The method for producing an organic processing solution for patterning a chemically amplified resist film according to [1], wherein the organic processing solution is an organic developer.
[3]
The method for producing an organic processing liquid for patterning a chemically amplified resist film according to [2] above, wherein the liquid containing the organic solvent is butyl acetate.
[4]
The method for producing an organic processing liquid for patterning a chemically amplified resist film according to [1], wherein the organic processing liquid is an organic rinsing liquid.
[5]
The method for producing an organic processing liquid for patterning a chemically amplified resist film according to the above [4], wherein the liquid containing the organic solvent is 4-methyl-2-pentanol or butyl acetate. [6]
The chemically amplified resist film according to any one of [1] to [5], wherein the filtration filter film is a polyethylene resin film, a fluororesin film, or a polyamide resin film having a pore size of 50 nm or less. Manufacturing method of organic processing liquid for patterning.
[7]
The liquid temperature in the liquid inlet portion (T _I) is, at 20 ° C. or higher 30 ° C. or less, the patterning organic treatment liquid chemically amplified resist film according to any one of claims 1 to 6 Production method.
[8]
An organic processing liquid for patterning a chemically amplified resist film produced by the method for producing an organic processing liquid for patterning a chemically amplified resist film according to any one of [1] to [7].
[9] (a) a step of forming a film with a chemically amplified resist composition, (b) a step of exposing the film, and (c) a step of developing the exposed film using an organic developer. A pattern forming method comprising:
A pattern forming method, wherein the organic developer is an organic developer produced by the method for producing an organic processing liquid for patterning a chemically amplified resist film according to the above [2] or [3].
[10]
The pattern forming method according to the above [9], further comprising a step of washing with an organic rinsing solution after the step of developing with the organic developer.
A pattern forming method, wherein the organic rinsing liquid is an organic rinsing liquid produced by the method for producing an organic processing liquid for patterning a chemically amplified resist film according to the above [4] or [5].
[11]
The organic developer is an organic developer produced by the method for producing an organic treatment liquid for patterning a chemically amplified resist film according to the above [3], and the organic rinse liquid is claim 5. The pattern forming method as described in [10] above, which is an organic rinsing liquid produced by the method for producing an organic processing liquid for patterning of the chemically amplified resist film according to the above.
[12]
The step of developing with the organic developer is a step of developing with a developing device equipped with a processing solution filter, and the organic developer is passed through the processing solution filter for development. The pattern forming method according to any one of [9] to [11], which is used.
[13]
The manufacturing method of an electronic device containing the pattern formation method of any one of said [9]-[12].
[14]
The electronic device manufactured by the manufacturing method of the electronic device as described in said [13].

  According to the present invention, the patterning of a chemically amplified resist film capable of reducing the generation of particles, particularly in a negative pattern forming technique for forming a fine pattern (for example, 30 nm node or less) using an organic developer. A method for producing an organic processing solution for use, and an organic processing solution for patterning a chemically amplified resist film, a pattern formation method, an electronic device manufacturing method, and an electronic device using the same.

It is the schematic explaining the manufacturing method of the organic type processing liquid for patterning of the chemically amplified resist film which concerns on embodiment of this invention.

Hereinafter, embodiments of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.
In addition, “exposure” in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, etc. The exposure with the particle beam is also included in the exposure.

FIG. 1 is a schematic diagram illustrating a method for producing an organic processing liquid for patterning a chemically amplified resist film according to an embodiment of the present invention.
As shown in the schematic diagram of FIG. 1, an organic processing liquid manufacturing system 100 includes a liquid tank 11 that can contain a liquid containing an organic solvent, a liquid amount adjustment valve 12, a pressure / flow rate / liquid thermometer 13, and a filtration device 21. , A flow rate / liquid thermometer 14, a flow switching valve 15, and a pump 16. The liquid can be circulated in the order of the liquid tank 11, the liquid amount adjusting valve 12, the pressure / flow rate / liquid thermometer 13, the filtering device 21, the liquid thermometer 14, the flow switching valve 15, the pump 16, the liquid tank 11. As described above, the organic processing liquid manufacturing system 100 is configured.

The liquid tank 11 can accommodate “liquid containing an organic solvent” (hereinafter, also referred to as “organic filtered liquid”) used for filtration, and usually adjusts the temperature of the organic filtered liquid. A possible temperature regulator is attached.
As the liquid tank 11, a known one can be adopted. A preferable material and the like of the liquid tank 11 will be described later together with preferable materials in other members constituting the organic processing liquid manufacturing system 100.
The organic filtrate to be filtered is a liquid that becomes an organic processing liquid for patterning a chemically amplified resist film by being filtered by the filtration device 21 of the organic processing liquid manufacturing system 100, and is preferably a chemically amplified liquid. This is a liquid that becomes an organic developer or an organic rinse of the resist film.
The organic processing liquid for patterning a chemically amplified resist film typically includes (a) a step of forming a film with a chemically amplified resist composition, (a) a step of exposing the film, and (c) exposure. An organic rinsing solution that the pattern forming method may further include after the step (c), or a step of developing the film using an organic developer. It is an “organic rinsing solution” in the cleaning process.

An organic developer means a developer containing an organic solvent.
The organic filtration target liquid (and consequently the organic developer) for producing the organic developer can contain one or more organic solvents.
The amount of the organic solvent used in the production of the organic developer is 90% by mass with respect to the total amount of the organic filtrate (and thus the organic developer). It is preferably 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and still more preferably 95% by mass or more and 100% by mass or less.

Organic filtered liquid for production of organic developer (and hence organic developer) includes polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. A solvent can be used.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl 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-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Can be mentioned.
Examples of the alcohol solvent 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, alcohols such as n-octyl alcohol, n-decanol, 4-methyl-2-pentanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, may be mentioned glycol monoethyl ether and methoxymethyl butanol.
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, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
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. However, in order to fully achieve the effects of the present invention, the water content of the organic filtered liquid (and thus the organic developing liquid) for producing the organic developing liquid as a whole should be less than 10% by mass. Preferably, it is more preferable not to contain water substantially.
In particular, the organic filtered liquid (and hence the organic developer) for producing an organic developer is selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. It is preferable to contain at least one organic solvent.

  The vapor pressure of the organic filtrate to be used for producing the organic developer (and hence the organic developer) is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is improved. To do.

An appropriate amount of a surfactant can be added to the organic filtrate to be produced (and consequently the organic developer) for producing an organic developer as necessary.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-334540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in the specifications of US Pat. 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 with respect to the total amount of the organic filtrate to be produced for the organic developer production (and hence the organic developer). %, More preferably 0.01 to 0.5% by mass.
The organic filtered liquid (and hence the organic developing solution) for producing the organic developing solution is preferably butyl acetate or 2-heptanone (methyl amyl ketone), and preferably butyl acetate.
Moreover, the organic to-be-filtered solution or organic developer for producing an organic developer may contain a nitrogen-containing compound as exemplified in paragraphs 0041 to 0063 of Japanese Patent No. 5056974. From the viewpoint of the storage stability of an organic filtrate for organic developer production or organic developer, nitrogen-containing organic filtrate for organic developer production or organic developer. The compound is preferably added immediately before the pattern formation method.

The organic rinsing liquid means a rinsing liquid containing an organic solvent.
The organic filtered liquid (and consequently the organic rinsing liquid) for producing the organic rinsing liquid can contain one or more organic solvents.
The amount of the organic solvent used in the production of the organic rinsing liquid (and hence the organic rinsing liquid) is 90% by mass relative to the total amount of the organic filtering liquid (and thus the organic rinsing liquid). It is preferably 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and still more preferably 95% by mass or more and 100% by mass or less.

There is no restriction | limiting in particular as long as a resist pattern is not melt | dissolved as an organic to-be-filtered liquid (as a result organic-based rinse liquid), The solution containing a general organic solvent can be used. The rinsing liquid preferably 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.
Specific examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents are the same as those described in the description of the organic filtrate for the production of organic developers. Can be mentioned.
Among them, the organic liquid to be filtered (and thus the organic rinsing liquid) preferably contains an alcohol solvent or an ester solvent, more preferably contains a monohydric alcohol, and a monohydric alcohol having 5 or more carbon atoms. It is still more preferable to contain.
Examples of monohydric alcohols include linear, branched, and cyclic monohydric alcohols. Specific examples 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, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pen Tanol, 3-methyl-1-butanol and the like can be used.
The organic rinsing liquid is preferably 4-methyl-2-pentanol or butyl acetate.

  The water content in the organic filtered liquid (and hence the organic rinsing liquid) is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

  The vapor pressure of the organic filtered liquid (and hence the organic rinsing liquid) is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and more preferably 0.12 kPa or more and 3 kPa at 20 ° C. The following are most preferred. By setting the vapor pressure to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse liquid is suppressed, and the dimensional uniformity in the wafer surface is good. Turn into.

  An appropriate amount of the above-mentioned surfactant can be added to the organic liquid to be filtered (and hence the organic rinsing liquid).

The liquid constituting the organic filtrate is preferably distilled. Thereby, it is possible to manufacture a higher-purity organic processing liquid suitable for patterning a chemically amplified resist film.
Distillation may be performed once or two or more times. A known method can be appropriately applied as the distillation method. For example, although distillation can be performed according to the methods described in JP-A-2006-305573, JP-A-62-161736, JP-A-58-211000, etc., it is limited only to these methods. It is not a thing.

The liquid amount adjusting valve 12 controls the flow rate of the organic filtrate to be filtered, and a known valve can be adopted.
As will be described later, the filtration rate and the filtration pressure of the organic filtrate can be adjusted by controlling the flow rate of the organic filtrate by the liquid amount adjusting valve 12.

The filtration device 21 includes a liquid inlet 21a, a first-stage filter F1 connected to the liquid inlet 21a, a second-stage filter F2 connected to the first-stage filter F1, and a liquid outlet connected to the second-stage filter F2. Part 21b.
Here, the liquid inlet portion 21a is connected to the liquid amount adjusting valve 12 side, and the liquid outlet portion 21b is connected to the flow switching valve 15 side.
The first-stage filter F1 and the second-stage filter F2 are accommodated in the first filter housing H1 and the second filter housing H2, respectively.
The first filter housing H1 and the second filter housing H2 are respectively provided with a filter and an air removal work in the filter housing, or a system for producing an organic night treatment liquid. Drains D1 and D2 for discharging from 100 circulation lines are provided, respectively.

  As described above, the organic processing liquid manufacturing system 100 employs the two-stage filtration method in which the two filters F1 and F2 are used in series.

The shape of the filters F1 and F2 is not particularly limited, but is generally a disk type or a cartridge type.
Each of the filters F1 and F2 includes a media support, a core or cage constituting a filter shape, an end cap, and an O-ring in addition to a filtration filter membrane (filter media) (not shown).
Therefore, the filtration filter membranes in the filters F1 and F2 are provided in the flow path connecting the liquid inlet portion 21a and the liquid outlet portion 21b.

The member constituting the filter is preferably a fluorine resin such as polytetrafluoroethylene (PTFE), a polyolefin resin such as polyethylene (PE) or polypropylene (PP), a polyamide resin such as nylon 6 or nylon 66, and the like. A resin, high-density polyethylene, polypropylene, or a polyamide resin is preferable, and a fluororesin is particularly preferable.
However, fluororesins are highly hydrophobic and may limit the solvents that can be filtered (for example, highly polar solvents). In this case, a highly polar liquid can be easily filtered by forming the filter with a fluororesin having a hydrophilic surface.
The pore size of the filtration filter membrane in each of the filters F1 and F2 is preferably 200 nm or less, more preferably 50 nm or less, and still more preferably 20 nm or less.
Here, when the pore size is 200 nm or less, the fine particles in the liquid containing the organic solvent can be sufficiently removed by the filtration filter membrane.
The pore size of the filtration filter membrane in the filters F1 and F2 is preferably as small as possible, but is usually 5 nm or more.

  The filtration filter membrane in the filters F1 and F2 is preferably a polyethylene resin membrane, a fluororesin membrane, or a polyamide resin membrane having a pore size of 50 nm or less.

  In the present specification, the pore size of the filter membrane means the average pore size of the filter, and is the manufacturer's nominal pore size value.

Since the filtration pressure affects the filtration accuracy, the pressure pulsation during filtration is preferably as small as possible.
In particular, when the amount of fine particles contained in the organic filtered liquid is large, the filter can be prevented from being clogged by removing the large particles step by step, and the productivity of the organic processing liquid can be improved. .
From these viewpoints, it is preferable to employ a multistage filtration method in which a plurality of filters are connected in series and the pore size of the filtration filter membrane is larger as the filtration is closer to the first stage.
That is, in the filtration device 21, the pore size of the filtration filter membrane in the first-stage filter F1 that performs the first-stage filtration is larger than the pore size of the filtration filter membrane in the second-stage filter F2 that performs the second-stage filtration. Is preferred.

  Moreover, as a method of removing foreign matters such as fine particles from the liquid with a filtration filter membrane, in addition to a method utilizing a sieving effect by setting the pore size of the filtration filter membrane to be smaller than the size of the foreign matter, the filtration filter membrane for foreign matters is used. A method of adsorbing on the surface of the filter is also known, and a filtration filter membrane that can adsorb and remove low molecular weight organic substances (for example, low molecular weight olefin compounds) considered as an object to be removed by the present invention is also preferable.

  Examples of commercially available cartridge filters that can be used as the filters F1 and F2 include, for example, Microguard Plus, Fluorogard AT / ATX, manufactured by Nihon Entegris Co., Ltd., PE-Clean, Enflon PF, Ulticlean Examples include Exceller, Ultiplez and P-Nylon.

The pressure / flow rate / liquid thermometer 13 is a measuring instrument that measures the pressure, flow rate, and temperature of the liquid at the liquid inlet portion 21a of the filtration device 21, and any known one can be employed.
The flow rate / liquid thermometer 14 is a measuring instrument that measures the temperature of the liquid at the liquid outlet 21b of the filtration device 21, and any known one can be employed. The pressure / flow rate / liquid thermometer 13 and the flow rate / liquid thermometer 14 mainly include the liquid temperature (T _I ) at the liquid inlet portion 21a and the liquid temperature (T _o ) at the liquid outlet portion 21b, which will be described in detail later. ), The absolute value of the difference (| T _I −T _o |), the filtration speed of the liquid in the filtration device 21, and the filtration pressure by the liquid in the filtration device 21. It is not essential for manufacturing itself. Therefore, the pressure / flow rate / liquid thermometer 13 and the flow rate / liquid thermometer 14 can be omitted except when the manufacturing conditions are confirmed.

  The flow switching valve 15 is a valve that can switch the flow of the liquid from the filtration device 21 between the pump 16 side (circulation side) and the liquid outlet 17 side (extraction side). Can also be adopted.

  The pump 16 is a pump for sending the liquid from the flow switching valve 15 to the liquid tank 11, and is provided with a drain D <b> 3 for discharging the liquid from the circulation line of the organic processing liquid manufacturing system 100. . Any known pump can be used as the pump 16, but a pump that generates less bubbles and less pulsation is particularly preferable in terms of minimizing the introduction of contamination into the liquid from the organic processing liquid manufacturing system 100. preferable.

In the organic processing liquid manufacturing system 100, a material constituting an inner wall that comes into contact with the liquid in the liquid tank 11 and a contact surface with respect to the liquid in a flow path (pipe, seal portion, joint member, etc.) other than the filtration device 21 described above. Is a resin different from “one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin”, or a metal that has been subjected to rust prevention and metal elution prevention treatment. Is preferred.
As for the liquid tank 11, when the liquid tank 11 further has a seal portion for sealing the organic filtered liquid, this seal portion is also “polyethylene resin, polypropylene resin, and polyethylene- It is preferably formed from a resin different from “one or more resins selected from the group consisting of polypropylene resins” or a metal that has been subjected to a rust prevention / metal elution prevention treatment.
Here, the said seal part means the member which can interrupt | block outside air, and can mention a packing, an O-ring etc. suitably.
The resin different from at least one resin selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin is preferably a perfluoro resin.

Examples of perfluororesins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), and tetrafluoride. Ethylene-ethylene copolymer resin (ETFE), ethylene trifluoride-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), ethylene trifluoride chloride copolymer resin (PCTFE), vinyl fluoride resin ( PVF) and the like.
Particularly preferred perfluoro resins include tetrafluoroethylene resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer resin.

Examples of the metal in the metal subjected to the rust prevention / metal elution prevention treatment include carbon steel, alloy steel, nickel chromium steel, nickel chromium molybdenum steel, chromium steel, chromium molybdenum steel, manganese steel and the like.
As the rust prevention / metal elution prevention treatment, it is preferable to apply a film technology.
There are three types of coating technology: metal coating (various plating), inorganic coating (various chemical conversion treatment, glass, concrete, ceramics, etc.) and organic coating (rust prevention oil, paint, rubber, plastics). .
Preferable film technology includes surface treatment with a rust preventive oil, a rust preventive agent, a corrosion inhibitor, a chelate compound, a peelable plastic, and a lining agent.
Among them, various chromates, nitrites, silicates, phosphates, carboxylic acids such as oleic acid, dimer acid, naphthenic acid, carboxylic acid metal soaps, sulfonates, amine salts, esters (glycerin esters of higher fatty acids) And chelating compounds such as ethylene diantetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethyl ethyl orange amine trisuccinic acid, diethylene triamine pentic acid, and fluororesin lining. Particularly preferred are phosphating and fluororesin lining.
In addition, compared with direct coating treatment, it does not directly prevent rust, but as a treatment method that leads to the extension of the rust prevention period by coating treatment, "pretreatment" is a stage before rust prevention treatment. It is also preferable to adopt.
As a specific example of such pretreatment, a treatment for removing various corrosive factors such as chlorides and sulfates existing on the metal surface by washing and polishing can be preferably mentioned.

In the organic processing liquid manufacturing system 100, by operating the pump 16, the liquid circulates in the system, and the organic filtered liquid stored in the liquid tank 11 passes through the filtration device 21, An organic processing solution for patterning a chemically amplified resist film is manufactured.
The produced organic processing liquid is taken out from the liquid outlet 17 by switching the flow switching valve 15 to the liquid outlet 17 side.
From the viewpoint of improving the uniformity of the filtration accuracy, the liquid may be circulated in the system for a certain time or longer by operating the pump for a certain time or longer. Further, the liquid coming out from the outlet 17 may be inspected periodically, and after the particle inspection result is stabilized, the pump may be stopped and the filtered liquid may be taken out from the outlet 17.

In general, the organic filtrate to be filtered has a small specific heat and a high volatility. Therefore, the liquid temperature fluctuates in a portion where the liquid temperature control is not sufficiently performed (particularly when passing through the filter). In addition, when the organic liquid to be filtered is a solvent having a high viscosity, the filtration time becomes longer, so that the influence of the liquid temperature fluctuation becomes larger.
The present inventors have found that the suppression of the temperature fluctuation is particularly effective in reducing the generation of particles in a negative pattern forming technique of forming a fine pattern (for example, 30 nm node or less) using an organic developer. Found to contribute.

That is, in the method for producing an organic processing liquid for patterning a chemically amplified resist film according to the present invention, first, the temperature (T _I ) of the liquid at the liquid inlet portion 21a of the filtration device 21 and the liquid outlet of the filtration device 21. The absolute value (| T _I −T _o |) of the difference from the liquid temperature (T _o ) in the part 21b is set to 3 ° C. or less.
When the absolute value | T _I −T _o | exceeds 3 ° C., the generation of particles that may be regarded as a problem is reduced in a negative pattern forming technique in which a fine pattern is formed using an organic developer. It becomes difficult.
As described above, the filter is composed of various components such as a filtration filter membrane (filter media), a media support, a core or cage constituting the filter shape, an end cap, and an O-ring, and is disliked by metal contamination. Because of the limitation of semiconductor manufacturing applications, the filter component is basically made of resin. Generally, various additives are contained in the resin in order to ensure the durability of the resin. In general, resin synthesis methods (radical method, thermal polymerization method) that are widely used include a low molecular weight polymer rather than the target resin molecular weight. These additives and low molecular weight polymers are soluble in the organic processing liquid and become a contamination of the processing liquid. In particular, it is considered that this contamination cannot be ignored in an organic processing liquid used in a negative pattern forming technique for forming a fine pattern (for example, a node of 30 nm or less). Since this contamination is caused by the solubility of the substance, in order to control the contamination to a minimum and constant, the liquid temperature control during the filtration (more specifically, the absolute value | T _I −T _o described above). It is presumed that the generation of the particles is reduced by performing temperature management in which | is 3 ° C. or lower.

The absolute value | T _I −T _o | is preferably 2 ° C. or less, more preferably 1 ° C. or less, more preferably 0.5 ° C. or less, and particularly preferably 0 ° C. preferable.

The temperature of the liquid affects the viscosity of the liquid to be filtered and the amount of impurities mixed into the organic processing liquid from the equipment constituting the manufacturing system.
When the temperature of the liquid is low, the viscosity of the liquid to be filtered becomes too high, the filtration flow rate is reduced, and the filtration pressure is increased, so that it is difficult to achieve both filtration accuracy and productivity.
On the other hand, the solubility of substances in the liquid is generally lower when the temperature of the liquid is lower. Therefore, the temperature of the liquid used for filtration is low to some extent, which indicates that the organic processing liquid from the equipment constituting the manufacturing system This is preferable from the viewpoint of reducing the amount of impurities mixed.
Therefore, in order to satisfy the filtration accuracy, the contamination contamination amount from the manufacturing process equipment to the organic processing, and the productivity, in addition to the absolute value | T _I −T _o |, the temperature of the liquid during filtration It is more preferable to manage itself.
Specifically, the temperature of the liquid before passing through the filter, that is, the temperature (T _I ) of the liquid at the liquid inlet 21a of the filtering device 21 is preferably 15 ° C. or higher and 35 ° C. or lower, and 20 ° C. or higher and 30 ° C. It is more preferable that the temperature is 20 ° C. or more and 25 ° C. or less.

As a method of adjusting the absolute value | T _I −T _o | and the temperature T _I , for example, the tank 11, the liquid inlet 21a of the filtration device 21, the first filter housing H1, the second filter housing H2, and The temperature management of the organic processing liquid manufacturing system 100 was performed by attaching a heat insulation facility (a well-known facility such as a heater or a water jacket) to at least one of the liquid outlet portions 21b and adjusting the temperature at each position. The method of installing in a clean room etc. can be mentioned preferably.

Further, the filtration rate affects the filtration accuracy, the amount of impurities mixed into the organic processing liquid from the filter, and the productivity.
In general, a low filtration rate is preferable in order to increase the filtration accuracy, but it can increase the amount of impurities mixed into the organic processing liquid from the filter and reduce productivity.
As a result of intensive studies, the inventors of the present invention have, as described above, the liquid temperature (T _I ) at the liquid inlet 21 a of the filtration device 21 and the liquid temperature (T _o ) at the liquid outlet 21 b of the filtration device 21. The absolute value of the difference (| T _I −T _o |) is 3 ° C. or lower, and the filtration speed is set to a predetermined value or higher while lowering the filtration pressure. It has been found that the generation of particles can be reduced in a negative pattern forming technique that forms a fine pattern (for example, a node of 30 nm or less) by using it (and that the productivity can be satisfied).

That is, in the method for producing an organic processing liquid for patterning a chemically amplified resist film of the present invention, the filtration rate of the liquid in the filtration device 21 is 0.5 L / min / m ² or more, and the filtration device 21 is used. The filtration pressure by the liquid in is set to 0.10 MPa or less.

On the other hand, if the filtration rate is less than 0.5 L / min / m ² or the filtration pressure is more than 0.10 MPa, a negative pattern is formed using an organic developer. In the technology, it becomes difficult to reduce the generation of particles that can be regarded as a problem.

The filtration rate is preferably 0.6 L / min / ^{m 2} or more, more preferably 0.75 L / min / ^{m 2} or more, still be at 1.0 L / min / ^{m 2} or more preferable.
The filter has a differential pressure resistance that assures filter performance (the filter will not break). If this value is large, the filtration speed can be increased by increasing the filtration pressure. That is, the upper limit of the filtration rate usually depends on the resistance to pressure difference of the filter, but is usually preferably 10.0 L / min / m ² or less.

The filtration pressure is preferably 0.01 MPa or more and 0.10 MPa or less, more preferably 0.03 MPa or more and 0.08 MPa or less, and particularly preferably 0.03 MPa or more and 0.06 MPa or less.
In addition, when the pore size of the filtration filter membrane decreases, the filtration speed decreases.For example, by connecting a plurality of filters equipped with the same type of filtration filter membrane in parallel, the filtration area is expanded and the filtration pressure is increased. This makes it possible to compensate for the reduction in filtration rate.

The filtration speed of the liquid in the filtration device can be determined using the filtration flow rate of the liquid flowing through the filtration device.
The filtration rate of the liquid in the filtration device can be defined as follows:

Filtration rate of liquid in the filtration device (L / min / m ² ) = filtration flow rate of liquid flowing through the filtration device (L / min) / total filtration surface area of all filtration filter membranes in the filtration device (m ² )
Here, the filtration flow rate of the liquid flowing through the filtration device is a flow meter attached to the liquid inlet portion or the liquid outlet portion of the filtration device (in the organic processing liquid production system 100, the pressure / flow rate / liquid thermometer 13, or The flow rate / liquid thermometer 14) can be measured.
As the filtration surface area (m ² ) of the filtration filter membrane, a value published by the manufacturer of the filtration filter membrane can be adopted.

  The filtration pressure by the liquid in the filtration device is the pressure of the liquid at the liquid inlet of the filtration device regardless of the arrangement of the filtration filter membrane. In the organic processing liquid production system 100, the pressure / flow rate / liquid The pressure value measured by the thermometer 13 can be used as the filtration pressure by the liquid in the filtration device 21.

  The filtration speed and filtration pressure of the liquid in the filtration device can be adjusted by changing the flow rate of the organic filtrate to be filtered by the liquid amount adjusting valve 12, the type of filter, the arrangement method of the filter, and the like.

As described above, the manufacturing method of the organic processing liquid for patterning of the chemically amplified resist film according to the embodiment of the present invention has been described. However, the manufacturing method of the organic processing liquid for patterning of the chemically amplified resist film of the present invention is as follows. However, the present invention is not limited to the above-described embodiment, and appropriate modifications and improvements can be made.
For example, in the above-described embodiment, the organic processing liquid manufacturing system 100 is configured so that the liquid that has passed through the filtration device 21 can be returned to the liquid tank 11, that is, a circulation line is formed. A type organic processing liquid production system may be adopted.
In addition, for example, in the above-described embodiment, the two-stage filtration method using two filters in series is used, but a plurality of filters are not used in series (for example, only one filter is used). Filtration may be used, or multistage filtration using three or more filters in series may be used.
If there is no hindrance in the compatibility between the production productivity and the production cost of the organic processing liquid, a four-stage or more filtration method may be used, but in view of the balance between the production productivity and the production cost, the two-stage or It is preferable to employ a three-stage filtration method.
For example, in the organic processing liquid manufacturing system 100 described above, the pump 16 is provided between the flow switching valve 15 and the liquid tank 11, but is provided between the liquid tank 11 and the filtration device 21. Also good.

  The present invention also relates to an organic processing liquid for patterning a chemically amplified resist film manufactured by the method for manufacturing an organic processing liquid for patterning a chemically amplified resist film according to the above-described embodiment of the present invention. .

  Next, the pattern formation method using the organic processing liquid manufactured by the manufacturing method of the organic processing liquid for patterning of the above-mentioned chemical amplification type resist film of this invention is demonstrated.

The pattern forming method of the present invention comprises:
(A) forming a film (chemically amplified resist film) from the chemically amplified resist composition;
(A) a step of exposing the film, and (c) a step of developing the exposed film using an organic developer,
including.
Here, the organic developer in the step (c) is an organic developer produced by the above-described method for producing an organic processing solution for patterning of the chemically amplified resist film of the present invention, and specific examples and preferable examples thereof. Examples are as described above.

The exposure in the exposure step may be immersion exposure.
It is preferable that the pattern formation method of this invention has a heating process after an exposure process.
Moreover, the pattern formation method of this invention may further have the process developed using an alkaline developing solution.
The pattern formation method of this invention can have an exposure process in multiple times.
The pattern formation method of this invention can have a heating process in multiple times.

  In the pattern forming method of the present invention, the exposure step and the development step can be performed by generally known methods.

It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step.
It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.
The heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. for both PB and PEB.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.

Although there is no restriction | limiting in the light source wavelength used for the exposure apparatus in this invention, Infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, an electron beam, etc. can be mentioned, Preferably it is 250 nm or less. More preferably 220 nm or less, particularly preferably far ultraviolet light having a wavelength of 1 to ₂₀₀ nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc., KrF excimer laser, ArF excimer laser, EUV or electron beam are preferable, and ArF excimer laser is more preferable.

Moreover, the immersion exposure method can be applied in the step of performing exposure according to the present invention.
Furthermore, it can be combined with super-resolution techniques such as the phase shift method and the modified illumination method that are currently being studied.

  When performing immersion exposure, (1) after forming the film on the substrate, before the exposure step and / or (2) after exposing the film via the immersion liquid, Prior to the heating step, a step of washing the surface of the membrane with an aqueous chemical may be performed.

  The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the film. In the case of an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.

When water is used, an additive (liquid) that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens element.
As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained.

  On the other hand, when an opaque substance or impurities whose refractive index is significantly different from that of water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. Therefore, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.

The electrical resistance of the water used as the immersion liquid is preferably 18.3 MΩcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.
Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

When the film formed using the composition of the present invention is exposed through an immersion medium, a hydrophobic resin (D) described later can be further added as necessary. By adding the hydrophobic resin (D), the receding contact angle of the surface is improved. The receding contact angle of the film is preferably 60 ° to 90 °, more preferably 70 ° or more.
In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head scanning the wafer at high speed to form the exposure pattern, so that the dynamic state is reached. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

In order to prevent the film from directly contacting the immersion liquid between the film formed using the composition of the present invention and the immersion liquid, an immersion liquid hardly soluble film (hereinafter also referred to as “top coat”). May be provided. Functions necessary for the top coat include suitability for application to the resist upper layer, transparency to radiation, particularly radiation having a wavelength of 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the upper layer of the resist.
From the viewpoint of transparency at 193 nm, the topcoat is preferably a polymer that does not contain aromatics.
Specific examples include hydrocarbon polymers, acrylic ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers, and fluorine-containing polymers. The above-mentioned hydrophobic resin (D) is also suitable as a top coat. When impurities are eluted from the top coat into the immersion liquid, the optical lens is contaminated. Therefore, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable.
There is preferably no or small difference in refractive index between the top coat and the immersion liquid. In this case, the resolution can be improved. When the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water as the immersion liquid. Therefore, the top coat for ArF immersion exposure is close to the refractive index of water (1.44). preferable. Moreover, it is preferable that a topcoat is a thin film from a viewpoint of transparency and a refractive index.

  The topcoat is preferably not mixed with the membrane and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the composition of the present invention. Further, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

In the present invention, the substrate on which the film is formed is not particularly limited, and silicon, SiN, inorganic substrates such as SiO ₂ and SiN, coated inorganic substrates such as SOG, semiconductor manufacturing processes such as IC, liquid crystal, and thermal head For example, a substrate generally used in a circuit board manufacturing process or other photofabrication lithography process can be used. Furthermore, if necessary, a known inorganic or organic antireflection film may be formed between the film and the substrate.

When the pattern forming method of the present invention further includes a step of developing using an alkali developer, examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia. Inorganic alkalis such as water, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, Alkaline aqueous solutions such as alcohol amines such as ethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.
By combining development with an organic developer and development with an alkaline developer, US Pat. No. 8,227,183B, FIG. As described in 1 to 11 and the like, it can be expected to resolve a pattern having a line width that is ½ of the mask pattern.

As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added.
In addition, after the developing process or the rinsing process, a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

As described above, the organic developer in the step of developing the exposed film using an organic developer is an organic type produced by the method for producing an organic processing solution for patterning a chemically amplified resist film according to the present invention. As a developing method, for example, a method of immersing the substrate in a tank filled with the developer for a certain period of time (dip method), a method of raising the developer on the surface of the substrate by surface tension and leaving it stationary for a certain period of time. Method of developing (paddle method), method of spraying developer on the substrate surface (spray method), and method of continuously discharging developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (Dynamic dispensing method) can be applied.
When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm ² or less, More preferably, it is 1.5 mL / sec / mm ² or less, More preferably, it is 1 mL / sec / mm ² or less. There is no particular lower limit on the flow rate, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied by the developer to the resist film will decrease, and the resist film / resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.

  Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.

  Moreover, you may implement the process of stopping image development, after substituting with another solvent after the process developed using the developing solution containing an organic solvent.

The developing device used in the step of developing with an organic developer is preferably a coating and developing device that can apply an organic developer. Examples of the coating and developing device include LITHIUS, LITHIUS i +, and LITHIUS manufactured by Tokyo Electron Limited. Pro, LITHIUS Pro-i, LITHIUS Pro V, LITHIUS Pro Vi, and RF ^3S manufactured by SOKUDO, SOKUDO DUO, and the like.
These coating and developing apparatuses are typically equipped with a connecting chemical solution filter (processing solution filter) called a POU filter.
Therefore, in the development process, a POU-mounted coating and developing device (a developing device equipped with a processing solution filter) is used, and the patterning organic processing solution (especially an organic developing solution) is allowed to pass through the POU filter. May be used for development.

It is preferable to carry out the following two points when used in a POU-mounted coating and developing apparatus.
1. When a new POU filter is used, a treatment liquid used immediately after the POU filter is set in the apparatus is passed in an amount of 30 L or more.
2. If there is time not to be used for more than 6 hours, perform a dummy dispense of 1L or more immediately before use.

The pattern forming method of the present invention preferably further includes a step of washing with an organic rinse after the step of developing with an organic developer.
Here, the organic rinsing liquid is an organic rinsing liquid manufactured by the above-described method for manufacturing an organic processing liquid for patterning a chemically amplified resist film of the present invention, and specific examples and preferred examples thereof are as described above. It is.

  In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is washed using the rinse solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

  The pattern forming method of the present invention further includes a step of washing with an organic rinsing solution after the step of developing with an organic developer, and the organic developer is a chemical amplification of the present invention described above. Butyl acetate as an organic processing liquid obtained by a method for producing an organic processing liquid for patterning of a resist film, and the organic rinsing liquid is an organic for patterning of the above-described chemically amplified resist film of the present invention. It is more preferable that it is butyl acetate as an organic type processing liquid obtained by the manufacturing method of the type | system | group processing liquid.

  The chemically amplified resist composition used in the pattern forming method of the present invention is not particularly limited as long as it is a resist composition in which a chemical reaction in the system triggered by exposure is chained catalytically, but typically A chemically amplified resist containing part or all of the following components is preferably used.

[1] (A) Resin whose polarity increases due to the action of an acid and decreases in solubility in a developer containing an organic solvent Resin whose polarity increases due to the action of an acid and decreases in solubility in a developer containing an organic solvent Examples of (A) include a group (hereinafter also referred to as an “acid-decomposable group”) that decomposes into the main chain or side chain of the resin, or both the main chain and the side chain, by the action of an acid to generate a polar group. ) (Hereinafter also referred to as “acid-decomposable resin” or “resin (A)”).
The acid-decomposable group preferably has a structure protected by a group capable of decomposing and leaving a polar group by the action of an acid. Preferred polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.

A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted 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 and 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. Moreover, when performing the pattern formation method of this invention by exposure by KrF light or EUV light, or electron beam irradiation, you may use the acid-decomposable group which protected the phenolic hydroxyl group with the acid leaving group.

The resin (A) preferably has a repeating unit having an acid-decomposable group.
Examples of the repeating unit include the following.
In specific examples, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Z represents a substituent, and when a plurality of Zs are present, the plurality of Zs may be the same as or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and preferred examples of the substituent that each group such as Rx _{1 to} Rx ₃ may have.

  In the following specific examples, Xa represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.

In the following specific examples, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

  One type of repeating unit having an acid-decomposable group may be used, or two or more types may be used in combination.

  The content of the repeating unit having an acid-decomposable group contained in the resin (A) (when there are a plurality of repeating units having an acid-decomposable group, the total) is based on the total repeating units of the resin (A), It is preferably 15 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, and particularly preferably 40 mol% or more.

The resin (A) may contain a repeating unit having a lactone structure or a sultone structure.
Specific examples of the repeating unit having a group having a lactone structure or a sultone structure are shown below, but the present invention is not limited thereto.

  Two or more types of repeating units having a lactone structure or a sultone structure can be used in combination.

  When the resin (A) contains a repeating unit having a lactone structure or a sultone structure, the content of the repeating unit having a lactone structure or a sultone structure is 5 to 60 mol% with respect to all the repeating units in the resin (A). Is more preferable, more preferably 5-55 mol%, still more preferably 10-50 mol%.

Moreover, the resin (A) may have a repeating unit having a cyclic carbonate structure. Although a specific example is given how, this invention is not limited to these.
In the following specific examples, R _A ¹ represents a hydrogen atom or an alkyl group (preferably a methyl group).

The resin (A) may have a repeating unit having a hydroxyl group or a cyano group.
Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.

Resin (A) may have a repeating unit having an acid group.
The resin (A) may or may not contain a repeating unit having an acid group, but when it is contained, the content of the repeating unit having an acid group is relative to all the repeating units in the resin (A). It is preferably 25 mol% or less, and more preferably 20 mol% or less. When resin (A) contains the repeating unit which has an acid group, content of the repeating unit which has an acid group in resin (A) is 1 mol% or more normally.

Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

The resin (A) further has an alicyclic hydrocarbon structure and / or an aromatic ring structure that does not have a polar group (for example, the acid group, hydroxyl group, cyano group), and has a repeating unit that does not exhibit acid decomposability. be able to.
Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  When the composition of the present invention is for ArF exposure, the resin (A) used in the composition of the present invention has substantially no aromatic ring from the viewpoint of transparency to ArF light (specifically, The ratio of the repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol%, that is, no aromatic group). The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

The form of the resin (A) in the present invention may be any of random type, block type, comb type, and star type. Resin (A) is compoundable by the radical, cation, or anion polymerization of the unsaturated monomer corresponding to each structure, for example. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.
When the composition of the present invention is for ArF exposure, the resin (A) used in the composition of the present invention has substantially no aromatic ring from the viewpoint of transparency to ArF light (specifically, The ratio of the repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol%, that is, no aromatic group). The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
When the composition of this invention contains resin (D) mentioned later, it is preferable that resin (A) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with resin (D).

  The resin (A) used in the composition of the present invention is preferably one in which all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.

  When the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, high energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin (A) has a repeating unit having an aromatic ring. May be. The repeating unit having an aromatic ring is not particularly limited, and is also exemplified in the above description of each repeating unit, but a styrene unit, a hydroxystyrene unit, a phenyl (meth) acrylate unit, a hydroxyphenyl (meth) acrylate. Examples include units. More specifically, the resin (A) is a resin having a hydroxystyrene-based repeating unit and a hydroxystyrene-based repeating unit protected by an acid-decomposable group, a repeating unit having the aromatic ring, and (meth) Examples thereof include a resin having a repeating unit in which the carboxylic acid moiety of acrylic acid is protected by an acid-decomposable group.

  The resin (A) in the present invention can be synthesized and purified according to a conventional method (for example, radical polymerization). For the synthesis method and purification method, see, for example, the descriptions in paragraphs 0201 to 0202 of JP-A-2008-292975.

  The weight average molecular weight of the resin (A) in the present invention is 7,000 or more, preferably 7,000 to 200,000, more preferably 7,000 as described above in terms of polystyrene by GPC method. 50,000 to 50,000, even more preferably 7,000 to 40,000, and particularly preferably 7,000 to 30,000. When the weight average molecular weight is less than 7000, the solubility in an organic developer becomes too high, and there is a concern that a precise pattern cannot be formed.

  The dispersity (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. Those in the range are used. The smaller the molecular weight distribution, the better the resolution and the resist shape, the smoother the sidewall of the resist pattern, and the better the roughness.

In the chemically amplified resist composition of the present invention, the blending ratio of the resin (A) in the entire composition is preferably 30 to 99% by mass, more preferably 60 to 95% by mass in the total solid content.
In the present invention, the resin (A) may be used alone or in combination.

  Hereinafter, although the specific example (composition ratio of a repeating unit is a molar ratio) of resin (A) is given, this invention is not limited to these. In addition, below, the aspect in case the structure corresponding to an acid generator (B) mentioned later is carry | supported by resin (A) is also illustrated.

  The resin exemplified below is an example of a resin that can be suitably used particularly during EUV exposure or electron beam exposure.

[2] (B) Compound that generates acid upon irradiation with actinic ray or radiation Usually, the composition in the present invention further includes compound (B) that generates acid upon irradiation with actinic ray or radiation (hereinafter referred to as “acid generation”). Also referred to as “agent”. The compound (B) that generates an acid upon irradiation with actinic rays or radiation is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation.
As the acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, irradiation of actinic ray or radiation used for micro resist, etc. The known compounds that generate an acid and mixtures thereof can be appropriately selected and used.

Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.
Among acid generators, particularly preferred examples are given below.

The acid generator can be synthesized by a known method. For example, [0200] to [0210] of JP-A No. 2007-161707, JP-A No. 2010-100595, and International Publication No. 2011/093280 [ [0051] to [0058], [0382] to [0385] of International Publication No. 2008/153110, Japanese Patent Application Laid-Open No. 2007-161707, and the like.
An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the compound that generates an acid upon irradiation with actinic rays or radiation in the composition is preferably 0.1 to 30% by mass, more preferably 0. 0% by mass based on the total solid content of the chemically amplified resist composition. It is 5-25 mass%, More preferably, it is 3-20 mass%, Most preferably, it is 3-15 mass%.

In addition, depending on the resist composition, there is also an embodiment (B ′) in which a structure corresponding to the acid generator is supported on the resin (A). Specific examples of such an embodiment include the structures described in JP2011-2448019 (particularly, structures described in paragraphs 0164 to 0191, structures included in the resin described in the examples in paragraph 0555), and the like. Can be mentioned. Incidentally, even if the structure corresponding to the acid generator is supported by the resin (A), the resist composition additionally contains an acid generator not supported by the resin (A). May be included.
Examples of the embodiment (B ′) include the following repeating units, but are not limited thereto.

[3] (C) Solvent The chemically amplified resist composition usually contains a solvent (C).
Solvents that can be used in preparing the chemically amplified resist composition include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably Examples thereof include organic solvents such as carbon number 4 to 10), monoketone compounds (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
Specific examples of these solvents can include those described in US Patent Application Publication No. 2008/0187860 [0441] to [0455].

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether ( PGME, also known as 1-methoxy-2-propanol), ethyl lactate is more preferred. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate are particularly preferred, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2 -Heptanone is most preferred.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

[4] Hydrophobic resin (D)
The chemical amplification resist composition according to the present invention contains a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (D)” or simply “resin (D)”), particularly when applied to immersion exposure. Also good. The hydrophobic resin (D) is preferably different from the resin (A).
As a result, the hydrophobic resin (D) is unevenly distributed in the film surface layer, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion liquid followability is improved. be able to.
The hydrophobic resin (D) is preferably designed to be unevenly distributed at the interface as described above. However, unlike the surfactant, the hydrophobic resin (D) does not necessarily need to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.

The hydrophobic resin (D) is selected from any one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have the above, and it is more preferable to have two or more.

The weight average molecular weight of the hydrophobic resin (D) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000. is there.
In addition, the hydrophobic resin (D) may be used alone or in combination.
The content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention. More preferably, it is 1-7 mass%.

  As for the hydrophobic resin (D), as in the resin (A), it is natural that the residual monomer and oligomer components are preferably 0.01 to 5% by mass, and more preferably less impurities such as metals. Is more preferably 0.01 to 3% by mass and 0.05 to 1% by mass. As a result, a chemically amplified resist composition having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

As the hydrophobic resin (D), various commercially available products can be used, and the hydrophobic resin (D) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.
The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described for the resin (A), but in the synthesis of the hydrophobic resin (D), The reaction concentration is preferably 30 to 50% by mass. For more details, refer to the description in paragraphs 0320 to 0329 of JP-A-2008-292975.

  Specific examples of the hydrophobic resin (D) are shown below. The following table shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

[5] Basic Compound The chemically amplified resist composition in the present invention preferably contains a basic compound.
The chemically amplified resist composition may contain, as a basic compound, a basic compound or an ammonium salt compound (hereinafter also referred to as “compound (N)”) whose basicity is reduced by irradiation with actinic rays or radiation. preferable.

  The compound (N) is preferably a compound (N-1) having a basic functional group or an ammonium group and a group that generates an acidic functional group upon irradiation with actinic rays or radiation. That is, the compound (N) is a basic compound having a basic functional group and a group capable of generating an acidic functional group upon irradiation with actinic light or radiation, or an acidic functional group upon irradiation with an ammonium group and active light or radiation. An ammonium salt compound having a group to be generated is preferable. Particularly preferred examples of this compound are shown below. In addition, the compounds exemplified as (A-1) to (A-23) from page 5 onwards in US2012 / 0156617A specification, the pages on and after page 9 in US2006 / 0264528A specification, (A-1) to The compounds mentioned as (A-44) are also preferred.

These compounds can be synthesized according to the synthesis example of JP-A-2006-330098.
The molecular weight of the compound (N) is preferably 500 to 1000.

  The chemically amplified resist composition in the present invention may or may not contain the compound (N), but when it is contained, the content of the compound (N) is based on the solid content of the chemically amplified resist composition. As for, 0.1-20 mass% is preferable, More preferably, it is 0.1-10 mass%.

The chemically amplified resist composition in the present invention contains a basic compound (N ′) that is different from the compound (N) as a basic compound in order to reduce the change in performance over time from exposure to heating. It may be.
Preferred examples of the basic compound (N ′) include compounds having a structure represented by the following formulas (A ′) to (E ′).

In general formulas (A ′) and (E ′):
RA ²⁰⁰ , RA ²⁰¹ and RA ²⁰² may be the same or different and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number). 6-20), where RA ²⁰¹ and RA ²⁰² may combine with each other to form a ring. RA ²⁰³ , RA ²⁰⁴ , RA ²⁰⁵ and RA ²⁰⁶ may be the same or different and each represents an alkyl group (preferably having 1 to 20 carbon atoms).
The alkyl group may have a substituent, and examples of the alkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, and a carbon atom having 1 to 20 carbon atoms. A cyanoalkyl group is preferred.
The alkyl groups in the general formulas (A ′) and (E ′) are more preferably unsubstituted.

  Specific examples of the basic compound (N ′) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, and more preferable specific examples include an imidazole structure. , Diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure compound, alkylamine derivative having hydroxyl group and / or ether bond, aniline derivative having hydroxyl group and / or ether bond Etc.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4. 0] Undecaker 7-ene and the like. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris (t-butylphenyl) Examples include sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. As a compound which has an onium carboxylate structure, the anion part of the compound which has an onium hydroxide structure turns into a carboxylate, For example, an acetate, an adamantane 1-carboxylate, a perfluoroalkyl carboxylate etc. are mentioned. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the compound having an aniline structure include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group. Specific examples thereof include, but are not limited to, compounds (C1-1) to (C3-3) exemplified in [0066] of US Patent Application Publication No. 2007/0224539. .

  Further, as one kind of basic compound, a nitrogen-containing organic compound having a group capable of leaving by the action of an acid can also be used. As an example of this compound, for example, specific examples of the compound are shown below.

  The said compound is compoundable according to the method as described in Unexamined-Japanese-Patent No. 2009-199021, for example.

  As the basic compound (N ′), a compound having an amine oxide structure can also be used. Specific examples of this compound include triethylamine pyridine N-oxide, tributylamine N-oxide, triethanolamine N-oxide, tris (methoxyethyl) amine N-oxide, tris (2- (methoxymethoxy) ethyl) amine = oxide. 2,2 ′, 2 ″ -nitrilotriethylpropionate N-oxide, N-2- (2-methoxyethoxy) methoxyethylmorpholine N-oxide, and other amine oxide compounds exemplified in JP-A-2008-102383 are used. Is possible.

  The molecular weight of the basic compound (N ′) is preferably 250 to 2000, more preferably 400 to 1000. From the viewpoint of further reduction in LWR and uniformity of local pattern dimensions, the molecular weight of the basic compound is preferably 400 or more, more preferably 500 or more, and even more preferably 600 or more. .

  These basic compounds (N ′) may be used in combination with the compound (N), or may be used alone or in combination of two or more.

  The chemically amplified resist composition in the present invention may or may not contain the basic compound (N ′), but when it is contained, the amount of the basic compound (N ′) used depends on the chemically amplified resist composition. Based on the solid content of the product, it is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass.

  Further, the chemically amplified resist composition of the present invention includes a compound included in the formula (I) of JP 2012-189777 A, a compound represented by the formula (I) of JP 2013-6827 A, and JP An onium salt structure and an acid anion structure in one molecule, such as a compound represented by formula (I) of 2013-8020 and a compound represented by formula (I) of JP 2012-252124 A A compound having both (hereinafter also referred to as betaine compound) can be preferably used. Examples of the onium salt structure include a sulfonium, iodonium, and ammonium structure, and a sulfonium or iodonium salt structure is preferable. The acid anion structure is preferably a sulfonate anion or a carboxylic acid anion. Examples of this compound include the following.

[6] (F) Surfactant The chemically amplified resist composition of the present invention may or may not further contain a surfactant, and if it contains, fluorine and / or silicon surfactant (fluorine-based surfactant). It is more preferable to contain any one of surfactants, silicon surfactants, surfactants having both fluorine atoms and silicon atoms, or two or more thereof.

When the chemically amplified resist composition of the present invention contains a surfactant, it provides a resist pattern with good sensitivity and resolution and less adhesion and development defects when using an exposure light source of 250 nm or less, particularly 220 nm or less. It becomes possible.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. For example, F-top EF301, EF303, (Shin-Akita Kasei Co., Ltd.) )), Florard FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by DIC Corporation), Surflon S-382 SC101, 102, 103, 104, 105, 106, KH-20 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toagosei Chemical Co., Ltd.) ), Surflon S-393 (Seimi Chemical Co., Ltd.), Ftop EF121, EF 22A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 230G, 218G 204D, 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the surfactant corresponding to the above, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC Corporation), acrylate having C ₆ F ₁₃ group (or methacrylate) and (poly (oxyalkylene)) acrylate (copolymer of or methacrylate), and acrylate having a C ₃ F ₇ group (or methacrylate) (poly (oxyethylene) and) acrylate (or methacrylate) (poly ( And a copolymer with oxypropylene)) acrylate (or methacrylate).

  In the present invention, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 can also be used.

  These surfactants may be used alone or in several combinations.

When the chemically amplified resist composition contains a surfactant, the amount of the surfactant used is preferably 0.0001 to 2% by mass, based on the total amount of the chemically amplified resist composition (excluding the solvent). More preferably, it is 0.0005-1 mass%.
On the other hand, the surface unevenness of the hydrophobic resin is increased by setting the addition amount of the surfactant to 10 ppm or less with respect to the total amount of the chemically amplified resist composition (excluding the solvent). Can be made more hydrophobic, and the water followability during immersion exposure can be improved.

[7] (G) Other Additives The chemically amplified resist composition in the present invention may contain a carboxylic acid onium salt. Examples of such carboxylic acid onium salts include those described in US Patent Application Publication No. 2008/0187860 [0605] to [0606].
When the chemically amplified resist composition contains a carboxylic acid onium salt, the content thereof is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total solid content of the composition. %, More preferably 1 to 7% by mass.

  Further, the chemically amplified resist composition of the present invention may contain a so-called acid proliferating agent as necessary. The acid proliferating agent is particularly preferably used when performing the pattern forming method of the present invention by EUV exposure or electron beam irradiation. Although it does not specifically limit as a specific example of an acid multiplication agent, For example, the following is mentioned.

In the chemically amplified resist composition of the present invention, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound that promotes solubility in a developer (for example, if necessary) , A phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound).
The chemically amplified resist composition in the present invention is preferably used in a film thickness of 30 to 250 nm, more preferably in a film thickness of 30 to 200 nm, from the viewpoint of improving resolution.
The solid content concentration of the chemically amplified resist composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, more preferably 2.0 to 5.3% by mass. %. By setting the solid content concentration within the above range, the resist solution can be uniformly applied on the substrate.
The solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the chemically amplified resist composition.

  The chemically amplified resist composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the mixed solvent, filtering the solution, and applying the solution on a predetermined support (substrate). The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.

The present invention also relates to an electronic device manufacturing method including the pattern forming method of the present invention described above, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).

An organic processing liquid was manufactured using the organic processing liquid manufacturing system 100 described above.
The inner wall that contacts the liquid in the liquid tank 11 and the flow path (pipe, seal part, joint member, etc.) other than the above-described filtration device 21 are all made of metal or fluororesin (PTFE, PFA, etc.) or lining with these materials.

[Example 1]

<Circulation line cleaning>
In a first-stage filter housing H1 wound with a water jacket set at 23 ° C., as a first-stage filter F1, Ulticlean 50 nm PTFE filter (model name ABF1UCFD3EH1; pore size 50 nm; filter size 1 per filter) 2m ² ) in a second-stage filter housing H2 wound with a water jacket set at 23 ° C. As a second-stage filter F2, a 20 nm PTFE filter manufactured by Nippon Pole (model name ABF1UCF3EH1; pore size 20 nm; per filter) Of filtration surface area of 1.2 m ² ).
The liquid tank 11 is charged with a sufficient amount of butyl acetate to fill the circulation line of the organic processing liquid production system 100, the flow rate adjustment valve 12 is opened, the flow switching valve 15 is set on the circulation side, and the pump 16 is operated. The amount of butyl acetate corresponding to 5 times the circulation line volume was circulated in the circulation line. After washing the circulation line, the flow switching valve 15 was set on the outlet side, and the butyl acetate in the circulation line was discharged. .
Further, butyl acetate in the circulation line was discharged as much as possible from the drains D1, D2, and D3.
The above-mentioned circulation line was washed twice.

<Preparation of liquid to be filtered>
Butyl acetate was newly added to the liquid tank 11, and the temperature of the liquid to be filtered was set to 23 ° C. by a temperature controller attached to the liquid tank 11.
At the same time, the temperature of the water jacket in the first stage filter housing H1 and the second stage filter housing H2 was set to 23 ° C.
Open the flow rate adjustment valve 12, set the flow switching valve 15 to the circulation side, operate the pump 16, and continue until the temperature indicated by the pressure / flow rate / liquid thermometer 13 reaches the set temperature before filtration (23 ° C.). While adjusting the temperature controller attached to the tank 11, butyl acetate was circulated in the circulation line of the organic processing liquid production system 100.
After confirming that the temperature indicated by the pressure / flow rate / liquid thermometer 13 has reached 23 ° C., the pump 16 is stopped, the flow switching valve 15 is switched to the take-out side, and the filtration pressure indicated by the pressure / flow rate / liquid thermometer 13 While adjusting the flow rate adjustment valve 12 and the temperature regulator attached to the liquid tank 11 so that the flow rate and temperature are 0.05 MPa, 2.5 L / min, and 23 ° C., respectively, the liquid outlet The liquid taken out from No. 17 was used as an organic processing liquid for evaluation.

<Wet particle evaluation>
The number of particles (N1) on an 8-inch silicon wafer was inspected by an AMAT wafer defect evaluation apparatus ComPLUS 3T (inspection mode 30T) installed in a class 1000 clean room.
On this silicon wafer, 5 mL of butyl acetate as an organic processing liquid for evaluation was discharged, and the silicon wafer was rotated at 1000 rpm for 1.6 seconds to diffuse butyl acetate on the silicon wafer. After standing for 20 seconds, spin drying was performed at 2000 rpm for 20 seconds.
After 24 hours, the number of particles (N2) on the silicon wafer was inspected by a wafer defect evaluation apparatus ComPLUS3T (inspection mode 30T) manufactured by AMAT, and N2-N1 was determined as the number of wet particles (N).
The evaluation results are shown in Table 5.

[Examples 2 to 8 and Comparative Examples 1 to 7]
Except for the conditions listed in Table 4, an organic treatment liquid was produced in the same manner as in Example 1, and wet particles were evaluated. In Example 8, two first-stage filters F1 are connected in parallel inside the first filter housing H1, and two second-stage filters F2 are connected inside the second filter housing H2. Connected in parallel. The evaluation results are shown in Table 5.

As described above, (i) the absolute value (| T _I −T _o |) of the difference between the temperature (T _I ) of the liquid at the liquid inlet 21 a and the temperature (T _o ) of the liquid at the liquid outlet 21 b is 3) or less, (ii) the filtration rate of the liquid in the filtration device 21 is 0.5 L / min / m ² or more, and (iii) the filtration pressure by the liquid in the filtration device 21 is 0.1 MPa or less. It was found that the production methods of Examples 1 to 8 that satisfy the above three conditions can greatly reduce the number of particles compared to the production methods of Comparative Examples 1 to 7 that do not satisfy at least one of these conditions.

[Examples 9 to 15]
<Synthesis Example (Synthesis of Resin A-1)>
102.3 parts by mass of cyclohexanone was heated to 80 ° C. under a nitrogen stream. While stirring this liquid, the monomer represented by the following structural formula M-1 22.2 parts by mass, the monomer represented by the following structural formula M-2 22.8 parts by mass, and represented by the following structural formula M-3. A mixed solution of 6.6 parts by mass of monomer, 189.9 parts by mass of cyclohexanone, dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] over 5 hours. It was dripped. After completion of dropping, the mixture was further stirred at 80 ° C. for 2 hours. The reaction solution is allowed to cool, then re-precipitated and filtered with a large amount of hexane / ethyl acetate (mass ratio 9: 1), and the obtained solid is vacuum-dried, whereby the resin (A-1) of the present invention is 41. 1 part by mass was obtained.

The weight average molecular weight (Mw: polystyrene conversion) obtained from GPC (carrier: tetrahydrofuran (THF)) of the obtained resin was Mw = 9500, and the dispersity was Mw / Mn = 1.60. ^The composition ratio (molar ratio) measured by ¹³ C-NMR was 40/50/10.

<Resin (A)>
Thereafter, Resins A-2 to A-3 were synthesized in the same manner. Hereinafter, the composition ratio (molar ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) of the repeating units in the resins A-2 to A-3 including the resin A-1 are shown below.

<Acid generator>
The following compounds were used as the acid generator.

<Basic compound>
The following compounds were used as basic compounds.

<Hydrophobic resin>
Resins D-1 to D-3 were synthesized in the same manner as Resin (A). The composition ratio (molar ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) of the repeating units in the resins D-1 to D-3 are shown below.

<Surfactant>
As the surfactant, the following were used.
W-1: Megafuck F176 (manufactured by DIC Corporation; fluorine-based)
W-2: Megafuck R08 (manufactured by DIC Corporation; fluorine and silicon)

<Solvent>
The following were used as the solvent.
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether (PGME)

<Lithography evaluation 1>
The components shown in Table 6 below were dissolved in a solvent shown in the table in a solid content of 3.8% by mass, and each was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a chemically amplified resist composition.
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. On top of that, the chemically amplified resist composition prepared as described above was applied and baked at 100 ° C. for 60 seconds to form a 90 nm thick chemically amplified resist film (resist film 1). .

<Example 9: Development / rinse process>
An ArF excimer laser immersion scanner [manufactured by ASML; XT1700i, NA 1.20, Dipole (outer σ: 0.981 / inner σ: 0.005] is formed on the resist film 1 formed of the chemically amplified resist composition I-1 shown in Table 6. 895), Y deflection], and pattern exposure through a halftone mask. Ultra pure water was used as the immersion liquid. Thereafter, baking was performed at 105 ° C. for 60 seconds. Next, development was carried out with butyl acetate produced by the production method of Example 1 as a developing solution for 30 seconds, and rinsing with 4-methyl-2-pentanol produced by the production method of Example 2 as a rinsing solution for 20 seconds. A pattern (resist pattern substrate 1) was obtained.

<Example 10: Development / rinseless process>
An ArF excimer laser immersion scanner [manufactured by ASML; XT1700i, NA 1.20, Dipole (outer σ: 0.981 / inner σ: 0. 0] is formed on the resist film 1 formed of the chemically amplified resist composition I-2 shown in Table 6. 895), Y deflection], and pattern exposure through a halftone mask. Ultra pure water was used as the immersion liquid. Thereafter, baking was performed at 105 ° C. for 60 seconds. Next, development was performed for 30 seconds with butyl acetate produced by the production method of Example 6 as a developer, and the developer was spin-dried at 2000 rpm for 20 seconds to obtain a pattern (resist pattern substrate 2).

Example 11 Development / Rinse Process
An ArF excimer laser immersion scanner [manufactured by ASML; XT1700i, NA 1.20, Dipole (outer σ: 0.981 / inner σ: 0. 0] is formed on the resist film 1 formed of the chemically amplified resist composition I-3 shown in Table 6. 895), Y deflection], and pattern exposure through a halftone mask. Ultra pure water was used as the immersion liquid. Thereafter, baking was performed at 105 ° C. for 60 seconds. Next, development is performed for 30 seconds with butyl acetate manufactured by the manufacturing method of Example 8 as a developing solution, and rinsing is performed for 2 seconds with butyl acetate manufactured by the manufacturing method of Example 1 as a rinsing solution. A substrate 3) was obtained.

  When the resist pattern substrates 1 to 3 were observed with a length-measuring scanning electron microscope (CG4100, manufactured by Hitachi, Ltd.), a 45 nm pattern with a line size and a space size of 1: 1 could be satisfactorily formed without pattern collapse. Confirmed that.

<Lithography evaluation 2>
A container containing a resist composition having the same composition as the resist composition I-1 in Table 6 was connected to a resist line of a coating and developing apparatus (RF3S manufactured by SOKUDO).
In addition, an 18 L canister can containing butyl acetate as a developer produced by the production method of Example 1 was connected to the coating and developing apparatus.
Further, an 18 L canister can containing 4-methyl-2-pentanol as a rinse liquid produced by the production method of Example 3 was connected to the coating and developing apparatus.
After mounting Integris Optimizer ST-L (product model number AWATMLKM1) as the POU filter for the developer and rinse solution in the coating and developing apparatus, the filter is vented in the usual manner in the coating and developing apparatus. In practice, 30 L of the processing solution (each of the developing solution and the rinsing solution) was passed through the POU filter.
Using the coating and developing apparatus, an organic antireflection film ARC29SR (manufactured by Nissan Chemical Co., Ltd.) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. The resist composition was applied thereon, and baked at 100 ° C. for 60 seconds to form a chemically amplified resist film (resist film 2) having a thickness of 90 nm.

Example 12 Development / Rinse Process
An ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, Dipole (outerσ: 0.981 / innerσ: 0.895), Y deflection) is used as a resist film 2 through a halftone mask. Exposed. Ultra pure water was used as the immersion liquid. Thereafter, baking was performed at 105 ° C. for 60 seconds. Next, the coating and developing apparatus was developed with the developer (ie, butyl acetate produced by the production method of Example 1) for 30 seconds, and the rinse solution (ie, 4-methyl produced by the production method of Example 3). Rinse with 2-pentanol) for 20 seconds to obtain a pattern (resist pattern substrate 4).

Example 13 Development / Rinseless Process
An ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, Dipole (outerσ: 0.981 / innerσ: 0.895), Y deflection) is used as a resist film 2 through a halftone mask. Exposed. Ultra pure water was used as the immersion liquid. Thereafter, baking was performed at 105 ° C. for 60 seconds. Next, the coating and developing apparatus is used to develop the developer as a developer (that is, butyl acetate produced by the production method of Example 1) for 30 seconds, spin-dry the developer for 20 seconds at 2000 rpm, A pattern (resist pattern substrate 5) was obtained.

  When the resist pattern substrates 4 and 5 were observed with a length-measuring scanning electron microscope (CG4100 manufactured by Hitachi, Ltd.), a 45 nm pattern with a line size and a space size of 1: 1 was formed satisfactorily without pattern collapse. I confirmed that it was made.

<Example 14>
Eight similar compositions were prepared except that the basic compound C-3 used in the chemically amplified resist composition I-3 was replaced with the above-described betaine compounds C1-1 to C1-8. As a result of evaluation in the same process, pattern formation could be performed.

<Example 15>
Evaluation was made in the same manner as in Example 9 except that tri-n-octylamine was added to butyl acetate so as to be 2% by mass with respect to the total amount of the developer immediately before connecting butyl acetate to the coating and developing apparatus. However, pattern formation could be performed.

Examples 16 and 17
<Resist preparation>
The components shown in Table 8 below were dissolved in the solvent shown in the same table so that the solid content was 1.6% by mass, and each was filtered through a polyethylene filter having a pore size of 0.05 μm, and shown in each Example. Actinic ray-sensitive or radiation-sensitive resin compositions (chemically amplified resist compositions) (I-4) and (I-5) were prepared.

  Regarding the abbreviations in Table 8, those not described above are as follows.

<Example 16>
(Formation of resist film)
The chemically amplified resist composition I-4 shown in Table 8 was applied onto a Si wafer that had been previously subjected to hexamethyldisilazane (HMDS) treatment, and dried on a hot plate at 100 ° C. for 60 seconds to obtain a film thickness of 50 nm. A resist film was obtained.

(Formation of resist pattern)
EUV exposure was performed on the wafer coated with the resist film. After irradiation, the plate was heated on a hot plate at 110 ° C. for 60 seconds, then paddled with butyl acetate produced by the production method of Example 1, and developed for 30 seconds. As a result, pattern formation could be performed.

<Example 17>
In the same manner as in Example 16, it was possible to form a resist pattern using the chemically amplified resist composition I-5 shown in Table 8.

DESCRIPTION OF SYMBOLS 11 Liquid tank 12 Liquid quantity adjustment valve 13 Pressure / flow rate / liquid temperature meter 14 Flow rate / liquid temperature meter 15 Flow switching valve 16 Pump 17 Liquid outlet 21 Filtration device 21a Liquid inlet part 21b Liquid outlet part 100 Organic processing liquid production System F1 First stage filter F2 Second stage filter H1 First filter housing H2 Second filter housing D1, D2, D3 Drain

That is, the present invention has the following configuration, whereby the above object of the present invention is achieved.
<1>
A step of allowing a liquid containing an organic solvent to pass through a filtration device having a liquid inlet part, a liquid outlet part, and a filtration filter membrane provided in a flow path connecting the liquid inlet part and the liquid outlet part. A process for producing an organic processing liquid for patterning a chemically amplified resist film,
The absolute value (| T _I −T _o |) of the difference between the temperature (T _I ) of the liquid at the liquid inlet and the temperature (T _o ) of the liquid at the liquid outlet is 3 ° C. or less. The filtration rate of the liquid in the filtration device is 0.5 L / min / m ² or more, and the filtration pressure by the liquid in the filtration device is 0.03 MPa or more and 0.08 MPa or less,
The filtration device includes a filtration filter membrane composed of a fluororesin, a polyolefin resin or a polyamide resin as the filtration filter membrane,
A method for producing an organic processing liquid for patterning a chemically amplified resist film, wherein the liquid containing the organic solvent is an ester solvent, a ketone solvent, or an alcohol solvent.
<2>
A step of allowing a liquid containing an organic solvent to pass through a filtration device having a liquid inlet part, a liquid outlet part, and a filtration filter membrane provided in a flow path connecting the liquid inlet part and the liquid outlet part. A process for producing an organic processing liquid for patterning a chemically amplified resist film,
The absolute value (| T _I −T _o |) of the difference between the temperature (T _I ) of the liquid at the liquid inlet and the temperature (T _o ) of the liquid at the liquid outlet is 3 ° C. or less. The filtration rate of the liquid in the filtration device is 0.6 L / min / m ² or more, and the filtration pressure by the liquid in the filtration device is 0.10 MPa or less,
The filtration device includes a filtration filter membrane composed of a fluororesin, a polyolefin resin or a polyamide resin as the filtration filter membrane,
A method for producing an organic processing liquid for patterning a chemically amplified resist film, wherein the liquid containing the organic solvent is an ester solvent, a ketone solvent, or an alcohol solvent.
<3>
The method for producing an organic processing solution for patterning a chemically amplified resist film according to <1> or <2>, wherein the organic processing solution is an organic developer.
<4>
The method for producing an organic processing liquid for patterning a chemically amplified resist film according to <3>, wherein the liquid containing the organic solvent is butyl acetate or methyl amyl ketone.
<5>
The method for producing an organic processing liquid for patterning a chemically amplified resist film according to <1> or <2>, wherein the organic processing liquid is an organic rinsing liquid.
<6>
The method for producing an organic processing liquid for patterning a chemically amplified resist film according to <5>, wherein the liquid containing the organic solvent is 4-methyl-2-pentanol or butyl acetate.
<7>
The method for producing an organic processing liquid for patterning a chemically amplified resist film according to any one of <1> to <6>, wherein the pore size of the filtration filter film is 50 nm or less.
<8>
The organic processing for patterning of the chemically amplified resist film according to any one of <1> to <7>, wherein the temperature (T _I ) of the liquid at the liquid inlet is 20 ° C. or higher and 30 ° C. or lower. Liquid manufacturing method.
<9>
(A) forming a film with a chemically amplified resist composition;
(A) exposing the film; and
(C) a step of developing the exposed film using an organic developer;
A pattern forming method comprising:
A pattern forming method, wherein the organic developer is an organic developer produced by the method for producing an organic processing liquid for patterning a chemically amplified resist film according to <3> or <4>.
<10>
The pattern forming method according to <9>, further including a step of washing with an organic rinsing solution after the step of developing with the organic developer.
The pattern formation method whose organic rinse liquid is the organic rinse liquid manufactured by the manufacturing method of the organic processing liquid for patterning of the chemically amplified resist film as described in <5> or <6>.
<11>
The organic developer is an organic developer produced by the method for producing an organic treatment liquid for patterning a chemically amplified resist film according to <4>, and the organic rinse liquid is <6>. <10> The pattern forming method according to <10>, which is an organic rinsing liquid manufactured by the method for manufacturing an organic processing liquid for patterning a chemically amplified resist film.
<12>
The step of developing with the organic developer is a step of developing with a developing device equipped with a processing solution filter, and the organic developer is passed through the processing solution filter for development. The pattern forming method according to any one of <9> to <11>, which is used.
<13>
<9>-<12> The manufacturing method of an electronic device containing the pattern formation method of any one of <12>.
In addition, although this invention is invention which concerns on said <1>-< 13 >, hereafter, it described for reference also about others.

Claims (8)

A step of allowing a liquid containing an organic solvent to pass through a filtration device having a liquid inlet part, a liquid outlet part, and a filtration filter membrane provided in a flow path connecting the liquid inlet part and the liquid outlet part. And the absolute value (| T _I −T _o |) of the difference between the temperature (T _I ) of the liquid at the liquid inlet and the temperature (T _o ) of the liquid at the liquid outlet is 3 Or less, the filtration rate of the liquid in the filtration device is 0.5 L / min / m ² or more, the filtration pressure by the liquid in the filtration device is 0.10 MPa or less, and the filtration device is For patterning a chemically amplified resist film, including a filtration filter film made of a fluororesin as the filtration filter film, and the liquid containing the organic solvent is an ester solvent, a ketone solvent, or an alcohol solvent Organic processing A manufacturing method for patterning organic processing liquid prepared chemically amplified resist film by,
An organic processing solution for patterning a chemically amplified resist film, wherein the number of wet particles (N) obtained by the following (1) to (3) is 120 or less.
(1) The number of particles (N1) on an 8-inch silicon wafer is inspected by an AMAT wafer defect evaluation apparatus ComPLUS 3T (inspection mode 30T) installed in a class 1000 clean room;
(2) 5 mL of the organic processing solution for patterning is discharged onto the silicon wafer, and the silicon wafer is rotated at 1000 rpm for 1.6 seconds, whereby the organic processing solution for patterning is transferred to the silicon wafer. Diffused above, allowed to stand for 20 seconds, then spin dried at 2000 rpm for 20 seconds;
(3) After 24 hours, the number of particles (N2) on the silicon wafer is inspected by a wafer defect evaluation apparatus ComPLUS3T (inspection mode 30T) manufactured by AMAT, and N2-N1 is set as the number of wet particles (N).   2. The organic processing solution for patterning a chemically amplified resist film according to claim 1, wherein the organic processing solution is an organic developer.   The organic processing liquid for patterning of the chemically amplified resist film according to claim 2, wherein the liquid containing the organic solvent is butyl acetate or methyl amyl ketone.   2. The organic processing liquid for patterning a chemically amplified resist film according to claim 1, wherein the organic processing liquid is an organic rinsing liquid.   The organic processing liquid for the patterning of the chemically amplified resist film according to claim 4, wherein the liquid containing the organic solvent is 4-methyl-2-pentanol or butyl acetate.   The organic processing liquid for patterning of the chemically amplified resist film according to any one of claims 1 to 5, wherein a pore size of the filtration filter film made of the fluororesin is 50 nm or less. The organic processing liquid for patterning of the chemically amplified resist film according to any one of claims 1 to 6, wherein the temperature (T _I ) of the liquid at the liquid inlet is 20 ° C or higher and 30 ° C or lower.   The organic processing liquid for patterning of the chemically amplified resist film according to claim 1, wherein the filtration device includes only a filtration filter film made of a fluororesin as the filtration filter film.

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