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WO2016190368A1 - Substrate processing method, resin composition, and method for producing electronic device - Google Patents

Substrate processing method, resin composition, and method for producing electronic device

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WO2016190368A1
WO2016190368A1 PCT/JP2016/065505 JP2016065505W WO2016190368A1 WO 2016190368 A1 WO2016190368 A1 WO 2016190368A1 JP 2016065505 W JP2016065505 W JP 2016065505W WO 2016190368 A1 WO2016190368 A1 WO 2016190368A1
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group
preferably
resin
atom
repeating
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PCT/JP2016/065505
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French (fr)
Japanese (ja)
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惠瑜 王
啓太 加藤
三千紘 白川
研由 後藤
大輔 浅川
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富士フイルム株式会社
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/039Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/30Imagewise removal using liquid means
    • G03F7/32Liquid compositions therefor, e.g. developers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/40Treatment after imagewise removal, e.g. baking
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Abstract

Provided is a substrate processing method including: (A) a step for forming a first film on a substrate using a resin composition (a); (B) a step for forming a second film on the first film using an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) having a polarity which changes due to the action of an acid; (C) a step for exposing the second film to light, and (D) a step for developing the exposed second film to form a pattern. The resin composition (a) contains a resin (P) having an Ohnishi parameter of more than 4.5.

Description

The substrate processing method, a resin composition and a method for manufacturing an electronic device

The present invention relates to a substrate processing method, the resin composition used in the substrate processing method, and a method of manufacturing an electronic device using the substrate processing method. More particularly, the present invention relates to a semiconductor manufacturing process such as IC, a liquid crystal, in the production of a circuit board such as a thermal head, more applicable substrate processing method to other photo-fabrication lithography process, in the substrate processing method resin composition used, and a method of manufacturing an electronic device using the substrate processing method, and an electronic device.

In a manufacturing process of a semiconductor device, first, generally using a resist composition comprising a photosensitive material, a resist film is formed on the substrate to be processed is subjected to exposure in a predetermined area of ​​the resist film, then the resist film the resist pattern to form the exposed portion or unexposed portion is removed by development treatment, the processable substrate is performed by dry etching further using the resist pattern as an etching mask.

In such processes, such as ultraviolet rays such as ArF excimer laser light is used as exposure light for performing exposure to the resist film. Currently, large scale integrated circuits; there is an increasing demand for miniaturization of (Large Scale Integration LSI) is more and more, there is the resolution required is less than the wavelength of the exposure light. With such resolution equal to or less than the wavelength of the exposure light, the exposure latitude, an exposure process margin such as focus margin is to be insufficient. Although in order to compensate for the lack of such an exposure process margin, it is effective to improve the resolution by reducing the thickness of the resist film, the resist film thickness required for the etching of the film to be processed on the one hand it becomes difficult to secure.

For this reason, the planarizing film having excellent etching resistance on a substrate to be processed, to form a resist film, and then, after forming a resist pattern by exposing and developing the resist film, the resist pattern the process of transferring the flattening film pattern by etching the planarization layer as a mask (hereinafter, also referred to as "multi-layer resist process") study of being performed.

For example, Patent Document 1, excellent as a resin composition for forming a planarizing layer having an etch-resistant, been proposed planarization film forming composition containing a polymer having alkynyloxy group in the side chain or the like there.

Further, for example, Patent Document 2, in the multilayer resist process, a substrate having a pre-patterned uneven structure as the substrate (hereinafter, referred to as. "Stepped substrate") when using the excellent burying property against stepped substrate, and, underlayer film forming resin composition capable of forming a flattening film having excellent etching resistance have been proposed.

Further, for example, Patent Document 3, when the multilayer resist process comprises an ion implant process, high dry etching resistance and ion implantation resistance in alkaline water without damaging the substrate after implantation or ion after dry etching peelable lower membrane capable of forming a lower layer film-forming resin composition has been proposed. Specifically, as the lower film-forming resin composition, a resin composition containing a novolac resin having a lactone ring is disclosed.

JP 2009-014816 JP JP 2012-0215842 No. JP 2015-18222 JP

While demand for further miniaturization for the semiconductor device is increased, but to improve the resolution by reducing the thickness of the resist film is desired, in the prior art described above in the manufacturing process of semiconductor devices, planarization layer increased etching resistance of, it has been found etching resistance of the resist film for etching resistance of the flattening film is low. In this case, improvement in the resolution by reducing the thickness of the resist film is difficult.

The present invention has been developed in view of the above circumstances, problems that can form a high resolution resist pattern, thereby to provide a substrate processing method capable of ultrafine semiconductor devices to. The present invention also provides a resin composition suitably used as a planarizing film or the like in the substrate processing method, and aims to provide a method of manufacturing an electronic device using the substrate processing method.

The invention, in one aspect, is as follows.
[1]
(A) Ohnishi parameter is 4.5 with a larger resin (P) a resin composition containing (a), forming a first film on the substrate,
(B) said on the first layer, forming a second film by using the actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) which changes polarity by the action of an acid,
(C) step of exposing the second layer and,
(D) developing the exposed second layer, the substrate processing method comprising steps a to form a pattern.

[2]
Ohnishi parameter of the resin (P) contained in the resin composition (a) is greater than the Ohnishi parameter the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition (A), in [1] the substrate processing method according.

[3]
The actinic rays or the resin contained in the radiation-sensitive resin composition (A) contains a silicon atom, a substrate processing method according to [1] or [2].

[4]
The first film is insoluble in the actinic ray-sensitive or radiation-sensitive resin composition, [1] The substrate processing method according to any one of - [3].
[5]
After the said step (D),
(G) a first layer, the substrate processing method according to any of the steps of peeling with a liquid, further comprising a [1] to [4].

[6]
The substrate processing method according to the liquid, and having a pH of greater than 8 solution [5].

[7]
After the said step (D),
(E) the pattern as a mask, the substrate processing method according to any one of further comprising [1] to [6], the step of etching the first film.

[8]
After the said step (D),
(F) The substrate processing method according to any one of further comprising an implantation step of introducing the metal ions into the substrate [1] to [7].

[9]
Wherein the developing in step (D) is performed using a developer containing an organic solvent, [1] The substrate processing method according to any one of to [8].

[10]
The resin composition (a) is the as the resin (P), poly (meth) acrylic resin contains at least one resin selected from the group consisting of polyester resins and polyether resins, [1] - [ the substrate processing method according to any one of 9].

[11]
The resin composition (a) is the as the resin (P), contains at least a resin having a repeating unit represented by the following general formula (1-1), according to any one of [1] to [10] the method for processing the substrate.

Figure JPOXMLDOC01-appb-C000004

In the formula,
R 1 represents a hydrogen atom or an organic group.
R 2 represents a hydrocarbon group having a hetero atom. However, for the number of carbon atoms contained in R 2, the ratio of the number of hetero atoms contained in R 2 is 0.30 or more.

[12]
In the general formula (1-1), R 2 is a lactone structure-containing group, a carbonate structure-containing group, an acetal structure-containing group, hydroxy group-containing group, or a group represented by the following general formula (P1), the substrate processing method according to [11].

Figure JPOXMLDOC01-appb-C000005

In the formula,
R A represents a divalent hydrocarbon group which may contain a hetero atom.
R B represents a monovalent hydrocarbon group which may contain a hetero atom.
n represents an integer of 1 or more. also is R A presence of a plurality if n is an integer of 2 or more may be the same or different.
* Represents a bonding position of the remainder of the repeating unit represented by formula (1-1).
However, the ratio of the number of heteroatoms for the general formula (P1) carbon atoms contained in is at least 0.30.

[13]
The resin composition (a) is the as the resin (P), contains at least a resin having a repeating unit represented by the following general formula (1-2), according to any one of [1] to [12] the method for processing the substrate.

Figure JPOXMLDOC01-appb-C000006

In the formula,
L represents an organic group.
X is, -O -, - S -, - CO -, - CO-O-, or represents -O-CO-.

[14]
In the substrate processing method according to any one of claims 1 to 13, the resin composition used as the resin composition (a).

[15]
Method of manufacturing an electronic device including a substrate processing method according to any one of claims 1 to 13.

The present invention makes it possible to form a high resolution resist pattern, thereby it has become possible to provide a substrate processing method capable of ultrafine semiconductor devices. Further, the present invention, the resin composition suitably used as a planarizing film or the like in the substrate processing method, and it has become possible to provide a method of manufacturing an electronic device using the substrate processing method.

Schematic cross-sectional view for explaining one step of the substrate processing method of the present invention. Schematic cross-sectional view for explaining one step of the substrate processing method of the present invention. Schematic cross-sectional view for explaining one step of the substrate processing method of the present invention. Schematic cross-sectional view for explaining one step of the substrate processing method of the present invention. Schematic cross-sectional view for explaining one step of the substrate processing method of the present invention. Schematic cross-sectional view for explaining one step of the substrate processing method of the present invention. Schematic cross-sectional view for explaining one step of the substrate processing method of the present invention.

In notation in group (atomic group) used in this specification, denoted without specifying whether substituted or unsubstituted, are intended to encompass also those having a substituent with those having no substituent. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group (substituted alkyl group) having a substituent group.

Also, the terms "actinic rays" and "radiation" as used herein, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray typified by excimer laser, extreme ultraviolet (Extreme ultra violet; EUV) rays, X-rays or an electron beam ( which means EB); Electron Beam. Also, "light" in the present invention means an actinic ray or radiation.

Also, the "exposure" in the present specification, unless otherwise specified, a mercury lamp, a far ultraviolet ray typified by excimer laser, not only exposure to X-ray and EUV light or the like, with a particle beam such as electron beam and ion beam drawing also included in the exposure.
It will be described in detail embodiments of the present invention.

The substrate processing method of the present invention,
(A) Ohnishi parameter is 4.5 with a larger resin (P) a resin composition containing (a), forming a first film on the substrate,
(B) said on the first layer, forming a second film by using the actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) which changes polarity by the action of an acid,
(C) step of exposing the second layer and,
(D) developing the exposed second layer, comprising the steps of forming a pattern.

Here, Ohnishi parameter of the resin is defined as follows.
(Ohnishi parameter of the resin) = sigma {(Ohnishi parameter of the repeating unit) × (the molar fraction of the repeating unit)}
Furthermore, Ohnishi parameter of the repeating units (units) is defined as follows.
(Ohnishi parameter of the repeating unit) = (total number of atoms in the repeating unit) / {(number of carbon atoms in the repeating unit) - (the sum of the number of oxygen atoms in the repeating unit and the number of sulfur atoms)}
In the case where the resin (P) does not contain a sulfur atom, in the above definition, the number of sulfur atoms is 0.

The substrate processing method of the present invention, the second film formed using the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as "actinic ray-sensitive or radiation-sensitive film" or "resist film" .) the first film (hereinafter as a lower layer of, also referred to as "planarization layer".) and Ohnishi parameter 4.5 resin composition containing a larger resin (P) (a) (hereinafter, " also referred to as planarizing film-forming resin composition ".) to the first aspect can be formed using a.

By Ohnishi parameter is used greater than 4.5 resin (P) in the planarization film, the etching resistance of the resist film for etching resistance of the flattening film is dramatically increased, to reduce the film thickness of the resist film since it is, it is possible to form a high resolution resist pattern.

The substrate processing method of the present invention, in one form, after forming a pattern in the step (D), this pattern as a mask, the step of the first film (flattening film) is etched (hereinafter, "step (E ) "also referred to.) further comprises a.

Further, the substrate processing method of the present invention, in another form, after the step (E), further comprising implantation step of introducing the metal ions into the substrate (hereinafter, also referred to as "step (F)".) The.

Further, the substrate processing method of the present invention, in another form, after the step (E) or the step (F), the step of the first film (flattening film) and the pattern is peeled off using a liquid (hereinafter, referred to as "step (G)".) further comprises a.

Hereinafter, an embodiment of a substrate processing method of the present invention will be described with reference to FIGS. 1A ~ FIG 1G.

In one form of the present invention, as shown in the schematic cross-sectional view of FIG. 1A, first, on the substrate 51, the planarizing film using a flat film-forming resin composition (a) (first film) 81 the form (step (a)).

Planarizing film forming resin composition (a), as described above, Ohnishi parameter 4.5 contains a larger resin (P). It will be described in detail later planarizing film forming resin composition (a).

In step (A), a method of forming a flattening film on a substrate, typically, as an be, a coating method by applying flattening film forming resin composition (a) on the substrate, conventional spin coating, spraying, roller coating, etc. can be used dipping method, preferably coated planarizing film forming resin composition (a) by spin coating.

The film thickness of the planarization layer is preferably from 30 ~ 300 nm, more preferably from 50 ~ 240 nm, further preferably 70 ~ 200 nm.

In one form of the present invention, the first film is preferably insoluble in the second actinic ray-used for forming the film or the radiation-sensitive resin composition to be laminated thereon.
Here, "insoluble" means that it is substantially insoluble, specifically, sensitive in QCM (Quartz Crystal Microbalance, quartz crystal microbalance) room temperature was measured using a sensor or the like (25 ° C.) the actinic ray-sensitive or radiation-sensitive resin composition, the dissolution rate of the average time of the first film was immersed for 1000 seconds (rate of decrease in the first film) may be at 0.5 nm / sec or less.

In the present invention, the substrate may be a stepped substrate as described in Figure 1A, it may not be stepped substrate. And stepped substrate is a substrate in which at least one step shape is formed on the substrate.

The substrate is not particularly limited, silicon, SiN, inorganic substrates such as SiO 2, SOG (Spin on Glass) coating-type inorganic substrate such as, IC (Integrated Circuit) semiconductor manufacturing process, such as, a liquid crystal, thermal head manufacturing process of a circuit board etc., and further it is possible to use a substrate generally used in the other photo-fabrication lithography process. Furthermore, it may also be formed between the planarizing film and the substrate underlying film such as an anti-reflection film as required. The underlayer film, an organic antireflection film, an inorganic antireflection film, it is possible to select other suitable. Underlayer film material Brewer Science, Inc., available from Nissan Chemical Industries, Ltd. and the like. Suitable underlayer film in the process of development using a developer containing an organic solvent, for example, lower layer film as described in WO 2012/039337.

The film thickness of the flattening film formed above the substrate, when the substrate is a stepped substrate means the height of the upper surface of the planarization film formed from the bottom surface of the stepped substrate.

The height from the bottom surface of the stepped substrate to the upper surface of the step shape is preferably smaller than the thickness of the planarization film, for example, less than 200 nm.

For example, in the case of fine processing such as ion implantation applications, it is preferable to use a stepped substrate as the substrate, the stepped substrate, the substrate fins and the gate is patterned on a planar substrate can be used. Thus on the step board fin and the gate is patterned, coated the planarizing film forming resin composition (a), the film thickness of the formed planarization film, formed from the upper surface of the fin and the gate rather than the top surface until the height of the planarization layer which is meant the height to the upper surface of the planarization film formed from the bottom surface of the stepped substrate as described above.

Fins and gate size (width, length, height, etc.), spacing, structures, etc. configuration, Vol Journal IEICE. 91, No. 1,2008 25-29 pages "advanced FinFET process integration technology" and, Jpn. J. Appl. Phys. Vol. 42 (2003) pp. 4142-4146Part1, No. 6B, can be suitably applied to those described in June 2003 "Fin-Type Double-GateMetal-Oxide-Semiconductor Field-Effect TransistorsFabricated by Orientation-Dependent Etching and ElectronBeamLithography".

The stepped substrate, for example, a groove width of less exposure wavelength (preferably 100nm or less, more preferably 40nm or less, typically, more than 15 nm), is 100nm or less depth (preferably 50 ~ 100nm, and more preferably 65 to and stepped substrate having a groove of 100nm), a diameter of less exposure wavelength (preferably 100nm or less, more preferably 40nm or less, typically, more than 15 nm), is 100nm or less depth (preferably 50 ~ 100nm, and more preferably such stepped substrate having a cylindrical recess 65 ~ 100 nm) and the like.

The stepped substrate having a groove that supra, a plurality of grooves, for example, the pitch 20 nm ~ 200 nm (preferably 50 ~ 150 nm, more preferably 70 ~ 120 nm), and the like stepped substrate having repeatedly at equal intervals.

As the stepped substrate having a cylindrical recess to supra, a plurality of cylindrical recesses, for example, the pitch 20 nm ~ 200 nm (preferably 50 ~ 150 nm, more preferably 70 ~ 120 nm), such as stepped substrate having repeating at equal intervals and the like.

The substrate processing method of the present invention, during step (A) and the step (B), prior to the heating step; it is also preferred to include (Prebake PB1).
Before heating temperature in the heating step (PB1) is preferably carried out at 70 ~ 130 ° C., and more preferably at 80 ~ 120 ° C..
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, more preferably 30 to 90 seconds.

The heating can be performed using a device attached to the normal exposure and development apparatus may be performed using a hot plate or the like.

Before the heating step (PB1) may include a plurality of heating steps.

Then, as shown in the schematic cross-sectional view of FIG. 1B, on the planarization film 81, the resist film 52 (second layer) is formed by using the actinic ray-sensitive or radiation-sensitive resin composition (step (B )).

In step (B), as a method of forming a resist film 52 with the actinic ray-sensitive or radiation-sensitive resin composition, the in step (A), the planarizing film forming resin composition onto a substrate (a ) those similar to the method of forming the flattening film using a.

Thick resist film is preferably from 50 ~ 800 nm, more preferably from 80 ~ 500 nm, further preferably 100 ~ 300 nm.

The substrate processing method of the present invention, between the step (B) and step (C), prior to the heating step; it is also preferred to include (Prebake PB2).

Further, the substrate processing method of the present invention, between the step (C) and step (D), post-exposure heating step; it is also preferred to include (Post Exposure Bake PEB).

The heating temperature is preferably performed at PB2, PEB both 70 ~ 130 ° C., and more preferably at 80 ~ 120 ° C..

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

The heating can be performed using a device attached to an ordinary exposure and developing apparatus, it may be performed using a hot plate or the like.

The reaction of the exposed portion is promoted by the baking, the sensitivity and pattern profile are improved.

At least one of the previous heating (PB2) process and post-exposure heating step may include a plurality of heating steps.

Then, as shown in the schematic cross-sectional view of FIG. 1C, the resist film 52 through a mask 61 is irradiated with actinic rays or radiation 71 by (i.e., exposure to) that, the exposed resist film 53 obtained (step (C)).

In step (C), the light source wavelength limit is not used for the exposure apparatus, there may be mentioned infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, electron beams or the like, preferably 250nm or less, more preferably 220nm or less, particularly preferably far ultraviolet light at a wavelength of 1 ~ 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F 2 excimer laser (157 nm), X-ray, EUV (13 nm), an electron beam or the like, KrF excimer laser, ArF excimer laser, EUV or electron beams are preferred, more preferably a KrF excimer laser or ArF excimer laser.

Step (C) may comprise a plurality of exposure processes.

In the step (C) can be applied to an immersion exposure method.

The immersion exposure method, as a technique for enhancing the resolving power, the projection lens and the liquid having a high refractive index between the sample (hereinafter also referred to as "immersion liquid") is a technology that meets the exposure at.

As described above, the "effect of immersion", assuming that the wavelength of exposure light in air lambda 0, the refractive index of the immersion liquid to air is n, the θ and convergence half of the light beam and when the NA 0 = sin [theta , when immersion, resolution and depth of focus can be expressed by the following equation. Here, k 1 and k 2 are coefficients related to the process.

(Resolving power) = k 1 · (λ 0 / n) / NA 0
(Depth of focus) = ± k 2 · (λ 0 / n) / NA 0 2
That is, the effect of immersion is equivalent to wavelength using the exposure wavelength of 1 / n. In other words, when the projection optical system of the same NA, liquid immersion, depth of focus can be n times. This is effective for all pattern profiles and can be combined current phase shift method being considered, with super resolution techniques such as modified illumination method.

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

The immersion liquid is transparent to the exposure wavelength, and so to minimize the distortion of an optical image projected on the resist film, but is preferably less liquid as possible the temperature coefficient of the refractive index, especially an exposure light source There ArF excimer laser (wavelength; 193 nm) when it is, in addition to the above viewpoint, easy availability, water is preferably used in terms such as to the easy handling.

When water is used, to reduce the surface tension of water, additives to increase the surface activity of the (liquid) may be added in a small ratio. This additive does not dissolve the resist layer on the wafer, and the influence on the optical coat at the undersurface of the lens element is preferable negligible.

As such a additive, for example, preferably an aliphatic alcohol having a refractive index approximately equal to that of water, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index nearly equal to that of water, the content concentration the alcohol component in water is evaporated even changed, the change of refractive index of the liquid as a whole it can be made extremely small.

On the other hand, when a substance being opaque and the refractive index with respect to 193nm light was significantly different impurities is mixed with water, the mixing would invite a distortion of optical image projected on the resist, the water used is preferably distilled water. Furthermore, use may be made of pure water filtered through an ion exchange filter or the like.

Electrical resistance of the water used as the immersion liquid is desirably not less than 18.3MΩcm, TOC (organic matter concentration) is desirably less 20 ppb, it is preferable that the degassing process.

Further, by increasing the refractive index of the immersion liquid, it is possible to improve the lithographic performance. From this point of view, or adding an additive suitable for refractive index increase in water may be used heavy water (D 2 O) in place of water.

The resist film, when exposed through an immersion medium, it may be further added later surface hydrophobic resin (HR), if necessary. By surface-hydrophobicized resin (HR) is added, the receding contact angle of the surface is improved. Receding contact angle of the resist film is preferably 60 ° ~ 90 °, more preferably 70 ° or more.

In the immersion exposure step, following the movement of an exposure head involving forming a scanned exposure pattern on the wafer at a high speed, since the immersion liquid must move over the wafer, in a dynamic state It becomes important contact angle of the immersion liquid with the resist film, without droplets remain, ability to follow the high-speed scanning of the exposure head in the resist obtained.

Between the resist film and the immersion liquid, the membrane directly, in order not to contact the immersion liquid, the immersion liquid sparingly soluble film (hereinafter, also referred to as "topcoat") may be provided. The functions required of the topcoat are suitability for coating the resist upper layer part, radiation, transparency, and include immersion liquid sparingly soluble, particularly for radiation having a wavelength of 193 nm. Topcoat is not mixed with the resist and can preferably be uniformly coated on the resist upper layer.

Topcoat, from the viewpoint of transparency at 193 nm, an aromatic-free polymer is preferred.

Specifically, hydrocarbon polymers, acrylic ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, a silicon-containing polymer, and a fluorine-containing polymer. Hydrophobic surface resin described later (HR) is suitable also as the topcoat. Since the impurities from the top coat into the immersion liquid is eluted the optical lens is contaminated, the residual monomer components of the polymer contained in the topcoat is preferably small.

On peeling off the topcoat, it may be used a developing solution may be used separately release agent. The releasing agent is preferably a solvent less permeating into the resist film.

It is preferred if there is a difference in refractive index or small between the topcoat and the immersion liquid. In this case, it is possible to improve the resolution. The exposure light source is an ArF excimer laser (wavelength: 193 nm) in the case of, since it is preferable to use water as the immersion liquid, the topcoat for ArF immersion exposure, to be close to the refractive index of water (1.44) preferable. From the viewpoint of transparency and refractive index, the topcoat is preferably a thin film.

Top coat does not mix with the resist film, it is preferable not to mix with further immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the topcoat is preferably a solvent for use in the compositions of the present invention in poorly soluble, and is non-aqueous media. Further, when the immersion liquid is an organic solvent, the topcoat may be water-insoluble even be water-soluble.

Then, as shown in the schematic cross-sectional view of FIG. 1D, the resist film 53 is exposed, to form a first pattern 54 is developed (step (D)).

In step (D), the developer which can be used in the step of forming a first pattern by developing the resist film, even organic developer may be an alkali developer.

The step (D), as the first pattern, forming a step of forming a negative pattern with a developer containing an organic solvent, as the first pattern, a positive pattern using an alkaline developer DOO can be preferably exemplified.

Thus, the first pattern 54 may be a negative pattern may be a positive pattern.

In step (D), the developer in the step of forming a first pattern by the resist film is developed using a developer containing an organic solvent (hereinafter, also referred to as organic developer) include ketone-based solvents, ester solvents, alcohol solvents, amide solvents, it is possible to use a polar solvent and a hydrocarbon solvent such as an ether solvent.

Examples of the ketone-based solvent include 1-octanone, 2-octanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, phenyl acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone and propylene carbonate.

Examples of the ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, cyclohexyl acetate, isobutyl isobutyrate, 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, can be mentioned propyl lactate.

As the alcohol solvent, e.g., methyl alcohol, ethyl alcohol, n- propyl alcohol, isopropyl alcohol, n- butyl alcohol, sec- butyl alcohol, tert- butyl alcohol, isobutyl alcohol, n- hexyl alcohol, n- heptyl alcohol, n- octyl alcohol, and alcohol n- decanol, ethylene glycol, diethylene glycol, and glycol-based solvent such as triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanoate It can be mentioned glycol ether solvents such as Le.

Examples of the ether-based solvent include, in addition to the glycol ether solvents, dioxane, tetrahydrofuran, phenetole, dibutyl ether and the like.

Examples of the amide solvents, e.g., N- methyl-2-pyrrolidone, N, N- dimethylacetamide, N, N- dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone It can be used.

Examples of the hydrocarbon solvents, such as toluene, aromatic hydrocarbon solvents such as xylene, pentane, hexane, octane, aliphatic hydrocarbon solvents decane.

The above solvents may be a mixture of a plurality may be used mixed with a solvent or water other than those described above. However, in order to sufficiently bring out the effects of the present invention preferably has a water content of the entire developer is less than 10 wt%, and more preferably substantially free of water.

That is, the amount of the organic solvent for the organic developer, based on the total amount of the developer, preferably at most 90 mass% to 100 mass%, preferably not more than 95 mass% to 100 mass%.

In particular, organic developer, ketone solvents, ester solvents, alcohol solvents, that is a developing solution containing at least one organic solvent selected from the group consisting of amide-based solvent and an ether-.

Vapor pressure of the organic developer, in the 20 ° C., is preferably from 5 kPa, more preferably less 3 kPa, and particularly preferably equal to or less than 2 kPa. By setting the vapor pressure of the organic developer below 5 kPa, is suppressed evaporation on the substrate of the developer or the developer cups, improved temperature uniformity in the wafer plane, the dimensions of the wafer surface uniformity as a result sex is improved.

Specific examples having a vapor pressure below 5 kPa, 1-octanone, 2-octanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, ketone solvents, acetic acid butyl and phenyl acetone, methyl isobutyl ketone, pentyl acetate, isopentyl acetate, amyl acetate, cyclohexyl acetate, isobutyl isobutyrate, 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-methylcarbamoyl 3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl, ester solvents such as propyl lactate, n- propyl alcohol, isopropyl alcohol, n- butyl alcohol, sec- butyl alcohol, tert- butyl alcohol, isobutyl alcohol, n- hexyl alcohol, n- heptyl alcohol, n- octyl alcohol, n- alcohol solvents decanol such as ethylene glycol, diethylene glycol, and glycol-based solvent such as triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene Recall monoethyl ether, triethylene glycol monoethyl ether and methoxymethyl butanol, tetrahydrofuran, phenetole, ether solvents such as dibutyl ether, N- methyl-2-pyrrolidone, N, N- dimethylacetamide, N, N- dimethylformamide amide system solvent, toluene, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.

Specific examples having 2kPa vapor pressure below are particularly preferred range, 1-octanone, 2-octanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone , ketone solvents, acetic acid butyl and phenyl acetone, amyl acetate, cyclohexyl acetate, isobutyl isobutyrate, 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, ethyl lactate, butyl lactate, propyl lactate Ester solvents, n- butyl alcohol, sec- butyl alcohol, tert- butyl alcohol, isobutyl alcohol, n- hexyl alcohol, n- heptyl alcohol, n- octyl alcohol, alcohol solvents n- decanol such as ethylene glycol, diethylene glycol , and glycol-based solvent such as triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycols such as methoxymethyl butanol ether solvents, phenetole, ether solvents such as dibutyl ether, N- methyl - - pyrrolidone, N, N- dimethylacetamide, N, N-dimethylformamide amide solvents, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.

The organic developer, can be added in an appropriate amount of a surfactant as required.

No particular limitation is imposed on the surfactant, for example, can be used such as ionic or nonionic fluorine-containing and / or silicon surfactants. These fluorine and / or silicon surfactants, for example, JP 62-36663, JP-Sho 61-226746, JP-Sho 61-226745, JP-Sho 62-170950, JP- JP 63-34540, JP-a No. 7-230165, JP-a No. 8-62834, JP-a No. 9-54432, JP-a No. 9-5988, JP-U.S. Patent 5,405,720, the 5360692 Pat, specification Nos. 5529881, specification Nos. 5296330, the 5436098 Pat, specification Nos. 5576143, specification Nos. 5294511, can be mentioned surfactants of the same 5824451 Pat wherein is preferably a non-ionic surfactant. No particular limitation is imposed on the nonionic surface active agent, it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.

The amount of surfactant based on the total amount of the developer is generally 0.001 to 5 mass%, preferably from 0.005 to 2 wt%, more preferably from 0.01 to 0.5 wt%.

Further, the organic developer may contain a basic compound as necessary. Examples of the basic compound, there are nitrogen-containing basic compound, for example, Japanese and nitrogen-containing compounds described in particular [0021] to [0063] of 2013-11833 and JP-resist composition described later is contained It includes good basic compounds also. By organic developing solution contains a basic compound, contrast enhancement during development, such as film reduction suppression can be expected.

In step (D), As the alkali developer in the step of forming a first pattern by developing with an alkaline developing solution, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, metasilicate sodium, alkaline aqueous solutions of inorganic alkalis such as ethylamine, a primary amine such as n- propylamine, diethylamine, secondary amines such as di -n- butylamine, triethylamine, tertiary amines such as diethylamine, dimethylethanolamine amines, alcohol amines such as triethanolamine, can be used tetramethylammonium hydroxide, quaternary ammonium salts such as tetraethyl ammonium hydroxide, pyrrole, an alkaline aqueous solution of a cyclic amine such as piperidine.

Further, alcohols of the above alkaline aqueous solution, after adding thereto a surfactant in an appropriate amount may be used. As the surfactant can be exemplified those described above.

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

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

In particular, an aqueous solution of 2.38% by weight tetramethylammonium hydroxide is preferred.

As a developing method, for example, a method of immersing the substrate a predetermined time in a tank filled with a developer (dip method), a method of developing in it still for a fixed time, raised by surface tension the developer on the substrate surface (puddle law), a method of spraying the developer on a substrate surface (spray method), a method of continuously ejecting the developer while scanning the developer ejecting nozzle at a constant speed on the substrate spinning at a constant speed (dynamic dispense method) or the like can be used.

In the case where the above case including the step of discharging the developer toward the resist film from the development nozzle of the developing apparatus, the discharge pressure of the discharged developer (flow rate per unit area of ​​the developer ejected) is preferably 2mL / sec / mm 2 or less, more preferably 1.5mL / sec / mm 2, more preferably not more than 1mL / sec / mm 2. The flow velocity has no particular lower limit, taking into account the throughput 0.2mL / sec / mm 2 or more.

By the discharge pressure of the developer ejected in the above range, it is possible to significantly reduce pattern defects attributable to the resist residue after development.

Although not certain details of this mechanism, presumably, the discharge pressure is adjusted within the above range, the developer is the pressure decreases to be applied to the resist film, the resist film resist pattern or collapse or scraped inadvertently There is believed to be suppressed.

Incidentally, the discharge pressure of the developing solution (mL / sec / mm 2) is the value at the outlet of a development nozzle in a developing device.

As a method for adjusting the ejection pressure of the developing solution, for example, a method of adjusting the discharge pressure such as a pump, may be mentioned a method of changing by adjusting the pressure in the supply from the pressure tank.

Further, after the step of development with a developer containing an organic solvent, by replacement with another solvent may be carried a step of stopping the development.

Further, the substrate processing method of the present invention, useful as step (D), forming a negative pattern with a developer containing an organic solvent, and forming a positive pattern using an alkaline developer it may be in. And development with an organic developer, by combining development with an alkaline developing solution, FIG-of US8,227,183B. Such as described in 1 to 11 it can be expected to resolve a pattern of half the line width of the mask pattern.

The substrate processing method of the present invention, after step (D), may include the step (rinsing step) of rinsing the film with a rinsing solution.

The rinsing solution used in the rinsing step after the step of performing development with a developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, the solution can be used, including common organic solvents . As the rinsing liquid, hydrocarbon solvents, ketone solvents, using a rinsing solution containing an ester solvent, an alcohol solvent, at least one organic solvent selected from the group consisting of an amide solvent and an ether solvent It is preferred.

Hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, specific examples of the amide-based solvent and ether-based solvents may be mentioned the same ones as described in the developer containing an organic solvent.

After the step of development with a developer containing an organic solvent, rinsing and more preferably, containing the ketone solvent, an ester solvent, an alcohol solvent, at least one organic solvent selected from the group consisting of an amide solvent performs the step of washing with a liquid, more preferably, a step of washing with a rinse liquid containing an alcohol solvent or an ester solvent, particularly preferably, by using a rinsing solution containing a monohydric alcohol a step of rinsing the film, most preferably, a step of washing with a rinsing solution containing a monohydric alcohol having 5 or more carbon atoms.

The monovalent alcohol used in the rinsing step, linear, branched, include monohydric alcohol which, specifically, 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 or the like can be used, particularly preferred monohydric alcohols having 5 or more carbon, 1-hexanol, 2-hexanol, 4-methyl - 2-pentanol, 1-pentanol, it is used as 3-methyl-1-butanol It can be.

The above components may be a mixture of a plurality may be used mixed with other organic solvents.

The water content in the rinsing solution is preferably 10 mass% or less, more preferably 5 mass% or less, particularly preferably 3 mass% or less. The water content to 10 mass% or less, it is possible to obtain a good development properties.

The vapor pressure of the rinse liquid used after the step of performing development with a developer containing an organic solvent, 20 ° C. to at by 0.05kPa or more, is preferably from 5 kPa, more 0.1 kPa, more preferably less 5 kPa, 0. 12kPa or more, most preferably at most 3 kPa. Above 0.05kPa vapor pressure of the rinse liquid, by the following 5 kPa, improved temperature uniformity in the wafer plane, is more suppressed swelling due to penetration of the rinse liquid, the dimensional uniformity in the wafer surface but it improved.

The rinsing solution used in the rinsing step after the step of developing using an alkaline developing solution, pure water is used, it is also possible to use a surfactant in an appropriate amount.

The method of cleaning in the rinsing step described above is not particularly limited, for example, a method (spin coating method) of continuously ejecting the rinsing solution on the substrate spinning at a constant speed, the substrate in a tank filled with the rinse liquid a method of immersing a predetermined time (dip method), a method of spraying the rinsing solution on a substrate surface (spray method) can be applied, etc., subjected to rinsing treatment by the spin coating method in this, 2000 rpm the substrate after cleaning - is rotated at a rotational speed of 4000 rpm, a rinsing solution is preferably removed from the substrate. It is also preferred to include a heating step after the rinsing step (Post Bake). Developer and rinsing solution remaining inside and between the pattern the pattern are removed by the baking. The heating step after the rinsing step is normally 40 - 160 ° C., preferably at 70 ~ 95 ° C., 10 seconds to 3 minutes usually, preferably from 30 to 90 seconds.

Also, after the development process or rinsing process, the developer or rinsing solution adhering on the pattern may be processed to remove the supercritical fluid.

Depending step (D), it is preferable that planarization film 81 is not substantially developed. To that end, the planarization film 81 is preferably not dissolved in the developing solution used in step (D).

The planarizing film is not substantially developed, typically, QCM (Quartz Crystal Microbalance, quartz crystal microbalance) in the developing solution at room temperature was measured using a sensor or the like (25 ° C.), a planarizing film the dissolution rate of the average when immersed for 1000 seconds (rate of decrease in flattening film) is less than 0.1 nm / sec., preferably less than 0.05 nm / sec, that more preferably less than 0.01 nm / sec show.

The above requirements, when the developing solution used in step (D) is an organic developing solution, such as by flattening film forming resin composition (a) (thus flattening film) contains a hydrophilic resin , when the developing solution is an alkali developing solution, the planarizing film forming resin composition (a) (thus planarizing film) is due to contain a hydrophobic resin, it is suitably accomplished.

Then, as shown in the schematic cross-sectional view of FIG. 1E, a first pattern 54 as a mask, with respect to the planarizing film 81, it was etched using an etching gas 75 and the like, a planarizing film 81 second into a pattern 82 (step (E)).

The method of etching is not particularly limited, either can be a known method, various conditions such as, according to the type of the layer to be subjected to an etching treatment, as appropriate, are determined. For example, SPIE Bulletin (Proc. Of SPIE) Vol. 6924,692420 (2008), it can be in accordance with JP 2009-267112 Laid to perform the etching.

Here, the first pattern can be cited suitably form containing a silicon atom.

This form by actinic ray-sensitive or radiation-sensitive resin composition contains a silicon atom (e.g., a resin having a silicon atom), and thus, the first pattern the silicon atom (for example, a resin having a silicon atom ) it is preferably in the form containing.

According to the above embodiment, by employing the etching reaction hardly occurs etching conditions for film containing silicon atoms, so that the etching rate of the planarizing film is sufficiently larger than the etch rate of the first pattern It is likely to set the etching conditions. Thus, the second pattern 82 pattern of the first pattern 54 is formed by transferring the planarization film 81 can be more easily formed.

When the substrate processing method of the present invention is a substrate processing method including an ion implantation process, and then, as shown in FIG. 1F, the first pattern 54 and second pattern 82 as a mask, a predetermined region of the substrate 51 relative to an ion implantation for implanting ions 76. As the method of ion implantation, any known method can be adopted.

Then, as shown in the schematic cross-sectional view of FIG. 1G, it may be removed first pattern 54 and second pattern 82 (step (G)).

Step (G) is, if removing the first pattern and the second pattern is not particularly limited with respect to the first pattern and the second pattern, etching, peeling by a liquid (hereinafter, "wet stripping" also referred.) by subjecting one or more treatment selected from, can be suitably implemented.

In wet cleaning, as the liquid which is used, for example, ammonia, ammonia consisting of ammonia and hydrogen peroxide and water hydrogen peroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, 1-butyl-1-methyl-pyrrolidinium hydroxide, 1-propyl-1-methyl-pyrrolidinium hydroxide, 1-butyl-1 methylpiperidinium hydroxide, 1-propyl-1-methyl-piperidinium hydroxide, trimethylsulfonium hydroxide, hydroxylamine, diethylamine, 2- butylamine Mino ethanol, 2,2-diethylaminoethanol, hydrazines, ethylene diamine, guanidines, diazabicycloundecene (1,8-diazabicyclo [5.4.0] undec-7-ene; DBU), diazabicyclononene (1 , 5-diazabicyclo [4.3 0.] non-5-ene; include DBN) or the like.

Also, in one embodiment of the present invention, liquid that can be used in wet strip is preferably pH at 25 ° C. is greater than 8 solution, and more preferably a pH of an aqueous solution of 9-14.

In the step (G), without damaging the substrate 51, removing the first pattern 54 and second pattern 82, in other words, the first pattern 54 and second pattern 82 since it is preferable to selectively remove, in the process illustrated above, it is preferable to adopt those which the first pattern 54 and second pattern 82 can be selectively removed.

In view of the like described above, when the first pattern 54 is removed by the etching process, step (G), to the first pattern 54, etching rates of the first pattern 54 of the second pattern 82 etched preferably includes a step of performing an etching process larger conditions than the speed.

Since the above-mentioned step (E) may be a step which also serves as a step (G). That is, the first pattern 54 as a mask, with respect to the planarizing film 81, etching process, in the process of converting the planarizing film 81 in the second pattern 82, by this etching process, at the same time, the first pattern 54 may be removed. In this case, the etching rate of the first pattern 54 may be the etching rate and the same degree of planarization layer 81.

The above etching conditions, a resist composition, and, and the content of each composition of the flattening film forming composition, the kind of etching gas as appropriate, but can be achieved by adjusting the above-mentioned etching conditions from the viewpoint of easier to achieve, the planarization film 81, as later described is also required to be a layer containing a resin having greater than 4.5 Ohnishi parameter.

It will now be described resin composition used in the substrate processing method of the present invention (a).

<Resin composition (a)>
Resin composition (a) is a resin composition used for forming the first film contains a resin (P) described below, typically further contains a solvent for. The first film is stepped substrate having the uneven surface (e.g., semiconductor substrate) are formed on the like, and has a role in providing a flat surface.

As described above, the first resin composition for use in forming a film (a) (flattening film forming composition) In the substrate processing method of the present invention, Ohnishi parameter is greater than 4.5 resin (hereinafter, " that the resin (P) ".) containing.

Flattening film forming composition for such a configuration is believed to desired effect. The reason is not clear, the etching resistance of the resin Ohnishi parameter of (P) is set to be larger than a certain value, the resist film (second film) with respect to the etching resistance of the flattening film (first film) There were dramatically improved, it is possible to reduce the thickness of the resist film, it is presumed that it is possible to form a high resolution resist pattern.

[Resin (P)]
As described above, the planarizing film forming resin composition (a) is Ohnishi parameter contains greater than 4.5 resin.

Ohnishi parameter of the resin (P) is preferably 20 or less, more preferably 6.0 to 20.

Here, Ohnishi parameter of the resin (P), as described above, is defined as follows.

(Ohnishi parameter of the resin) = sigma {(Ohnishi parameter of the repeating unit) × (the molar fraction of the repeating unit)}
Furthermore, Ohnishi parameter of the repeating units (units) is defined as follows.

(Ohnishi parameter of the repeating unit) = (total number of atoms in the repeating unit) / {(number of carbon atoms in the repeating unit) - (the sum of the number of oxygen atoms in the repeating unit and the number of sulfur atoms)}
For example, Ohnishi parameter of A-1 used in the examples to be described later is calculated as follows.

First repeating units from the left A-1, since the total number of atoms is 22, the number of carbon atoms is 8, the number of oxygen atoms is 4, the Ohnishi parameter is 22 / (8-4) = 5.5 it is.

Second repeating units from the left A-1, since the total number of atoms is 23, the number of carbon atoms is 7, the number of oxygen atoms is 4, the Ohnishi parameter, 23 / (7-4) ≒ 7.7 it is.

For the third repeating units from the left A-1 is the total number of atoms is 23, the number of carbon atoms is 7, the number of oxygen atoms is 4, the Ohnishi parameter, 43 / (13-6) ≒ 6.1 it is.

Mole fraction of the first repeat units from the left A-1 0.3 mole fraction of the second repeat units from the left A-1 is 0.5, the third repeat from the left of A-1 since the mole fraction of units is 0.2, considering the Ohnishi parameter of each repeating unit described above, Ohnishi parameter of a-1 is, 5.5 × 0.3 + 7.7 × 0.5 + 6.1 × 0 a .2 ≒ 6.7.

Here, Ohnishi parameter of the resin (P) refers to the Ohnishi parameter of the resin (P) of the part remains as a pattern after the lithography process.

In the present invention, Ohnishi parameter of the resin (P) is preferably larger than the Ohnishi parameter of the resin (A) contained in the actinic ray-sensitive or radiation-sensitive resin composition described later. As with Ohnishi parameter of the resin (P) is greater than 4.5, further elicit the effect of the resist film (second film) etching resistance is enhanced present invention for etching resistance of the flattening film (first film) it becomes possible. Here, Ohnishi parameter of the resin (A) contained in the actinic ray-sensitive or radiation-sensitive resin composition has the same definition as Ohnishi parameter in the above-described resin (P).

In one form of the present invention, the resin composition (a) and Ohnishi parameter of the resin (P) contained in the (flattening film forming composition) (Xp), the actinic ray-sensitive or radiation-sensitive resin composition the relationship between the Ohnishi parameter of the resin (a) contained (Xa), 0 <is preferably Xp-Xa <20, more preferably 3 <Xp-Xa <20, 8 <Xp-Xa <further preferably 20.

The resin (P) is not particularly limited as long as Ohnishi parameter is greater than 4.5 the resin, and specific examples thereof include poly (meth) acrylic resins, polyester resins, polyether resins, polystyrene resins, polyvinyl alcohol resins, poly such as siloxane resin and the like. Among them, poly (meth) acrylic resin, that is at least one resin selected from the group consisting of polyester resins and polyether resins.
Resin (P) is preferably free of aromatic rings.

But the glass transition temperature of the resin (P) (Tg) is not particularly limited, preferably at 200 ° C. or less, more preferably 0.99 ° C. or less. The lower limit of Tg is not particularly limited, but usually, -100 ° C. or higher. For reasons embedding and flatness more excellent, Tg is preferably low.

Incidentally, Tg is differential scanning calorimetry; is measured using a (Differential Scanning Calorimetry DSC).

Although the weight-average molecular weight of the resin (P) is not particularly limited, preferably from 500 to 100,000, among others, preferably 20,000 or less, more preferably 15,000 or less, 10 , even more preferably 000 or less.

In the present specification, the weight average molecular weight, the following conditions of gel permeation chromatography; a standard polystyrene equivalent value determined from (Gel Permeation Chromatography GPC). Column type: TSK SuperAWM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 150 mm, developing solvent: NMP (N-methyl-2-pyrrolidinone (N-methylpyrrolidone)) · Column temperature: 50 ° C., flow rate: 0 .35mL / min · sample injection amount:. 20μL · device name: HLC-8220GPC (Tosoh Co., Ltd.)
<First preferred embodiment>
The resin (P) preferably has a repeating unit represented by the following general formula (1-1). Resin (P) may contain a repeating unit represented by the following general formula (1-1) of two or more.

Figure JPOXMLDOC01-appb-C000007

In the formula,
R 1 represents a hydrogen atom or an organic group.

R 2 represents a hydrocarbon group having a hetero atom. However, for the number of carbon atoms contained in R 2, the ratio of the number of hetero atoms contained in R 2 is 0.30 or more.

As described above, in the general formula (1-1), R 1 represents a hydrogen atom or an organic group. The organic group represented by R 1, for example, fluorine atom, a alkyl group which may have a substituent such as a hydroxyl group. As R 1, for example, a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, and the like are preferable.

As described above, in the general formula (1-1), R 2 represents a hydrocarbon group having a hetero atom. But it is not heteroatoms R 2 has particularly limited, specific examples, a nitrogen atom, an oxygen atom and a sulfur atom. Among them, preferably an oxygen atom.

Hydrocarbon groups having heteroatoms is not particularly limited, aliphatic hydrocarbon groups having heteroatoms (e.g., 1 to 10 carbon atoms) (linear, branched or cyclic), aromatic with heteroatoms carbide hydrogen group (e.g., 6 to 20 carbon atoms), an alicyclic heterocyclic group, such group in combination an aromatic heterocyclic group, or a thereof.

However, for the number of carbon atoms contained in R 2, the ratio of the number of the heteroatom contained in R 2 (hereinafter, also referred to as "hetero atom ratio") is 0.30 or more. Among them, it is preferably 0.50 or more. The upper limit heteroatoms ratio is not particularly limited, but usually, it is 1.00 or less.

As the R 2, for example, the ratio heteroatom of 0.30 or more, respectively, an aliphatic hydrocarbon group (e.g., 1 to 10 carbon atoms) (linear, branched or cyclic), aromatic hydrocarbon group (e.g., 6 to 20 carbon atoms), a lactone structure-containing group, a carbonate structure-containing group, an acetal structure-containing group, hydroxy group-containing group, or include a group represented by the general formula (P1) to be described later, Naka But heteroatom content of 0.30 or more, respectively, lactone structure-containing group, a carbonate structure-containing group, an acetal structure-containing group, hydroxy group-containing group, or a group represented by the general formula (P1) to be described later it is preferable.

The lactone structure-containing group is a group having a lactone structure (a cyclic ester structure).

Specific examples of the lactone structure include lactone structures in the "repeating unit having a lactone structure" which may contain a resin (A) is described below.

The carbonate structure-containing group represents a group containing a carbonate structure (cyclic carbonate structure). Specific examples of the carbonate structure include the cyclic carbonate structure in "repeating unit having a cyclic carbonate structure" which may contain a resin (A) is described below.

The acetal structure-containing group represents a group containing an acetal structure.
Here, acetal structure is represented by the following general formula (Q).

Figure JPOXMLDOC01-appb-C000008

In the formula,
R 1 ~ R 4 each independently represent a hydrocarbon group. R 1 ~ R 4 may be bonded to each other to form a ring.

Hydrocarbon group as R 1 ~ R 4 are not particularly limited, for example, aliphatic hydrocarbon groups (e.g., 1 to 10 carbon atoms) (linear, branched or cyclic), aromatic hydrocarbon group (e.g., 6 to 20 carbon atoms) and the like. Among them, aliphatic hydrocarbon groups are preferred.

The hydroxy group-containing group represents a group containing a hydroxy group (-OH). Among them, it is preferably a hydrocarbon group containing a hydroxy group. Specific examples and preferred embodiments of the hydrocarbon group are the same as R 1 ~ R 4 in general formula (Q).
The hydroxy group-containing group is preferably a group containing a hydroxy group or two.

It will be described group represented by the general formula (P1) below.

Figure JPOXMLDOC01-appb-C000009

In the formula (P1),
R A represents a divalent hydrocarbon group which may contain a hetero atom.
R B represents a monovalent hydrocarbon group which may contain a hetero atom.
n represents an integer of 1 or more. also is R A presence of a plurality if n is an integer of 2 or more may be the same or different.
* Represents a bonding position of the remainder of the repeating unit represented by formula (1-1).

However, the ratio of the number of heteroatoms for the general formula (P1) carbon atoms contained in is at least 0.30.

As mentioned above, R A represents a divalent hydrocarbon group. Specific examples and preferred embodiments of the hydrocarbon group are the same as R 1 ~ R 4 in above formula (Q).

As described above, R B represents a monovalent hydrocarbon group. Specific examples and preferred embodiments of the hydrocarbon group are the same as R 1 ~ R 4 in above formula (Q).

As described above, n is an integer of 1 or more. n is preferably an integer of 1-10.

In a first preferred embodiment, the resin (P) the recurring units represented by the above formula (1-1) in: ratio of (R 2 lactone structure-containing group) is preferably 10 ~ 80 mol% , and more preferably 10 ~ 60 mol%.

In a first preferred embodiment, the resin (P) above repeating unit represented by formula (1-1) in: ratio of (R 2 a carbonate structure-containing group) is preferably 10 ~ 80 mol% , and more preferably 10 ~ 50 mol%.

In a first preferred embodiment, the resin (P) above repeating unit represented by formula (1-1) in: ratio of (R 2 acetal structure-containing group) is preferably 10 ~ 80 mol% , and more preferably 10 ~ 30 mol%.

In a first preferred embodiment, the recurring unit represented by the above equation in the resin (P) (1-1): the ratio of (R 2 group represented by the above-mentioned formula (P1)) is 10 ~ it is preferably 80 mol%, more preferably 10 ~ 30 mol%.

In a first preferred embodiment, has a repeating unit represented by the resin of the repeating unit represented by the above equation in (P) (1-1) (the above Expression (1-1) two or more If the percentage of total) is not particularly limited, preferably from 10 ~ 100 mol%, and more preferably 80 ~ 100 mol%.

In a first preferred embodiment, the resin (P) is a repeating unit represented by formula (1-1) above: preferably has a (R 2 group represented by the formula (P1) as described above), among them, the repeating unit represented by formula (1-1): is more preferred that the proportion of the (R 2 group represented by the above-mentioned formula (P1)) is not less than 15 mol%, among them, the repeating unit represented by the formula (1-1): Apart from the (R 2 group represented by the above-mentioned formula (P1)), the repeating unit represented by the above formula (1-1) (R 2: and more preferably a group) containing two or more hydroxy groups.

In a first preferred embodiment, the resin (P) may contain a repeating unit other than the repeating unit represented by the formula (1-1) described above. For example, the ratio hetero atom and repeating units of less than 0.30 in the formula (1-1) described above. <Second preferred embodiment>
The resin (P) preferably has a repeating unit represented by the following general formula (1-2). Resin (P) may contain a repeating unit represented by the following general formula (1-2) of two or more.

Figure JPOXMLDOC01-appb-C000010

In the formula,
L represents an organic group.
X is, -O -, - S -, - CO -, - CO-O-, or represents -O-CO-.

As described above, L is an organic group.
As the organic group, for example, there are mentioned hydrocarbon group, specific examples and preferred embodiments of the hydrocarbon group are the same as R 1 ~ R 4 in general formula (Q).

The hydrocarbon group may have a substituent, as the substituent, for example, a hydrocarbon group having 1 to 20 carbon atoms, hydroxy group, and the like.

Further, the hydrocarbon group may contain one or more functional groups, as the functional group, for example, -O -, - S -, - CO -, - CO-O -, - O- CO-, and the like.

In a second preferred embodiment, the ratio of the repeating unit represented by the above equation in the resin (P) (1-2): the ratio of (X -O-) is preferably 20 ~ 100 mol% , more preferably 50 ~ 100 mol%, and more preferably 80 ~ 100 mol%.

In a second preferred embodiment, having a repeating unit represented by the resin of the repeating unit represented by the above equation in (P) (1-2) (the above Expression (1-2) two or more If the percentage of total) is not particularly limited, preferably from 10 ~ 100 mol%, and more preferably 80 ~ 100 mol%.

In the resin composition of the present invention (a), the content of the resin (P) is not particularly limited, the total solid content, it is preferably 10 to 100 mass%, 80 to 100 mass% more preferable.

Further, the resin composition of the present invention (a), may contain one resin (P), may be used in combination of two or more resins (P).

[Optional Components]
The resin composition of the present invention (a) may contain a component other than the resin (P). Such ingredients include a resin (P) other than the resin, a solvent, such as surfactants. Examples of solvents and surfactants are the same as the actinic ray-sensitive or radiation-sensitive resin composition described later. The resin composition of the present invention (a) preferably contains a solvent.

Next, the actinic ray-sensitive or radiation-sensitive resin composition is described.
<Actinic ray-sensitive or radiation-sensitive resin composition>
The actinic ray-sensitive or radiation-sensitive resin composition is a composition used for forming the second layer contains a resin (A) which changes polarity by the action of an acid. The actinic ray-sensitive or radiation-sensitive resin composition further contains a compound capable of generating an acid upon irradiation with actinic rays or radiation, hydrophobic resins, acid diffusion control agents, solvents, surfactants or other additives it may be.

[1] Resin Resin polarity is changed by the action of an acid (A) is a resin whose polarity is changed by the action of an acid, the main chain or side chain of the resin, or in both the main chain and side chain, acid group decomposed increased polarity by the action of (hereinafter referred to as "acid-decomposable group".) resin having a (hereinafter, also referred to as "acid-decomposable resin".) is preferably. Before and after the irradiation with an actinic ray or radiation, by the polarity of the acid-decomposable resin is greatly changed, improved dissolution contrast when development with an alkaline developer or an organic solvent-based developing solution, using an alkali developer when development Te takes aspects of positive pattern, when development with an organic solvent-based developing solution, it is possible to take the aspects of the negative pattern.

The resin (A), more preferably contains a repeating unit having an acid-decomposable group. The repeating unit having an acid-decomposable group, a repeating unit having a decomposed group to produce alkali-soluble group by the action of an acid are preferred.

[Repeating unit having an acid-decomposable group]
As described above, the resin (A) preferably contains a repeating unit having an acid decomposable group.

Here, the acid decomposable group is decomposed by the action of an acid, refers to a group produce a polar group.

Acid-decomposable group preferably has a decomposition protected structure desorption radicals (leaving) by the action of the polar group acid.

The polar group is not particularly limited as long as it is a group of poorly soluble or insoluble in a developer containing an organic solvent, a phenolic hydroxyl group, a carboxyl group, a fluoroalcohol group (preferably hexafluoroisopropanol group), a sulfonic acid group , a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, an (alkylsulfonyl) (alkylcarbonyl) imide group, a bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, a bis (alkyl sulfonyl) methylene group, bis (alkylsulfonyl) imide group, a tris (alkylcarbonyl) methylene group, is used as a developer of acidic groups (conventional resist such as tris (alkylsulfonyl) methylene group, 2.38 wt% tetra Mechiruan Group dissociates in onium hydroxide aqueous solution), or alcoholic hydroxyl group.

Note that the alcoholic hydroxyl group, a hydroxyl group bonded to a hydrocarbon group, an electron withdrawing nice hydroxyl other than hydroxyl group bonded directly on an aromatic ring (phenolic hydroxyl groups), position α as hydroxyl and fluorine atom aliphatic alcohol substituted with sexual group (e.g., a fluorinated alcohol group (such as hexafluoroisopropanol group)) shall be excluded. The alcoholic hydroxyl group, it is preferred pKa (acid dissociation constant) of 12 or more and 20 or less hydroxyl group.

Preferred polar group, a carboxyl group, a fluoroalcohol group (preferably hexafluoroisopropanol group) and a sulfonic acid group.

The group preferred as the acid-decomposable group is a group obtained by substituting a group capable of leaving a hydrogen atom of these groups with an acid.

In the desorption radicals (leaving) the acid, for example, -C (R 36) (R 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02) (can be exemplified OR 39) or the like.

Wherein, R 36 ~ 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 represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

Alkyl group R 36 ~ R 39, R 01 and R 02, cyclohexyl preferably an alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, n- butyl group, sec- butyl group to, it can be exemplified group, an octyl group.

Cycloalkyl group R 36 ~ R 39, R 01 and R 02 may be monocyclic or polycyclic. The monocyclic, a cycloalkyl group having 3 to 8 carbon atoms Preferably, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, for example, adamantyl group, norbornyl group, isobornyl group, a dicyclopentyl group, alpha-camphonyl group, tricyclodecanyl group, tetracyclododecyl group, and androstanyl group. It may be substituted by at least one hetero atom such as carbon atoms the oxygen atoms in the cycloalkyl group.

Aryl group R 36 ~ R 39, R 01 and R 02 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthryl group.

Aralkyl group R 36 ~ R 39, R 01 and R 02 is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group.

Alkenyl group R 36 ~ R 39, R 01 and R 02 is an alkenyl group having 2 to 8 carbon atoms is preferable, and examples thereof include a vinyl group, an allyl group, a butenyl group and a cyclohexenyl group.

The ring and R 36 and R 37 are formed by bonding, it is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group, a cyclopentyl group, a monocyclic cycloalkyl group such as cyclohexyl group, norbornyl group, tetra tricyclodecanyl group, tetracyclododecanyl group, a polycyclic cycloalkyl group such as an adamantyl group. More preferably a monocyclic cycloalkyl group having 5 or 6 carbon atoms, particularly preferably a monocyclic cycloalkyl group having 5 carbon atoms.

Preferably, the acid-decomposable group is a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, a tertiary alkyl ester group.

The resin (A), a repeating unit having an acid-decomposable group preferably has a repeating unit represented by the following formula (AI). Repeating unit represented by formula (AI) is intended to generate a carboxyl group as a polar group by the action of an acid, in a plurality of carboxyl groups, to show a high interaction by hydrogen bonding, a negative type formed pattern, in the solvent of the actinic ray-sensitive or radiation-sensitive resin composition described above, more reliably, can be insoluble or hardly soluble.

Figure JPOXMLDOC01-appb-C000011

In the general formula (AI),
Xa 1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.

T represents a single bond or a divalent linking group.

Rx 1 ~ Rx 3 each independently represents an alkyl group or a cycloalkyl group.

Rx 1 two of ~ rx 3 may combine to form a ring structure.

Examples of the divalent linking group T, then the alkylene group, -COO-Rt- group, -O-Rt- group, and a phenylene group. In the formulas, Rt represents an alkylene group or a cycloalkylene group.

T represents a single bond or a group of the formula -COO-Rt- preferred. Rt is preferably an alkylene group having 1 to 5 carbon atoms, -CH 2 - group, - (CH 2) 2 - group, - (CH 2) 3 - group are more preferable. T is more preferably a single bond.

Alkyl group X a1 as well, substituents may have a substituent, for example, a hydroxyl group, (preferably, a fluorine atom) a halogen atom.

Alkyl group X a1 is preferably those having 1 to 4 carbon atoms, a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group and the like, preferably a methyl group.

X a1 is preferably a hydrogen atom or a methyl group.

The alkyl group of Rx 1, Rx 2 and Rx 3, be linear, it may be branched, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, such as t- butyl group preferably. The number of carbon atoms of the alkyl group preferably has 1 to 10, 1 to 5 and more preferable.

The cycloalkyl group of Rx 1, Rx 2 and Rx 3, cyclopentyl group, a monocyclic cycloalkyl group such as cyclohexyl group, norbornyl group, tetra tricyclodecanyl group, tetracyclododecanyl group, polycyclic, such as adamantyl group preferred cycloalkyl groups are.

The ring structure is two formed by the bonding of Rx 1, Rx 2 and Rx 3, cyclopentyl ring, monocyclic cycloalkane ring such as a cyclohexyl ring, norbornane ring, tetracyclo decane ring, tetracyclododecane ring, adamantane ring polycyclic cycloalkyl group such as is preferred. Cycloalkane ring monocyclic 5 or 6 carbon atoms are particularly preferred.

Rx 1, Rx 2 and Rx 3 are each independently preferably an alkyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

Each of these groups may have a substituent, examples of the substituent include an alkyl group (1-4 carbon atoms), a cycloalkyl group (having 3-8 carbon atoms), a halogen atom, an alkoxy group (carbon 1 to 4), a carboxyl group, can be mentioned an alkoxycarbonyl group (2-6 carbon atoms), preferably 8 or less carbon atoms. Among them, from the viewpoint of further improving dissolution contrast for an organic solvent-containing developer before and after acid decomposition, an oxygen atom, a nitrogen atom, more preferably a substituent group having no hetero atom such as a sulfur atom (e.g. , more preferably not such an alkyl group substituted with a hydroxyl group), more preferably a group consisting of only hydrogen and carbon atoms, straight-chain or branched alkyl group, particularly preferably a cycloalkyl group .

In formula (AI), Rx 1 ~ Rx 3 are each independently an alkyl group, it is preferable not to form the two members ring structure of Rx 1 ~ Rx 3. This can suppress an increase in the volume of the group represented by -C as groups decomposing and leaving (Rx 1) (Rx 2) (Rx 3) by the action of an acid, an exposure step, and, after the exposure step in good post-exposure heating step be carried, it tends to be suppressed volumetric shrinkage of the exposed portion.

Specific examples of the repeating unit represented by formula (AI) are shown below, but the present invention is not limited to these specific examples.

In specific examples, Rx represents a hydrogen atom, CH 3, CF 3, or CH 2 OH. Rxa, Rxb each independently represents an alkyl group (preferably having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms). Xa 1 represents a hydrogen atom, CH 3, CF 3, or CH 2 OH. Z represents a substituent, if there are a plurality, a plurality of Z may be different be the same as each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as specific examples and preferred examples of the substituents may have the respective groups such Rx 1 ~ Rx 3.

Figure JPOXMLDOC01-appb-C000012

Figure JPOXMLDOC01-appb-C000013

Figure JPOXMLDOC01-appb-C000014

Further, resin (A), a repeating unit having an acid-decomposable group, it also preferably contains a repeating unit described in JP 2014-202969 JP paragraphs [0057] - [0071].

Further, resin (A), a repeating unit having an acid-decomposable group, which may have a repeating unit produce an alcoholic hydroxyl group described in JP 2014-202969 JP paragraphs [0072] to [0073] good.

Repeating unit having an acid-decomposable group may be one kind or in combination of two or more thereof.

Based on all repeating units in the resin (the sum case where the repeating unit having an acid-decomposable group is more present) The content of the repeating unit having an acid-decomposable group included in (A), the resin (A), preferably 20 to 90 mol%, more preferably 40 to 80 mol%. Among them, which has a repeating unit of the resin (A) is represented by the general formula (AI), the amount of content to the total repeating units of the repeating unit represented by formula (AI) resin (A) is 40 mol it is preferably at least%.

[Repeating unit having a silicon atom]
The resin (A), a silicon atom (hereinafter, "Si atom") preferably contains, it is more preferable to oil-containing repeating units having a Si atom. When the resin (A) contains a silicon atom increases the etching resistance. In this case, it becomes possible to reduce the thickness of the second layer, it enhances the resolution of the pattern.

In the present invention, the content of Si atoms in the resin (A) is preferably from 1 to 30% by weight, it more preferably 8 to 30 mass%, 13 to 30 mass% further preferable. Here, the Si content of the resin (A), means Si content of the resin (A) of the portion that remains as a pattern after the lithography process.

In this specification, repeating units having both Si atoms and acid decomposable group in the repeating unit having an Si atom, shall be applicable to the repeating unit having an acid decomposable group. For example, a resin consisting of a repeating unit having both Si atoms and the acid-decomposable group corresponds to a resin including a repeating unit having a repeating unit and an acid-decomposable group having an Si atom.

Repeating unit having a Si atom is not particularly limited if it has the Si atom. For example, a silane-based repeating unit (-SiR 2 -: R 2 is an organic group), a siloxane-based repeating unit (-SiR 2 -O-: R 2 is an organic group), with a Si atoms (meth) acrylate repeating units, vinyl-based repeating unit having an Si atom.

Repeating unit having a Si atom preferably has a silsesquioxane structure. Even a silsesquioxane structure in the main chain may have a side chain, but is preferably in a side chain.

The silsesquioxane structure, for example, cage silsesquioxane structure, ladder-type silsesquioxane structure (a ladder silsesquioxane structure), such as random-type silsesquioxane structure. Among them, the cage silsesquioxane structure is preferable.

Here, the cage silsesquioxane structure, a silsesquioxane structure having a cage-like skeleton. That cage silsesquioxane structure may be a complete cage silsesquioxane structure, it may be incomplete cage silsesquioxane structure, a complete cage silsesquioxane structure preferable.

Further, the ladder-type silsesquioxane structure, a silsesquioxane structure having a ladder-like skeleton.

Further, a random-type silsesquioxane structure, skeleton silsesquioxane structure randomly.

The cage silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).

Figure JPOXMLDOC01-appb-C000015

In the above formula (S), R represents a monovalent organic group. Plural R may be the same or different.

The organic group is not particularly limited, and specific examples include a halogen atom, hydroxy group, a nitro group, a carboxy group, an alkoxy group, an amino group, a mercapto group, a blocked mercapto group (e.g., an acyl group block (protect) mercapto group), an acyl group, an imido group, a phosphino group, a phosphinyl group, a silyl group, vinyl group, hydrocarbon group which may have a hetero atom, and (meth) acrylic group-containing group and an epoxy group-containing group and the like.

As the halogen atom, e.g., fluorine atom, chlorine atom, bromine atom, and an iodine atom.

The heteroatom of the hydrocarbon group which may have the hetero atom such as oxygen atom, nitrogen atom, sulfur atom, and phosphorus atom.

The hydrocarbon group of a hydrocarbon group which may have the hetero atom, for example, aliphatic hydrocarbon group, aromatic hydrocarbon group or the like group which is a combination of these, and the like.

The aliphatic hydrocarbon group may be linear, branched, it may be any of circular. Specific examples of the aliphatic hydrocarbon group, a linear or branched alkyl group (particularly, 1 to 30 carbon atoms), a linear or branched alkenyl group (particularly, 2 to 30 carbon atoms), linear or branched alkynyl group (particularly, 2 to 30 carbon atoms) and the like.

Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms such as naphthyl group.

Repeating unit having a Si atom is preferably represented by the following formula (I).

Figure JPOXMLDOC01-appb-C000016

In the above formula (I), L represents a single bond or a divalent linking group.

Examples of the divalent linking group include an alkylene group, -COO-Rt- group, -O-Rt- group and the like. In the formulas, Rt represents an alkylene group or a cycloalkylene group.

L represents a single bond or a group of the formula -COO-Rt- preferred. Rt is preferably an alkylene group having 1 to 5 carbon atoms, -CH 2 - group, - (CH 2) 2 - group, - (CH 2) 3 - group are more preferable.

In the above formula (I), X represents a hydrogen atom or an organic group.

As the organic group, for example, a fluorine atom, and an alkyl group which may have a substituent such as a hydroxyl group, a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group is preferable.

In the above formula (I), A represents a Si-containing group. Among them, preferably a group represented by the following formula (a) or (b).

Figure JPOXMLDOC01-appb-C000017

In the above formula (a), R represents a monovalent organic group. Plural R may be the same or different. Specific examples and preferred embodiments of R are the same as above formula (S). In the case A in the above formula (I) is a group represented by the above formula (a), the formula (I) is represented by the following formula (I-a).

Figure JPOXMLDOC01-appb-C000018

Figure JPOXMLDOC01-appb-C000019

In the above formula (b), R b represents a hydrocarbon group which may have a hetero atom. Specific examples and preferred embodiments of the hydrocarbon group which may have a hetero atom is the same as R in the above formula (S).

Repeating unit having a Si atom resin (A) contains may be the one may be in combination of two or more.

To the total repeating units of the resin (A), the is not particularly limited content of the repeating unit having an Si atom is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.

The resin (A), lactone structure, sultone structure, and that includes a repeating unit having at least one of carbonate structural preferred.

The lactone structure or sultone structure, can be used any one as long as it has a lactone structure or a sultone structure, preferably 5 to 7-membered ring lactone structure or a 5 to 7-membered ring sultones structure, 5-7 membered ring lactone structure bicyclo structure to which another ring structure in the form of forming a spiro structure is condensed, or bicyclo structure 5 to 7-membered ring sultones structure, other in the form of forming a spiro structure the ring which structure is condensed, but more preferable. Lactone structure represented by any one of the following formulas (LC1-1) ~ (LC1-21), or sultone structure represented by any one of the following general formula (SL1-1) ~ (SL1-3), more preferably has a repeating unit having a. Further, a lactone structure or a sultone structure may be bonded directly to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), a (LCl-17), in particular preferred lactone structures are (LCI -4). LER by using such a specific lactone structure, and development defect are improved.

Figure JPOXMLDOC01-appb-C000020

The lactone structure moiety or sultone structure moiety may or may not have have a substituent (Rb 2). Preferred examples of the substituent (Rb 2), an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferably an alkyl group having 1 to 4 carbon atoms, a cyano group and an acid-decomposable group. n 2 represents an integer of 0-4. When n 2 is 2 or more, plurality of substituents (Rb 2) may be the same or different. It may also be bonded to form a ring substituent (Rb 2) between the plurality of.

Repeating unit having a lactone structure or sultone structure, usually an optical isomer, may be any of optical isomers. Moreover, even with a single type of optical isomer alone and to use a mixture of a plurality of optical isomers. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.

Repeating unit having a lactone structure or sultone structure is preferably a repeating unit represented by the following general formula (III).

Figure JPOXMLDOC01-appb-C000021

In the above formula (III),
A represents an ester bond (-COO- group represented by) or an amide bond (a group represented by -CONH-).

R 0 is expressed independently represents an alkylene group when there are a plurality, a cycloalkylene group, or a combination thereof.

Z are each independently in the presence of two or more, a single bond, an ether bond, an ester bond, an amide bond, a urethane bond

Figure JPOXMLDOC01-appb-C000022

Or a urea bond

Figure JPOXMLDOC01-appb-C000023

A representative. Here, R represents each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

R 8 represents a monovalent organic group having a lactone structure or sultone structure.

n is the repetition number of the structure represented by -R 0 -Z-, represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, -R 0 -Z- is not present, the single bond.

R 7 represents a hydrogen atom, a halogen atom or an alkyl group.

Alkylene group R 0, cycloalkylene group may have a substituent.

Z is preferably an ether bond, an ester bond, particularly preferably an ester bond.

Alkyl group R 7 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group an ethyl group, a methyl group is particularly preferred.

Alkylene group R 0, a cycloalkylene group, an alkyl group in R 7 may be respectively substituted, as the substituent, for example, a fluorine atom, a chlorine atom, a halogen atom or a mercapto group such as a bromine atom, a hydroxyl group, methoxy group, an ethoxy group, an isopropoxy group, t-butoxy group, an alkoxy group such as benzyloxy group, acyloxy group such as acetyloxy group and propionyloxy group.

R 7 is a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group is preferable.

Preferably chain alkylene of 1 to 10 carbon atoms are preferred chain alkylene group in R 0, more preferably 1 to 5 carbon atoms, e.g., methylene, ethylene, propylene, and the like. Preferred cycloalkylene group, a cycloalkylene group having 3 to 20 carbon atoms, for example, a cyclohexylene group, a cyclopentylene group, a norbornylene group and an adamantylene group. Chain alkylene group is more preferred to express the effects of the present invention, a methylene group is particularly preferred.

A monovalent organic group having a lactone structure or sultone structure represented by R 8 is not limited as long as it has a lactone structure or a sultone structure formula as a specific example (LC1-1) ~ ( LC1-21) and, (SL1-1) ~ (SL1-3) either a lactone structure or sultone structure represented by may be mentioned among the structures represented by the among these (LCI -4) are particularly preferable. Further, n 2 is more preferably of 2 or less in (LC1-1) ~ (LC1-21).

Further, the monovalent organic group having a lactone structure or sultone structure of R 8 is unsubstituted, or a methyl group, a monovalent organic group having a lactone structure or sultone structure having a cyano group or an alkoxycarbonyl group as a substituent preferably a monovalent organic group having a lactone structure (cyanolactone) having a cyano group as a substituent are more preferable.

Specific examples of the repeating unit containing a group having a lactone structure or sultone structure below, the present invention is not limited thereto.

Figure JPOXMLDOC01-appb-C000024

Figure JPOXMLDOC01-appb-C000025

Figure JPOXMLDOC01-appb-C000026

To enhance the effect of the present invention, it is also possible to use a repeating unit having two or more lactone structure or sultone structure.

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 based on all the repeating units in the resin (A), 5 ~ 60 mole% by weight, more preferably 5-55 mol%, more preferably 10 to 50 mol%.

The resin (A) may have a repeating unit having a carbonate structure (cyclic carbonate structure).

The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).

Figure JPOXMLDOC01-appb-C000027

In formula (A-1), R A 1 represents a hydrogen atom or an alkyl group.

R A 2 are each independently of when n is 2 or more, it represents a substituent.

A represents a single bond or a divalent linking group.

Z represents an atomic group forming a monocyclic or polycyclic structure together with a group represented by -O-C in the formula (= O) -O-.

n represents an integer of 0 or more.

It will be described in detail the general formula (A-1).

The alkyl group represented by R A 1 may have a substituent such as a fluorine atom. R A 1 represents a hydrogen atom, preferably represents a methyl group or a trifluoromethyl group, and more preferably a methyl group.

Substituents represented by R A 2 is, for example, an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, an amino group, an alkoxycarbonylamino group. Preferably an alkyl group having 1 to 5 carbon atoms, such as methyl group, ethyl group, propyl group, a linear alkyl group having 1 to 5 carbon atoms such as butyl group; an isopropyl group, an isobutyl group, t- butyl group it can be mentioned branched alkyl group having a carbon number of 3-5 and so on. Alkyl group may have a substituent such as a hydroxyl group.

n is an integer of 0 or greater which represents the number of substituents. n is, for example, preferably from 0 to 4, more preferably 0.

Examples of the divalent linking group represented by A, for example, an alkylene group, a cycloalkylene group, an ester bond, an amide bond, ether bond, urethane bond, urea bond, or combinations thereof. The alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, e.g., methylene, ethylene, propylene, and the like.

In one form of the invention, A is preferably a single bond, an alkylene group.

Represented by Z, The monocyclic ring containing -O-C (= O) -O- , e.g., in the cyclic carbonate represented by the following general formula (a), an n A = 2 ~ 4 5 to 7-membered ring, and it is preferably a 5- or 6-membered ring (n a = 2 or 3), more preferably a 5-membered ring (n a = 2).

Represented by Z, The polycyclic ring containing -O-C (= O) -O-, e.g., cyclic carbonate together with one or more other ring structure represented by the following general formula (a) and structure forming a condensed ring, include the structures form a spiro ring. As "other ring structure" capable of forming a fused ring or spiro ring may be a cycloaliphatic hydrocarbon radical may be an aromatic hydrocarbon group may be a heterocyclic ring .

Figure JPOXMLDOC01-appb-C000028

Monomers, for example, Tetrahedron Letters, Vol corresponding to the repeating unit represented by the general formula (A-1). 27, No. 32 p. 3741 (1986), Organic Letters, Vol. 4, No. 15 p. 2561 (2002) described the like, by a conventional method, it can be synthesized.

The resin (A), one of the repeating unit represented by formula (A-1) may be included alone, it may contain two or more kinds.

In the resin (A), the repeating unit (preferably, formula (repeating unit represented by A-1)) having a cyclic carbonate structure content of the total repeating units constituting the resin (A) , preferably from 3 to 80 mol%, from 3 to more preferably from 60 mol%, particularly preferably from 3 to 30 mol%, and most preferably 10 to 15 mol%. With such a content, developability as a resist, low defectivity, low LWR (Line Width Roughness), low PEB (Post Exposure Bake) temperature dependence, it is possible to improve the profile.

The following general formula Specific examples of the repeating unit represented by (A-1) (repeating unit (A-1a) ~ (A-1w)), but the present invention is not limited thereto.

Incidentally, R A 1 in the following specific examples are the same meaning as R A 1 in the general formula (A-1).

Figure JPOXMLDOC01-appb-C000029

The resin (A) may contain a repeating unit having a hydroxyl group or a cyano group. Examples of such a repeating unit, for example, a repeating unit described in JP 2014-098921 JP paragraphs [0081] - [0084].

The resin (A) may contain a repeating unit having an alkali-soluble group. Carboxyl group as the alkali-soluble group, a sulfonamide group, a sulfonylimide group, bis sulfonyl imide groups, alpha-position substituted aliphatic alcohols (e.g., hexafluoroisopropanol group) with an electron-withdrawing group. The repeating unit having an alkali-soluble group include a repeating unit described in JP 2014-098921 JP paragraphs [0085] to [0086].

The resin (A) may further polar group (e.g., alkali-soluble group, a hydroxyl group, a cyano group, etc.) having an alicyclic hydrocarbon structure having no, having a repeating unit and not exhibiting acid decomposability. Examples of such a repeating unit, for example, a repeating unit described in JP 2014-106299 JP paragraphs [0114] - [0123].

The resin (A) may, for example, may contain a repeating unit described in JP 2009-258586 JP paragraphs [0045] - [0065].

Resin (A) used in the method of the present invention, in addition to the above-dry etching resistance, standard developing solution aptitude, adhesion to substrate, resist profile, resolution and generally required properties of the resist, heat resistance, can have a variety of repeating structural units for the purpose of and sensitivity. As these repeating structural units include repeating structural units corresponding to the monomers described below, but the invention is not limited thereto.

Accordingly, the performance required of the resin (A) used in the method of the present invention, in particular, (1) solubility in a coating solvent, (2) film-forming property (glass transition point), (3) alkali developability, (4) film loss (hydrophilic, hydrophobic or alkali-soluble group selection), (5) adhesion of unexposed area to substrate, and (6) dry etching resistance, can be finely adjusted like.

As such monomers, such as acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, compounds having one addition polymerizable unsaturated bond selected from vinyl esters and the like can be given.

Other than these, unsaturated compound monomers copolymerizable with addition polymerizable corresponding to the above-described various repeating structural units may be copolymerized.

In the resin (A), the molar ratio of respective repeating structural units to adjust dry etching resistance, standard developer suitability of substrate adhesion, resist profile and resolution is a common requisite characteristics of the resist, heat resistance, sensitivity It is appropriately set to adjust the like.

The actinic ray-sensitive or radiation-sensitive resin composition, when it is for ArF exposure, the resin (A) from the viewpoint of transparency to ArF light is preferably has substantially no aromatic groups. More specifically, in all repeating units in the resin (A), is preferably that the repeating unit having an aromatic group is not more than 5 mol% of the total, more preferably 3 mol% or less, ideally 0 mol%, i.e. it is more preferably has no repeating unit having an aromatic group. The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

The resin (A), from the viewpoint of compatibility with the later-described hydrophobic resin (D), preferably contains no fluorine atom and a silicon atom.

Preferably the resin (A) is one in which all repeating units are composed of a (meth) acrylate repeating units. In this case, all repeating units may be a methacrylate-based repeating unit, all of the repeating units are acrylate-based repeating unit, also all repeating units of any of those of a methacrylate-based repeating unit and an acrylate-based repeating unit may be used, it is preferred for the acrylate repeating units is less than 50 mol% of all repeating units.

Resin (A) can be synthesized (for example, radical polymerization) in a conventional manner. For example, as ordinary methods, a monomer species and an initiator are dissolved in a solvent, bulk polymerization method in which polymerization is carried out by heating a solution of monomer species and an initiator dropwise over 1 to 10 hours in heated solvent such as dropping polymerization method of adding Te, and the like, dropping polymerization method is preferred. Examples of the reaction solvent include tetrahydrofuran, 1,4-dioxane, ethers or methyl ethyl ketone, such as diisopropyl ether, ketones such as methyl isobutyl ketone, ester solvents such as ethyl acetate, dimethyl formamide, amide solvents such as dimethylacetamide, Furthermore propylene glycol monomethyl ether acetate described later, propylene glycol monomethyl ether, a solvent capable of dissolving the actinic ray-sensitive or radiation-sensitive resin composition, such as cyclohexanone. It is preferred to perform the polymerization using the same solvent as employed in the compositions of the present invention. Thus, generation of particles during storage can be suppressed.

The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. Commercially available radical initiator as a polymerization initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. Azo initiators are preferred as the radical initiator, an ester group, a cyano group, an azo initiator having a carboxyl group is preferable. Preferred initiators, azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methyl propionate) and the like. If desired, the initiator is added additionally or in parts, after completion of the reaction, is charged into a solvent and the desired polymer is recovered powder or solid recovery method. The reaction concentration is from 5 to 50 wt%, preferably 10 to 30 mass%. The reaction temperature is usually 10 ° C. ~ 0.99 ° C., preferably from 30 ° C. ~ 120 ° C., more preferably 60 ~ 100 ° C..

As described above, the content of Si atoms in the resin (A) is 1.0 to 30 mass%.

However, the repeating unit having an Si atom described above has a structure in which the polar groups are protected with a leaving group capable of decomposing and leaving by the action of an acid, and, when the leaving group have a Si atom, the resin the amount of Si atom in the leaving group on the content of Si atoms in (a) is not included. That is, even if Si atom in the leaving group, the amount of the Si atoms are not included in the content of Si atoms in the resin (A).

For example, although the repeating units from the left third of the comparative resin 2 given later has an Si atom derived from the TMS (trimethylsilyl group), the repeating unit is below a leaving group (*: bonding position) with polar groups (- because having a COOH) is protected structure, the amount of Si atom derived from the TMS in the leaving group is not included in the content of Si atoms in the resin (a).

The content of Si atoms in the resin (A) is preferably 3 to 25 mass%, and particularly preferably from 5 to 20 mass%.

Figure JPOXMLDOC01-appb-C000030

The weight average molecular weight of the resin (A) is preferably from 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably from 3,000 to 15,000, particularly preferably 3, is 000 to 11,000. The weight average molecular weight is from 1,000 to 200,000, it is possible to prevent deterioration of heat resistance, dry etching resistance and or developability is deteriorated, that film-forming property higher viscosity deteriorates it is possible to prevent that.

Polydispersity (molecular weight distribution) is usually 1.0-3.0, preferably 1.0 to 2.6 and more preferably 1.0-2.0, particularly preferably 1.1-2.0 the range is used. The lower the molecular weight distribution, excellent resolution, resist profile, side wall of the resist pattern is smoother, and the roughness property.

In this specification, the weight average molecular weight is a standard polystyrene equivalent value determined from the following conditions by gel permeation chromatography (GPC). Column type: TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm, developing solvent: THF (tetrahydrofuran) Column temperature: 40 ° C., flow rate: 1 ml / min, sample injection amount: 10μl · device name: HLC-8120 (Tosoh Co., Ltd.)
The content of the resin (A) in the total solid content of the composition of the present invention is 20 mass% or more. Among them, preferably 40 mass% or more, more preferably is 60 mass% or more, more preferably 80 mass% or more. The upper limit is not particularly limited, preferably 90 mass% or less.

In the present invention, the resin (A) may be used singly, or in combination.

[2] an actinic ray or compounds actinic ray-sensitive or radiation-sensitive resin composition generates an acid by irradiation of radiation, a compound capable of generating an acid upon irradiation with actinic rays or radiation (hereinafter, also referred to as "acid generator" ) containing. The acid generator is not particularly limited, it is preferably exposed to actinic rays or radiation is a compound capable of generating an organic acid.

As the acid generator, a photoinitiator for photo cationic polymerization, a photoinitiator for photoradical polymerization, photo-decoloring agents of dyes, are used in photochromic agent, microresists or the like, irradiation with an actinic ray or radiation known compounds generating an acid and selected mixtures thereof suitably can be used by, for example, compounds described in JP 2010-61043 JP paragraphs [0039] - [0103], JP Although like compounds described in the open 2013-4820 JP paragraphs [0284] - [0389], the present invention is not limited thereto.

For example, mention may be made of diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, the o- nitrobenzyl sulfonate.

As the acid generator actinic ray-sensitive or radiation-sensitive resin composition contains, for example, the following general formula (3) generating an acid upon irradiation with actinic rays or radiation is represented by a compound (specific acid generator) it can be mentioned favorably.

Figure JPOXMLDOC01-appb-C000031

(Anion)
In the general formula (3),
Xf each independently represents a fluorine atom, or an alkyl group substituted with at least one fluorine atom.

R 4 and R 5 are each independently a hydrogen atom, a fluorine atom, an alkyl group, or, R 4, R 5 when representing at least one alkyl group substituted with a fluorine atom, there exist a plurality of respectively identical But it may be different.

L represents a divalent linking group, L when existing in plural numbers may be the same or different.

W represents an organic group containing a cyclic structure.

o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1-4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Xf is preferably a fluorine atom or CF 3. In particular, it is preferred that both Xf is a fluorine atom.

R 4 and R 5 are each independently a hydrogen atom, a fluorine atom, an alkyl group, or, R 4, R 5 when representing at least one alkyl group substituted with a fluorine atom, there exist a plurality of respectively identical But it may be different.

The alkyl group as R 4 and R 5 may have a substituent, preferably from 1 to 4 carbon atoms. R 4 and R 5 are preferably hydrogen atoms.

Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as specific examples and preferred embodiments of the Xf of the general formula (3).

L represents a divalent linking group, L when existing in plural numbers may be the same or different.

Examples of the divalent linking group, e.g., -COO - (- C (= O) -O -), - OCO -, - CONH -, - NHCO -, - CO -, - O -, - S -, - SO -, - SO 2 -, an alkylene group (preferably having a carbon number of 1 to 6), a cycloalkylene group (preferably having from 3 to 10 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), or a combination of these multiple such divalent linking group of the like. Among them, -COO -, - OCO -, - CONH -, - NHCO -, - CO -, - O -, - SO 2 -, - COO- alkylene group -, - OCO- alkylene group -, - CONH- alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.

W represents an organic group containing a cyclic structure. It is preferably Among them cyclic organic group.

The cyclic organic group, for example, alicyclic, aryl groups, and heterocyclic groups.

Alicyclic group may be monocyclic or may be a polycyclic. The alicyclic group monocyclic, for example, a cyclopentyl group, and a monocyclic cycloalkyl group such as cyclohexyl group, and cyclooctyl group. The polycyclic alicyclic group, e.g., norbornyl group, tricyclodecanyl group, tetra tricyclodecanyl group, a polycyclic cycloalkyl group such as tetracyclododecanyl group and adamantyl group. Among them, a norbornyl group, tricyclodecanyl group, tetra tricyclodecanyl group, tetracyclododecanyl group, and an alicyclic group having a bulky structure having 7 or more carbon atoms such as adamantyl group, PEB (post-exposure heating) step from the viewpoint of improving the film diffusion in suppression and MEEF (Mask Error Enhancement Factor).

Aryl groups may be monocyclic or may be a polycyclic. As the aryl group include a phenyl group, a naphthyl group, a phenanthryl group and an anthryl group. Among them, the absorbance at 193nm is relatively low naphthyl group are preferred.

Heterocyclic group may be monocyclic or may be a polycyclic, but towards the polycyclic is possible suppress the diffusion of more acid. Further, the heterocyclic group may have aromaticity or may not have aromatic character. The heterocyclic ring having aromaticity, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, a dibenzofuran ring, and a pyridine ring and the like. Examples of the heterocyclic ring not having aromaticity include a tetrahydropyran ring, a lactone ring include sultone ring and decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group, furan ring, thiophene ring, pyridine ring, or a decahydroisoquinoline ring is particularly preferred. In addition, examples of the lactone ring and the sultone ring include exemplified lactone structure and sultone structure in the aforementioned resin.

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (straight-chain, may be either branched, preferably having 1 to 12 carbon atoms), a cycloalkyl group (monocyclic, polycyclic, be either a spirocyclic well, preferably 3 to 20 carbon atoms), an aryl group (having 6 to 14 carbon atoms is preferred), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamido group, and sulfonic acid include ester groups. Incidentally, (carbon contributing to ring formation) carbon constituting the cyclic organic group may be a carbonyl carbon.

o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

In one embodiment, o in formula (3) is an integer from 1 to 3, p is an integer from 1 to 10, and preferably q is 0. Xf is preferably a fluorine is atomic, preferably R 4 and R 5 are both hydrogen atoms, W is preferably a polycyclic hydrocarbon group. o is more preferably 1 or 2, more preferably 1. More preferably p is an integer of 1 to 3, more preferably 1 or 2, 1 is particularly preferred. W is more preferably a polycyclic cycloalkyl group, more preferably an adamantyl group or a diamantyl group. (Cation)
In the general formula (3), X + represents a cation.

X + is not particularly limited as long as cation, suitable embodiments include the corresponding general formula (ZI), (ZII) or (ZIII) in cation - include (Z portions other than). (A preferred embodiment)
As a preferred embodiment of a specific acid generator, for example, the following formulas (ZI), include compounds represented by (ZII) or (ZIII).

Figure JPOXMLDOC01-appb-C000032

In formula (ZI),
R 201, R 202 and R 203 independently represents an organic group.

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

It is also possible to form the two members ring structure of R 201 ~ R 203, an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R 201 ~ R 203, there can be mentioned an alkylene group (e.g., butylene, pentylene).

And Z - represents an anion of the general formula (3), specifically, an anion of the following.

Figure JPOXMLDOC01-appb-C000033

The organic group represented by R 201, R 202 and R 203, for example, corresponding groups in the compounds (ZI-1), (ZI -2), the corresponding groups in (ZI-3) and (ZI-4) it can be mentioned.

The structure may be a compound having a plurality represented by formula (ZI). For example, the general formula at least one of R 201 ~ R 203 of a compound represented by (ZI), at least one of R 201 ~ R 203 of another compound represented by formula (ZI), a single bond or structure bonded through a linking group may be a compound having a.

Further preferred (ZI) components, there can be mentioned the following compounds (ZI-1), it can be exemplified (ZI-2), or (ZI-3) described and (ZI-4).

First, a description for compound (ZI-1).

The compound (ZI-1) is at least one of aryl group R 201 ~ R 203 of formula (ZI), arylsulfonium compounds, namely, compounds containing an arylsulfonium as a cation.

Arylsulfonium compound, all of R 201 ~ R 203 may be an aryl group or a part of R 201 ~ R 203 is an aryl group and the remainder may be an alkyl group or a cycloalkyl group.

As the arylsulfonium compounds, e.g., a triarylsulfonium compound, a diaryl alkyl sulfonium compounds, diarylcycloalkylsulfonium compounds, diarylalkylsulfonium compounds, can be an aryldicycloalkylsulfonium compound.

As the aryl group include phenyl group in the arylsulfonium compound, a naphthyl group are preferred, more preferably a phenyl group. The aryl group, an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and the like. In the case where the arylsulfonium compound has two or more aryl groups, these two or more aryl groups may be be the same or different.

Alkyl group or a cycloalkyl group that the arylsulfonium compound has according to necessity is preferably a straight-chain or branched alkyl group or cycloalkyl group having a carbon number of 3 to 15 1 to 15 carbon atoms, such as methyl group, ethyl, propyl, n- butyl group, sec- butyl group, t- butyl group, a cyclopropyl group, a cyclobutyl group and a cyclohexyl group.

Aryl group R 201 ~ R 203, an alkyl group, cycloalkyl group, (1-15 e.g. carbon atoms) alkyl group, a cycloalkyl group (e.g. having 3 to 15 carbon atoms), an aryl group (e.g., having from 6 to 14 carbon atoms) , (1-15 e.g. carbon atoms) alkoxy group, a halogen atom, a hydroxyl group or a phenylthio group.

Next, a description for compound (ZI-2).

The compound (ZI-2) is, R 201 ~ R 203 in formula (ZI) wherein each independently represents an organic group having no aromatic ring. The aromatic ring here, but also includes an aromatic ring containing a hetero atom.

The organic group having no aromatic ring as R 201 - R 203 is generally from 1 to 30 carbon atoms, preferably from 1 to 20 carbon atoms.

R 201 ~ R 203 each independently, preferably an alkyl group, a cycloalkyl group, an allyl group, a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxy carbonyl methyl group, particularly preferably a straight-chain or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R 201 ~ R 203, preferably a linear or branched alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group) having 1 to 10 carbon atoms, carbon and a cycloalkyl group having 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl).

R 201 ~ R 203 is a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, a description for compound (ZI-3).

Compound (ZI-3) is a compound represented by the following formula (ZI-3), a compound having a phenacyl sulfonium salt structure.

Figure JPOXMLDOC01-appb-C000034

In the general formula (ZI-3),
R 1c ~ R 5c are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyl group, cycloalkylcarbonyl group, a halogen atom, a hydroxyl group represents a nitro group, an alkylthio group or an arylthio group.

R 6c and R 7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

R x and R y independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Any two or more of R 1c ~ R 5c, R 5c and R 6c, R 6c and R 7c, R 5c and R x, and R x and R y may form a respective coupling ring structure well, the ring structure may contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.

As the ring structure, an aromatic or non-aromatic hydrocarbon ring, aromatic or non-aromatic heterocyclic ring, or, and a polycyclic condensed ring of these rings formed by combining two or more. The ring structure includes a 3- to 10-membered ring, preferably 4 to 8-membered ring, and more preferably 5 or 6-membered ring.

R 1c ~ any two or more of R 5c, R 6c and R 7c, and as the group R x and R y are formed by combined include a butylene group and a pentylene group.

R 5c and R 6c and, as the group R 5c and R x are formed by bonding is preferably a single bond or an alkylene group, the alkylene group include a methylene group, an ethylene group, etc. .

Zc - represents an anion of the general formula (3), specifically, as described above.

Specific examples of the alkoxy group in the alkoxycarbonyl group as R 1c ~ R 5c are the same as specific examples of the alkoxy group as the R 1c ~ R 5c.

Specific examples of the alkyl group in the alkylcarbonyloxy group and alkylthio group as R 1c ~ R 5c are the same as specific examples of the alkyl group of the R 1c ~ R 5c.

Specific examples of the cycloalkyl group in the cycloalkyl carbonyl group as R 1c ~ R 5c are the same as specific examples of the cycloalkyl group of the R 1c ~ R 5c.

Specific examples of the aryl group in the aryloxy group and arylthio group as R 1c ~ R 5c are the same as specific examples of the aryl group of the R 1c ~ R 5c.

As the cation in the compound of the present invention (ZI-2) or (ZI-3) can be mentioned cations described in U.S. Patent Application Publication No. 2012/0076996 Pat paragraphs [0036] and later.

Next, a description for compound (ZI-4).

Compound (ZI-4) is represented by the following formula (ZI-4).

Figure JPOXMLDOC01-appb-C000035

In the general formula (ZI-4),
R 13 represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group. These groups may have a substituent.

R 14, when there are a plurality of independently each a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a group having a cycloalkyl sulfonyl group, or a cycloalkyl group a representative. These groups may have a substituent.

R 15 independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R 15 may combine with each other to form a ring. When two R 15 are combined to form a ring together, in the ring skeleton, an oxygen atom, it may contain a hetero atom such as nitrogen atom. In one embodiment, two R 15 is an alkylene group, it is preferable to form a ring structure.

l represents an integer of 0 to 2.

r represents an integer of 0 to 8.

And Z - represents an anion of the general formula (3), specifically, as described above.

In formula (ZI-4), the alkyl group of R 13, R 14 and R 15, may be linear or branched, preferably having 1 to 10 carbon atoms, a methyl group, an ethyl radical, n - butyl group, a t- butyl group and the like are preferable.

The cation of the compound represented by formula (ZI-4) in the present invention, JP 2010-256842 JP paragraph [0121], [0123], [0124], and, JP 2011-76056 paragraph [0127], [0129] may be the cation of [0130] the like.

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

In formula (ZII), (ZIII), R 204 ~ R 207 each independently represents an aryl group, an alkyl group or a cycloalkyl group.

Phenyl group and a naphthyl group are preferred as the aryl group of R 204 ~ R 207, more preferably a phenyl group. Aryl group R 204 ~ R 207 represents an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. As the skeleton of the aryl group having a heterocyclic structure include, for example, pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like.

The alkyl group and cycloalkyl group in R 204 ~ R 207, preferably a linear or branched alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group) having 1 to 10 carbon atoms, carbon and a cycloalkyl group having 3 to 10 (e.g., cyclopentyl, cyclohexyl, norbornyl).

Aryl group R 204 ~ R 207, an alkyl group, a cycloalkyl group may have a substituent. Aryl group R 204 ~ R 207, examples of the alkyl group, substituent that the cycloalkyl group have, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (e.g., carbon atoms 3 to 15 ), an aryl group (e.g. having 6 to 15 carbon atoms), 1 to 15 alkoxy groups (e.g., carbon atoms), a halogen atom, a hydroxyl group and a phenylthio group.

And Z - represents an anion of the general formula (3), specifically, as described above.

Acid generator (including the specific acid generator. Forth.) May be in the form of a low-molecular compound, may be in a form that is an integral part of the polymer. It may be used in combination form an integral part of the polymer in the form of low-molecular compounds.

Acid generating agent, be in the form of a low-molecular compound, it is preferred that the molecular weight is 580 or more, more preferably 600 or more, more preferably 620 or more, and particularly preferably 640 or more . The upper limit is not particularly limited but is preferably 3000 or less, more preferably 2000 or less, more preferably 1000 or less.

Acid generating agent, is part incorporated in form of a polymer, may be incorporated into a part of the resin as described above, it may be incorporated in a different resin from the resin.

The acid generator can be synthesized by a known method, for example, it can be synthesized according to the method described in JP-A-2007-161707.

Acid generators may be used in combination one kind alone, or two or more kinds.

The content of the acid generator in the composition is (the sum if present more species), based on the total solids of the composition, preferably from 0.1 to 30 mass%, more preferably from 0.5 to 25 mass%, more preferably 3 to 20 mass%, particularly preferably 3 to 15 mass%.

As an acid generator, the content of the acid generator case, contained in a composition comprising a compound represented by the above general formula (ZI-3) or (ZI-4) (the sum if the present s) based on the total solids of the composition, preferably 5 to 35 mass%, more preferably 8 to 30 mass%, more preferably 9-30 wt%, particularly preferably 9-25 wt%.

[3] The hydrophobic resin actinic ray-sensitive or radiation-sensitive resin composition, the hydrophobic resin (hereinafter, also referred to as "hydrophobic resin (D)" or simply "resin (D)") may contain . Incidentally, the hydrophobic resin (D) is preferably different from the resin (A).

Hydrophobic resin (D), which is preferably designed as unevenly distributed to the interface, unlike a surfactant, need not have a hydrophilic group necessarily the molecule, uniform mixing of polar / nonpolar substances it may not contribute to.

The effect of adding a hydrophobic resin, control of the static / dynamic contact angle of the resist film surface for water, improved followability of immersion liquid, such as outgassing suppression can be mentioned.

Hydrophobic resin (D), from the viewpoint of uneven distribution in the film surface layer, "fluorine atom", "silicon atom", and, any one of "CH 3 partial structure contained in the side chain portion of the resin" preferably has a higher, more preferably has two or more.

Hydrophobic resin (D), when containing a fluorine atom and / or silicon atoms, the hydrophobic resin (D) in the in the fluorine atom and / or silicon atom may be contained in the main chain of the resin , it may be included in the side chain.

When the hydrophobic resin (D) contains a fluorine atom, a partial structure having a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or, a resin having an aryl group having a fluorine atom there it is preferable.

Alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more number of 1 to 4 carbon atoms preferably) is a straight-chain or branched alkyl group having at least one hydrogen atom is substituted with a fluorine atom, a fluorine atom it may have other substituents.

Aryl group having a cycloalkyl group and fluorine atom having a fluorine atom, respectively, an aryl group having one cycloalkyl group and fluorine atom which a hydrogen atom has been substituted with a fluorine atom, a substituent other than a fluorine atom it may have.

Alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, and aryl groups containing a fluorine atom, preferably, there can be mentioned groups represented by the following formula (F2) ~ (F4), the invention is not limited thereto.

Figure JPOXMLDOC01-appb-C000036

In formula (F2) ~ (F4),
R 57 ~ R 68 each independently represent a hydrogen atom, a fluorine atom or an alkyl group (linear or branched). Provided that at least one of R 57 ~ R 61, at least one of R 62 ~ R 64, and at least one of R 65 ~ R 68 are each independently, a fluorine atom or at least one hydrogen atom is a fluorine atom substituted alkyl group (preferably having from 1 to 4 carbon atoms).

R 57 ~ R 61 and R 65 ~ R 67, it is preferred that all are a fluorine atom. R 62, R 63 and R 68 are, be at least one hydrogen atom (preferably having 1 to 4 carbon atoms) alkyl group substituted with a fluorine atom is a perfluoroalkyl group preferably having 1 to 4 carbon atoms A further preferred. R 62 and R 63 may be bonded to each other to form a ring.

Hydrophobic resin (D) may contain a silicon atom. As a partial structure having a silicon atom is preferably an alkylsilyl structure (preferably a trialkylsilyl group) is a resin having a cyclic siloxane structure.

Examples of the repeating unit having a fluorine atom or a silicon atom, may be mentioned those exemplified in US2012 / 0251948A1 [0519].

Further, as described above, the hydrophobic resin (D), it is also preferred to include CH 3 partial structure side chain moiety.

Here, CH 3 partial structure contained in the side chain moiety in the hydrophobic resin (D) (hereinafter, simply referred to as "side chain CH 3 partial structure") The, CH 3 partial structure an ethyl group, and a propyl group having it is intended to embrace.

On the other hand, the surface of the methyl groups directly bonded to the main chain of the hydrophobic resin (D) (e.g., a repeating unit having a methacrylic acid structure α- methyl groups), hydrophobic resin under the influence of the backbone (D) for contribution to uneven distribution is small, and shall not be included in the CH 3 partial structures in the present invention.

Repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond - More specifically, the hydrophobic resin (D) is, for example, of a repeating unit represented by the following general formula (M), carbon a case including, if R 11 ~ R 14 is CH 3 "itself", the CH 3 is not included in the CH 3 partial structure contained in the side chain portion in the present invention.

Meanwhile, CH 3 partial structure exists through some atoms from C-C backbone, and those falling under CH 3 partial structures in the present invention. For example, if R 11 is an ethyl group (CH 2 CH 3), a CH 3 partial structure in the present invention shall have "one".

Figure JPOXMLDOC01-appb-C000037

In the general formula (M),
R 11 ~ R 14 each independently represents a side chain moiety.

The R 11 ~ R 14 of side chain moiety, a hydrogen atom, and the like monovalent organic group.

The monovalent organic groups for R 11 ~ R 14, an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkyl aminocarbonyl group, arylaminocarbonyl group, and these groups may further have a substituent.

Hydrophobic resin (D) is preferably a resin having a repeating unit having a CH 3 partial structure side chain moiety, as such repeating units, the repeating unit represented by the following general formula (II), and , and more preferably has at least one repeating unit (x) of the repeating unit represented by the following general formula (III).

It will now be described in detail repeating unit represented by the general formula (II).

Figure JPOXMLDOC01-appb-C000038

In the general formula (II), X b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R 2 has one or more CH 3 partial structure represents a stable organic radical to acid. Here, stable organic groups relative to the acid, and more specifically, is preferably an organic group having no "acid-decomposable group" described in the resin P.

Alkyl group X b1 is preferably those having 1 to 4 carbon atoms, a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group and the like, preferably a methyl group.

X b1 is preferably a hydrogen atom or a methyl group.

The R 2, has one or more CH 3 moiety, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and, aralkyl groups. The above cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and aralkyl group may further have an alkyl group as a substituent.

R 2 has one or more CH 3 moiety, the alkyl group or alkyl-substituted cycloalkyl groups are preferred.

Acid stable organic group having one or more CH 3 partial structure as R 2 preferably has a CH 3 partial structure more than 10 or less, and more preferably has 8 or less 2 or more.

Specific preferred examples of the repeating unit represented by formula (II) given below. The present invention is not limited thereto.

Figure JPOXMLDOC01-appb-C000039

The repeating unit represented by formula (II), is preferably a stable (non-acid-decomposable) repeating units acid, specifically, is decomposed by the action of an acid, groups that produce a polar group it is preferably a repeating unit having no.

Will now be described in detail repeating unit represented by formula (III).

Figure JPOXMLDOC01-appb-C000040

In the general formula (III), X b2 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R 3 has one or more CH 3 partial structure represents a stable organic radical to acid, n represents an integer from 1 to 5.

Alkyl group X b2 is preferably those having 1 to 4 carbon atoms, a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group and the like, it is preferred that a hydrogen atom.

X b2 is preferably a hydrogen atom.

R 3 are the stable organic radical to acid, and more specifically, is preferably an organic group having no "acid-decomposable group" described in the resin P.

The R 3, with one or more CH 3 moiety include alkyl groups.

Acid stable organic group having one or more CH 3 partial structure as R 3 preferably has a CH 3 partial structure 1 or more 10 or less, more preferably has 1 or more 8 or less, more preferably has 1 or more 4 or less.

n represents an integer from 1 to 5, more preferably represents an integer of 1 to 3, and more preferably represents 1 or 2.

Specific preferred examples of the repeating unit represented by formula (III) listed below. The present invention is not limited thereto.

Figure JPOXMLDOC01-appb-C000041

The repeating unit represented by formula (III), is preferably a stable (non-acid-decomposable) repeating units acid, specifically, is decomposed by the action of an acid, groups that produce a polar group it is preferably a repeating unit having no.

Hydrophobic resin (D) is a case where the side chain portion comprises a CH 3 partial structure, further, especially if no fluorine atom and a silicon atom, the repeating unit represented by the general formula (II) and, content of at least one repeating unit out of the repeating unit represented by formula (III) (x) is preferably based on all repeating units in the hydrophobic resin (D), at least 90 mol%, and more preferably 95 mol% or more. Content, based on all repeating units in the hydrophobic resin (D), typically at 100 mol% or less.

Hydrophobic resin (D), the repeating unit represented by the general formula (II), and the general formula at least one repeating unit out of the repeating unit represented by (III) (x), the hydrophobic resin (D on all repeating units), by containing 90 mol% or more, the surface free energy of the hydrophobic resin (D) is increased. As a result, the hydrophobic resin (D) is unlikely to localized on the surface of the resist film, the static / dynamic contact angle of the resist film for water firmly increased, to improve the followability of immersion liquid it can.

Further, the hydrophobic resin (D), (i) in the case of containing a fluorine atom and / or silicon atom, even when containing a CH 3 partial structure (ii) side chain moiety, the following (x) ~ (z a group selected from the group consisting of) may have at least one.

(X) group,
(Y) a group having a lactone structure, an acid anhydride group, or an acid imide group,
The group decomposable group (x) by the action of (z) an acid, a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl ) methylene group, an (alkylsulfonyl) (alkylcarbonyl) imide group, a bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, a bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imido group, a tris (alkyl carbonyl) methylene group, a tris (alkylsulfonyl) methylene group.

Preferred acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, bis (alkylcarbonyl) methylene group.

The repeating unit having an acid group (x), acrylic acid, in the main chain of the resin, such as repeating unit by methacrylic acid, directly repeating unit group is bonded, or the resin through a linking group a repeating unit that groups in its main chain bonds are exemplified, and further can also be introduced into the polymer chain terminal by using a polymerization initiator or chain transfer agent having an acid group at the time of polymerization, in either case preferable. Repeating unit having an acid group (x) may have at least either a fluorine atom or a silicon atom.

The content of the repeating unit having an acid group (x) based on all the repeating units in the hydrophobic resin (D), is preferably 1 to 50 mol%, more preferably from 3 to 35 mol%, more preferably 5 to is 20 mol%.

Specific examples of the repeating unit having an acid group (x) below, the present invention is not limited thereto. In the formulas, Rx represents a hydrogen atom, CH 3, CF 3, or represents a CH 2 OH.

Figure JPOXMLDOC01-appb-C000042

Figure JPOXMLDOC01-appb-C000043

Examples of the group having a lactone structure, an acid anhydride group, or an acid imide group (y), a group having a lactone structure is particularly preferable.

Repeating units containing these groups is, for example, a repeating unit such as repeating unit by an acrylic acid ester and methacrylic acid esters, this group directly to the main chain of the resin bonded. This repeating unit may be a repeating unit where the group is bonded to the main chain of the resin through a linking group. This repeating unit a polymerization initiator or chain transfer agent containing the group using the time of polymerization, or may be introduced into the terminal of the resin.

The repeating unit having a group having a lactone structure, for example, those similar to the repeating unit having a lactone structure described above in the paragraph of the above resin (A).

The content of the repeating unit having a group having a lactone structure, an acid anhydride group or an acid imide group, is based on the total repeating units in the hydrophobic resin (D), is preferably 1 to 100 mol%, more preferably 3 to 98 mol%, more preferably 5 to 95 mol%.

In the hydrophobic resin (D), the repeating unit having (z) a group capable of decomposing by the action of an acid, are the same as those of the repeating unit having an acid-decomposable group described for the resin (A). The repeating unit having a group decomposable by the action of an acid (z) may have at least either a fluorine atom or a silicon atom. The content of the repeating unit having (z) a group capable of decomposing by the action at, the acid in the hydrophobic resin (D), based on all the repeating units in the resin (D), is preferably from 1 to 80 mol%, more preferably 10 to 80 mol%, more preferably 20 to 60 mol%.

Hydrophobic resin (D) may further have other repeating units than the repeating units described above.

Repeating unit containing a fluorine atom, all the repeating units of 10 to 100 mol% is preferably contained in the hydrophobic resin (D), more preferably 30 to 100 mol%. Also, the silicon atom-containing repeating unit, based on all repeating units contained in the hydrophobic resin (D), preferably 10 to 100 mol%, more preferably 20 to 100 mol%.

On the other hand, especially if the hydrophobic resin (D) comprises a CH 3 partial structure side chain moiety, a hydrophobic resin (D) is a form that does not contain a fluorine atom and a silicon atom substantially also preferred. Further, the hydrophobic resin (D) is a carbon atom, an oxygen atom, a hydrogen atom, only a repeating unit consisting only of atoms selected from a nitrogen atom and a sulfur atom preferably be configured substantially.

The standard polystyrene-reduced weight average molecular of the hydrophobic resin (D) is preferably from 1,000 to 100,000, more preferably 1,000 to 50,000.

Further, the hydrophobic resin (D) may be used singly, or in combination.

The content in the composition of the hydrophobic resin (D), based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition, preferably from 0.01 to 10 wt%, 0.05-8 wt % is more preferable.

Hydrophobic resin (D) is preferably residual monomers or oligomer components is from 0.01 to 5 mass%, more preferably 0.01 to 3 mass%. The molecular weight distribution (Mw / Mn, also called dispersity index) is in the range of 1 to 5 by weight, more preferably in the range of 1-3.

Hydrophobic resin (D) can either be used various commercially available products, it can be synthesized (for example, radical polymerization) in a conventional manner.

[4] Acid diffusion controller actinic ray-sensitive or radiation-sensitive resin composition preferably contains an acid diffusion controller. Acid diffusion control agent is to trap the acid generated from the exposure acid generator or the like, due to the extra acid generated is one that acts reaction of the acid-decomposable resin in the unexposed area as suppressing quencher. As the acid diffusion controller, a basic compound, a nitrogen atom, a low molecular compound having a group capable of leaving by the action of an acid, a basic compound basicity upon irradiation with an actinic ray or radiation is reduced or eliminated, or it can be used onium salts to be relatively weak with respect to acid generator.

The basic compound can preferably be a compound having a structure represented by the following formula (A) ~ (E).

Figure JPOXMLDOC01-appb-C000044

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

R 203, R 204, R 205 and R 206, which may be the same or different, each represents a number of 1 to 20 alkyl group carbon.

As for the alkyl group, the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms preferred.

The alkyl group in these formulas (A) and (E) is more preferably unsubstituted.

Preferred examples of the compound include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, can be mentioned piperidine, further preferred compounds, imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, a compound having an aniline structure or a pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, and a hydroxyl group and / or an aniline derivative having an ether bond.

Specific examples of preferred compounds, mention may be made of compounds illustrated in US2012 / 0219913A1 [0379].

As preferred basic compounds, an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, and an ammonium salt compound having an amine compound and a sulfonic ester group having a sulfonic acid ester group.

These basic compounds may be used one kind alone or may be used in combination of two or more.

The actinic ray-sensitive or radiation-sensitive resin composition, a basic compound may or may not contain but, if contained, the content of the basic compound, based on the solid content of the composition, usually, 0.001 to 10 wt%, preferably from 0.01 to 5 mass%.

The ratio of the acid generator in the composition and the basic compound, acid generator / basic compound (molar ratio) 2.5 to 300, more preferably from 5.0 to 200, still more preferably 7. it is 0 to 150.

A nitrogen atom, a low molecular compound having a group capable of leaving by the action of an acid (hereinafter, also referred to as "compound (C)".), The amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom it is preferable that.

As groups capable of leaving by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, hemiaminal ether group are preferred, carbamate groups, and particularly preferably a hemiaminal ether group .

The molecular weight of the compound (C) is preferably from 100 to 1000, more preferably 100 to 700, particularly preferably 100-500.

Compound (C) may have a carbamate group having a protective group on the nitrogen atom. The protective group constituting the carbamate group can be represented by the following general formula (d-1).

Figure JPOXMLDOC01-appb-C000045

In formula (d-1),
Rb is each independently a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group ( preferably represents 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). Rb may form a ring with each other.

Rb is an alkyl group shown, cycloalkyl group, aryl group, aralkyl group, a hydroxyl group, a cyano group, an amino group, pyrrolidino group, piperidino group, morpholino group and oxo group, alkoxy group, substituted with a halogen atom it may be. Rb is the same to the alkoxyalkyl group represented by.

As Preferably Rb, linear or branched alkyl group, a cycloalkyl group, an aryl group. More preferably, linear or branched alkyl group, a cycloalkyl group.

As the ring two Rb is formed by interconnected, alicyclic hydrocarbon group, aromatic hydrocarbon group, heterocyclic hydrocarbon group, or a derivative thereof.

As specific structures of the group represented by the general formula (d-1), there may be mentioned the structure disclosed in US2012 / 0135348 A1 [0466], but is not limited thereto.

Compound (C) is particularly preferably has a structure represented by the following general formula (6).

Figure JPOXMLDOC01-appb-C000046

In the general formula (6), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, two Ra's may be the same or different, two Ra may form a heterocyclic ring together with the nitrogen atom in the formula interconnected. The heterocyclic ring may contain a hetero atom other than nitrogen atom in the formula.

Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same.

l represents an integer of 0 ~ 2, m represents an integer of 1 to 3, satisfying the l + m = 3.

In the general formula (6), the alkyl group as Ra, cycloalkyl group, aryl group, aralkyl group, the above-described alkyl group, a cycloalkyl group, an aryl group, group which may be aralkyl groups substituted as Rb it may be substituted with the same groups as groups.

Alkyl group of the above Ra, cycloalkyl group, aryl group and aralkyl group, (these alkyl groups, cycloalkyl group, aryl group and aralkyl group, is the group may be substituted with) Specific examples of, It includes the same groups as specific examples described above for rb.

Specific examples of particularly preferred compounds (C) in the present invention, US2012 / 0135348 A1 there may be mentioned the compounds disclosed in [0475], but is not limited thereto.

Compound represented by the general formula (6) can be synthesized based JP 2007-298569 and JP etc. JP 2009-199021.

In the present invention, low-molecular compound having a group capable of leaving by the action of an acid on the nitrogen atom (C), even if either individually or in combination of two or more can be used.

The content of the compound in the actinic ray-sensitive or radiation-sensitive resin composition (C), based on the total solids of the composition, preferably from 0.001 to 20 mass%, more preferably 0.001 to 10% by weight, more preferably 0.01 to 5 mass%.

An actinic ray or radiation basic compounds basicity decreases or disappears upon irradiation (hereinafter, also referred to as "compound (PA)".) Has a proton acceptor functional group, and, exposed to actinic rays or radiation is decomposed by, proton acceptor is reduced, lost, or a compound which changes to acidic proton acceptor.

The proton acceptor functional group, a functional group having a group or electron capable of electrostatically interacting with a proton and, for example, a functional group having a macro-cyclic structure such as cyclic polyether, a π-conjugated It means a functional group having a nitrogen atom having an unshared electron pair not contributing. The nitrogen atom having an unshared electron pair not contributing to π-conjugated, for example, a nitrogen atom having a partial structure represented by the following formula.

Figure JPOXMLDOC01-appb-C000047

Preferred examples of the partial structure of the proton acceptor functional group may be, for example, crown ethers, aza-crown ethers, primary to tertiary amines, pyridine, imidazole, etc. pyrazine structure.

Compound (PA) is proton acceptor decomposing upon irradiation with an actinic ray or radiation is decreased, loss, or to generate a compound changed to acidic proton acceptor. Here reduction of the proton acceptor, loss, or a change to an acidic proton acceptor, a proton acceptor of change due to the addition proton to proton acceptor functional group, specifically the, when the proton adduct is produced a compound having a proton acceptor functional group and (PA) from the proton, which means a reduction in at equilibrium constant on the chemical equilibrium.

Proton acceptor can be confirmed by measuring the pH.

In the present invention, the acid dissociation constant pKa of an actinic ray or compound by irradiation (PA) compounds occur in decomposition is, it is preferable to satisfy the pKa <-1, more preferably -13 <pKa <-1 , and still more preferably from -13 <pKa <-3.

In the present invention, the acid dissociation constant pKa, indicates that the acid dissociation constant pKa in an aqueous solution, for example, Chemical Handbook (II) (revised 4th edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.) to are those described, indicate that higher acid strength the value is low is large. Acid dissociation constant pKa in aqueous solution, specifically, using the infinite dilution aqueous solution, can be measured by measuring the acid dissociation constant at 25 ° C., also using the following software packages 1, Hammett of a value based on a database substituent constant and known literature values, it can also be obtained by calculation. The value of pKa as described herein, shows all the values ​​obtained by calculation using the software package.

Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

Compound (PA) as the proton adduct generated by decomposition upon irradiation with an actinic ray or radiation, for example, to generate a compound represented by the following general formula (PA-1). The compound represented by formula (PA-1), by having an acidic group with a proton acceptor functional group, decreases proton acceptor as compared with compound (PA), disappearance, or the proton acceptor is a compound that changes to acidic.

Figure JPOXMLDOC01-appb-C000048

In the general formula (PA-1),
Q represents -SO 3 H, -CO 2 H, or -W 1 NHW 2 R f. Here, R f is an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), W 1 and W 2, each independently, -SO 2 - represents a or -CO-.

A represents a single bond or a divalent linking group.

X is, -SO 2 - represents a or -CO-.

n represents 0 or 1.

B represents a single bond, an oxygen atom, or -N (R x) R y - represents a. Here, R x represents a hydrogen atom or a monovalent organic group, R y represents a single bond or a divalent organic group. R x is may form a ring with R y, may form a ring with R.

R represents a monovalent organic group having a proton acceptor functional group.

Compound (PA) is preferably an ionic compound. The proton acceptor functional group an anion portion may is also be included in any of the cation, it is preferably contained in the anionic sites.

In the present invention, the general formula (PA-1) generating a compound represented by a compound other than the compound (PA) is also appropriately selected. For example, an ionic compound may be a compound having a proton acceptor site in the cation moiety. More specifically include compounds represented by the following general formula (7).

Figure JPOXMLDOC01-appb-C000049

In the formula, A represents a sulfur atom or an iodine atom.

m represents 1 or 2, n represents 1 or 2. Provided that when A is a sulfur atom, m + n = 3, A is when iodine atom, a m + n = 2.

R represents an aryl group.

R N represents an aryl group substituted with a proton acceptor functional group. X - represents a counter anion.

X - it includes specific examples of can be the same as the anion of the acid generator described above.

Specific examples of the aryl group of R and R N is a phenyl group are preferably exemplified.

Specific examples of the proton acceptor functional group R N are the same as those of the proton acceptor functional group described in the foregoing formula (PA-1).

Hereinafter, specific examples of the ionic compound having a proton acceptor site in the cation moiety, may be mentioned compounds exemplified in US2011 / 0269072A1 [0291].

Such a compound can be synthesized, for example, by the method described in Reference like in JP 2009-122623 and JP 2007-230913 JP.

Compound (PA) may be used one kind alone or may be used in combination of two or more.

The content of compound (PA), based on the total solids of the composition, preferably from 0.1 to 10 mass%, more preferably 1-8 wt%.

The actinic ray-sensitive or radiation-sensitive resin composition can be used onium salts to be relatively weak with respect to acid generator as an acid diffusion controller.

And an acid generating agent, when used by mixing an onium salt capable of generating an acid is relatively weak against acid generated from the acid generator, an actinic ray or radiation acid generated from the acid generator by irradiation of There when colliding with an onium salt having a weak acid anion unreacted produces an onium salt having a strong acid anion by releasing weak by salt exchange. Since strong acid in this process is replaced with a less catalytic ability weak, apparently acid can be controlled acid diffusion deactivated.

The onium salt comprising a relatively weak against acid generator is preferably a compound represented by the following general formula (d1-1) ~ (d1-3).

Figure JPOXMLDOC01-appb-C000050

Wherein, R 51 is a hydrocarbon group which may have a substituent, Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon adjacent to S the fluorine atom and non-substituted), R 52 is an organic group, Y 3 represents a linear, branched or cyclic alkylene group or an arylene group, Rf is a fluorine atom a hydrocarbon group comprising, M + is independently a sulfonium or iodonium cation.

Preferred examples of the sulfonium cation or an iodonium cation represented as M +, can be mentioned exemplified iodonium cations exemplified sulfonium cation and the general formula in formula (ZI) (ZII).

Preferred examples of the anion portion of the compound represented by formula (d1-1), can be mentioned exemplary structure in paragraph [0198] of JP 2012-242799.

Preferred examples of the anion portion of the compound represented by formula (d1-2), can be mentioned exemplary structure in paragraph [0201] of JP 2012-242799.

Preferred examples of the anion portion of the compound represented by formula (d1-3), can be mentioned illustrated structures paragraphs JP 2012-242799 [0209] and [0210].

Onium salt comprising a relatively weak against acid generator, (C) has a cationic site and an anionic site in the same molecule, and compounds in which the cation sites and anion sites are covalently linked ( hereinafter, it may be a "compound (CA)" and also referred to.).

As the compound (CA), it is preferably a compound represented by any one of the following formulas (C-1) ~ (C-3).

Figure JPOXMLDOC01-appb-C000051

In formula (C-1) ~ (C-3),
R 1, R 2, R 3 represents one or more substituents carbon atoms.

L 1 represents a divalent linking group or a single bond linking the cationic site and an anionic site.

-X - it is, -COO -, -SO 3 - represents an anion portion selected from -R 4 -, -SO 2 -, -N. R 4 is a linking site with the adjacent N atom, a carbonyl group: -C (= O) -, a sulfonyl group: -S (= O) 2 - , a sulfinyl group: -S (= O) - 1 with It represents the valence of the substituent.

R 1, R 2, R 3 , R 4, L 1 may be bonded together to form a ring structure. Further, (C-3) in, the combined two of R 1 ~ R 3, N atom and it may form a double bond.

The substituent having 1 or more carbon atoms in R 1 ~ R 3, an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyl group, an aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylamino carbonyl group, and arylaminocarbonyl groups. Preferably, an alkyl group, a cycloalkyl group, an aryl group.

L 1 as the divalent linking group, a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and two of these group and the like comprising a combination of more. L 1 is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, and a group formed by combining two or more of them.

Preferred examples of the compound represented by formula (C-1), JP 2013-6827 JP paragraphs [0037] ~ [0039] and JP 2013-8020 JP paragraphs [0027] - [0029 exemplified compounds may be mentioned in].

Preferred examples of the compound represented by formula (C-2), can be mentioned compounds exemplified in paragraphs [0012] - of JP 2012-189977 [0013].

Preferred examples of the compound represented by formula (C-3), can be mentioned compounds exemplified in paragraphs [0029] ~ of JP 2012-252124 [0031].

The content of the onium salt to be relatively weak with respect to the acid generator, on a solids basis of the composition, preferably 0.5 to 10.0 mass%, 0.5-8.0 mass % more preferably, more preferably 1.0 to 8.0 mass%.

[5] Solvent actinic ray-sensitive or radiation-sensitive resin composition usually contains a solvent.

The solvent which can be used in preparing the composition, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ethers, alkyl lactate, alkoxyalkyl propionate alkyl, cyclic lactone (preferably 4 carbon atoms 10), the ring also good monoketone compound having (preferably 4 to 10 carbon atoms), it may be mentioned alkylene carbonate, alkoxy alkyl acetate, the organic solvent an alkyl pyruvate.

Specific examples of these solvents include those described in U.S. Patent Application Publication 2008/0187860 Pat [0441] to [0455].

In the present invention, it may be used a solvent containing a hydroxyl group in the structure as the organic solvent, a mixed solvent obtained by mixing a solvent having no hydroxyl group.

Solvent containing a hydroxyl group and the solvent not containing a hydroxyl group but compounds exemplified above can be suitably selected, as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, an alkyl lactate or the like are preferable, propylene glycol monomethyl ether ( Propylene Glycol monomethyl Ether; PGME, another name: l-methoxy-2-propanol), ethyl lactate, and methyl 2-hydroxyisobutyrate more preferred. The solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetates, alkyl alkoxy propionate, ring which may monoketone compound containing, cyclic lactone, such as alkyl acetate are preferred, propylene glycol monomethyl ether Among these acetate (propylene glycol monomethyl ether acetate; PGMEA, another name: l-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, .gamma.-butyrolactone, cyclohexanone and butyl acetate are preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone are most preferred.

Mixing ratio of the solvent not containing a solvent and a hydroxyl group containing a hydroxyl group (by mass), 1 / 99-99 / 1, is preferably 10 / 90-90 / 10, more preferably 20 / 80-60 / 40 . The solvent not containing a hydroxyl group is mixed solvent containing 50 mass% or more is preferred in view of coating uniformity.

The solvent preferably contains propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate alone solvent or is preferably a mixed solvent of two or more species including propylene glycol monomethyl ether acetate.

[6] Surfactant actinic ray-sensitive or radiation-sensitive resin composition may or may not contain a further surfactant, when containing, fluorine-containing and / or silicon surfactants (a fluorine-containing surfactants, silicone surfactants, or surfactant) having both a fluorine atom and a silicon atom, or more preferably contains two or more.

By actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, 250 nm or less, particularly when using the following exposure light source 220 nm, with good sensitivity, resolution, adhesiveness and resist pattern with less development defects it is possible to give.

As the fluorinated and / or siliconized surfactants, there can be mentioned surfactants described in U.S. Patent Application Publication No. 2008/0248425, paragraphs [0276].

In the present invention, as described in U.S. Patent Application Publication No. 2008/0248425 in paragraphs [0280], it is also possible to use a fluorocarbon and / or silicon surfactants other than other surfactants.

These surfactants may be used alone or may be used in some combination.

When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, the amount of surfactant, relative to the total solids of the composition, preferably from 0.0001 to 2 mass%, more preferably is 0.0005 to 1 mass%.

On the other hand, the addition amount of the surfactant, based on the total amount of the composition (excluding the solvent), by a 10ppm or less, unevenly distributed to the surface of the hydrophobic resin, thereby more hydrophobic the surface of the resist film it can be, it is possible to improve followability of water at the immersion exposure.

[7] Other Additives actinic ray-sensitive or radiation-sensitive resin composition may or may not contain an onium carboxylate. Such onium carboxylate include those described in U.S. Patent Application Publication 2008/0187860 Pat [0605] ~ [0606].

These onium carboxylates can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide or ammonium hydroxide and carboxylic acid with silver oxide in an appropriate solvent.

When the actinic ray-sensitive or radiation-sensitive resin composition contains a carboxylic acid onium salt, the content thereof relative to the total solids content of the composition is generally from 0.1 to 20 wt%, preferably 0 .5 to 10 wt%, more preferably from 1 to 7 mass%.

The actinic ray-sensitive or radiation-sensitive resin composition, further optionally, acid amplifier, dyes, plasticizers, photosensitizers, light absorbing agents, dissolving the alkali-soluble resin, a dissolution inhibitor and a developer compound capable of increasing the sexual (e.g., phenolic compound of 1000 or less molecular weight, alicyclic having a carboxyl group, or an aliphatic compound), it may be contained.

Such phenolic compound of 1000 or less molecular weight, for example, JP-A-can be easily synthesized, JP-A-2-28531, U.S. Patent No. 4,916,210, European and the method described in Reference Patent No. 219,294, etc., it can be easily synthesized by those skilled in the art.

Alicyclic having a carboxyl group, or 219294. Specific examples of the aliphatic compounds, deoxycholate, carboxylic acid derivatives having a steroid structure, such as lithocholic acid, adamantane carboxylic acid derivative, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Although such dicarboxylic acids are not limited thereto.

The solid content of the actinic ray-sensitive or radiation-sensitive resin composition is generally 1.0-10 wt%, preferably 2.0 to 5.7 wt%, more preferably from 2.0 to 5. 3% by mass. The solid concentration in the above range, the resist solution can be uniformly coated on a substrate, and further it is possible to form an excellent resist pattern line width roughness. The reason is not clear, presumably, the solid content concentration of 10 mass% or less, preferably 5.7 mass% or less, the resist solution in the material, especially the aggregation of the photoacid generator is suppressed , as a result, a uniform resist film can be formed.

The solids concentration, relative to the total weight of the composition, the weight percentage of the weight of resist components except solvent.

Process for the preparation of the actinic ray-sensitive or radiation-sensitive resin composition is not particularly limited, predetermined organic solvent the above components, preferably dissolved in the mixed solvent, preferably filtration. Pore ​​size of the filter used for filtration is 0.1μm or less, more preferably 0.05μm or less, more preferably 0.03μm or less of polytetrafluoroethylene, polyethylene or nylon having preferred. In filtration, for example, Japanese as in 2002-62667, JP-circulating filtration may be performed, or may be connected to a plurality of types of filters in series or in parallel or followed by filtration. Further, it may be filtered multiple times composition. Further, before and after filtration, it may be subjected to deaeration treatment the composition.

Various materials used in the present invention (e.g., solvent, developer, rinsing liquid, etc.) is preferably free of impurities such as metals. The content of impurities contained in these materials, preferably 1ppm or less, more preferably 10 ppb, more preferably less 100 ppt, less, and particularly preferably 10 ppt, it is below the detection limit of substantially free (measuring device it) is most preferred.

Hereinafter, detailed explanation of the present invention examples, but the present invention is not limited thereto.
<Synthesis of Resin (P)>
Synthesis Example 1: Synthesis nitrogen stream resin (P-1), placed in a 3-neck flask PGME73.9G, and heated at 80 ° C.. Thereto, BMB (following structure) 10.2 g, and, DIOH (following structure) 16.0 g, PME-200 (the following structure) 11.1 g and, polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd. ), and a 4 mol% based on the combined total of the three monomers, it was added dropwise over 6 hours, dissolved in PGME 137.3 g. After the addition, the mixture was allowed to react for 2 hours at further 80 ° C.. The reaction solution was added dropwise over 20 minutes to a mixed solution of cool after heptane 1217.8G / ethyl acetate 521.9g of the powder precipitated was collected by filtration and dried, following P-1 resin was obtained 33.7g It was. The composition ratio of the repeating units of the obtained resin (molar ratio) 30/50/20, weight average molecular weight is 26000 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 2.03. Further, in the same manner, it was synthesized resin P-2 ~ P-16 given later.

Figure JPOXMLDOC01-appb-C000052

Synthesis Example 2: Synthesis nitrogen stream resin (P-27), three-neck flask, EGDE (following structure) 8.7 g, and, DGA (following structure) 6.7 g and the catalyst as tetrabutylammonium bromide ( produced by Wako Pure Chemical Industries), and 5 mol% based on the combined total of the two monomers, and PGME23.1G, placed in a 3-neck flask, and heated to 100 ° C., and allowed to react for 48 hours. The reaction solution was allowed to cool, was added dropwise over 10 minutes to water 274.8G, extracting a high viscosity liquid deposited and dried, the following resins P-27 were obtained 14.1 g. Of the obtained resin, the weight average molecular weight in terms of standard polystyrene in 2300, polydispersity (Mw / Mn) was 2.12. Further, in the same manner, it was synthesized resin P-19, P-24 ~ P-26 given later.

Figure JPOXMLDOC01-appb-C000053

<Preparation of the planarization film forming resin composition>
The ingredients shown in Table 1 solids were dissolved in the solvent shown in the same table to be 6 wt%, which flattening film forming resin composition was filtered through a polyethylene filter having a pore size of 0.03μm to give the X-1 ~ X-29.

The calculation method of Ohnishi parameter in each composition (Ohnishi P) referred to below.

(Ohnishi parameter of the resin) = sigma {(Ohnishi parameter of the repeating unit) × (the molar fraction of the repeating unit)}
Furthermore, Ohnishi parameter of the repeating units (units) is defined as follows.

(Ohnishi parameter of the repeating unit) = (total number of atoms in the repeating unit) / {(number of carbon atoms in the repeating unit) - (the sum of the number of oxygen atoms in the repeating unit and the number of sulfur atoms)}

Figure JPOXMLDOC01-appb-T000054

<Preparation of Resist Composition>
The ingredients shown in Table 2, were dissolved in the solvent shown in the table so as to have a solid matter concentration of 3-5 wt%, the resist composition 1 was filtered through a polyethylene filter having a pore size of 0.03μm this 6 was obtained.

Referred to as the calculation method of Ohnishi parameter to the following.

(Ohnishi parameter of the resin) = sigma {(Ohnishi parameter of the repeating unit) × (the molar fraction of the repeating unit)}
Furthermore, Ohnishi parameter of the repeating units (units) is defined as follows.

(Ohnishi parameter of the repeating unit) = (total number of atoms in the repeating unit) / {(number of carbon atoms in the repeating unit) - (the sum of the number of oxygen atoms in the repeating unit and the number of sulfur atoms)}
Incidentally, the Ohnishi parameter and Si content in the Table, the resist 1-5 resin of the exposed portion, the resist 6 is the value of the resin of the unexposed portion. That is the value of the resin portion remains as a pattern after the lithography process.

Figure JPOXMLDOC01-appb-T000055

Code described in Table 1 and Table 2 represent the following compounds.

[Resin P-1 ~ P-27]

Figure JPOXMLDOC01-appb-C000056

Figure JPOXMLDOC01-appb-C000057

[Resin A-1 ~ A-6]

Figure JPOXMLDOC01-appb-C000058

[Acid-generating agent]

Figure JPOXMLDOC01-appb-C000059

[Acid diffusion controller]

Figure JPOXMLDOC01-appb-C000060

[Hydrophobic resin]

Figure JPOXMLDOC01-appb-C000061

[Surfactant]
E-1: PF6320 (OMNOVA Inc.)
E-2: Megafac R94 (DIC Co., Ltd.)
[solvent]
PGMEA: propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether CyHx: Cyclohexanone gamma-BL: .gamma.-butyrolactone (γ-butyrolactone)
EL: ethyl lactate (ethyl lactate)
MEK: Methyl ethyl ketone MeOH: methanol as comparative composition, were prepared a resin composition according to (Y-1) and (Y-2) in Table 3 below.

Figure JPOXMLDOC01-appb-T000062

<Calculation of the etching rate>
The resist composition prepared above on a silicon wafer or a flat film-forming resin composition was applied to obtain a resist film or a planarization film was heated for 60 seconds at 90 ° C. or 120 ° C..

The resulting wafer was etched using a plasma etching apparatus (Hitachi ECR plasma etching apparatus U-621), was determined etching rate (plasma conditions: Ar500ml / min, N 2 500ml / min, O 2 10ml / min) . Note etch rate is the average rate up to 5 seconds to start the etching.

<Resist collapse performance evaluation>
From the etching speed obtained in the above, the film thickness of the flattening film when the 200 nm, was calculated film thickness of the resist film required to etch the flattening film.

The planarizing film-forming resin composition on the stepped substrate was coated to obtain a flattening film of heated 200nm thickness 60 seconds at 120 ° C.. This flattening film, the resist composition is coated and heated 90 ° C. 60 seconds to form a resist film. Using an ArF excimer laser scanner (NA: 0.75) to the obtained resist film, pitch 180 nm, through a 6% half-tone mask of the light-shielding portion 90 nm, was subjected to pattern exposure. After heating for 60 seconds at 90 ° C., in Examples 1 to 10 and 13 to 32, Comparative Examples 1 and 2, and paddle development for 30 seconds with butyl acetate developer, to obtain a line-and-space pattern. In Examples 11 and 12, and paddle development for 30 seconds with 2.3 wt% TMAH (Tetramethylammonium hydroxide) developer to obtain a line-and-space pattern. Pattern has a dimension fallen the most narrow line width, which was resolved. Collapse dimensions good resolution of smaller value resist. The evaluation results are shown in Table 4.

<Release property>
After evaluating the collapse dimensions, Examples 1 to 10 and 13 to 16 23 ° C. of 2.3 wt% TMAH aqueous solution (pH = 13.0), ammonia was heated in Example 11 and 12 70 ° C. peroxide mixture ( pH = 11.6), examples 17 to 32 were immersed substrate, respectively 20 wt% of guanidine solution of 23 ℃ (pKa = 11.8) 60 seconds. The cross section immersion after the substrate was observed with an electron microscope to confirm the peeling of the planarizing film forming resin composition. It was possible residual difference no peeling in any.

Figure JPOXMLDOC01-appb-T000063

From the above results, Ohnishi parameter by using greater than 4.5 planarizing film-forming resin composition, falling dimensions improved, it can be seen that enables finer patterning.

51 ... substrate 52 ... resist film (second film) 53 ... exposed resist film (second film) 54 ... first pattern 61 ... mask 71 ... activity rays or radiation 75 ... etching gas 76 ... ion 81 ... flattening film (first film) 82 ... second pattern

Claims (15)

  1. (A) Ohnishi parameter is 4.5 with a larger resin (P) a resin composition containing (a), forming a first film on the substrate,
    (B) said on the first layer, forming a second film by using the actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) which changes polarity by the action of an acid,
    (C) step of exposing the second layer and,
    (D) developing the exposed second layer, the substrate processing method comprising steps a to form a pattern.
  2. Ohnishi parameter of the resin (P) contained in the resin composition (a) is greater than the Ohnishi parameter the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition (A), in claim 1 the substrate processing method according.
  3. The actinic rays or the resin contained in the radiation-sensitive resin composition (A) contains a silicon atom, a substrate processing method according to claim 1 or 2.
  4. The first film is insoluble in the actinic ray-sensitive or radiation-sensitive resin composition, the substrate processing method according to any one of claims 1-3.
  5. After the said step (D),
    (G) a first layer, the substrate processing method according to any one of claims 1 to 4, further comprising the step, of peeling with liquid.
  6. Wherein the liquid, the substrate processing method according to claim 5, wherein the pH is greater than 8 solution.
  7. After the said step (D),
    (E) the pattern as a mask, the first film is etched step further substrate processing method according to any one of claims 1 to 6 including.
  8. After the said step (D),
    (F) The substrate processing method according to any one of claims 1 to 7, characterized in that said substrate further comprises a implantation step of introducing the metal ions.
  9. Wherein the developing in step (D) is performed using a developer containing an organic solvent, the substrate processing method according to any one of claims 1-8.
  10. The resin composition (a) is the as the resin (P), poly (meth) acrylic resin contains at least one resin selected from the group consisting of polyester resins and polyether resins, claim 1-9 the substrate processing method according to any one of.
  11. The resin composition (a) is the as the resin (P), contains at least a resin having a repeating unit represented by the following general formula (1-1), according to any one of claims 1 to 10 the method for processing the substrate.
    Figure JPOXMLDOC01-appb-C000001
    In the formula,
    R 1 represents a hydrogen atom or an organic group.
    R 2 represents a hydrocarbon group having a hetero atom. However, for the number of carbon atoms contained in R 2, the ratio of the number of hetero atoms contained in R 2 is 0.30 or more.
  12. In the general formula (1-1), R 2 is a lactone structure-containing group, a carbonate structure-containing group, an acetal structure-containing group, hydroxy group-containing group, or a group represented by the following general formula (P1), the substrate processing method according to claim 11.
    Figure JPOXMLDOC01-appb-C000002
    In the formula,
    R A represents a divalent hydrocarbon group which may contain a hetero atom.
    R B represents a monovalent hydrocarbon group which may contain a hetero atom.
    n represents an integer of 1 or more. also is R A presence of a plurality if n is an integer of 2 or more may be the same or different.
    * Represents a bonding position of the remainder of the repeating unit represented by formula (1-1).
    However, the ratio of the number of heteroatoms for the general formula (P1) carbon atoms contained in is at least 0.30.
  13. The resin composition (a) is the as the resin (P), contains at least a resin having a repeating unit represented by the following general formula (1-2), according to any one of claims 1 to 12 the method for processing the substrate.
    Figure JPOXMLDOC01-appb-C000003
    In the formula,
    L represents an organic group.
    X is, -O -, - S -, - CO -, - CO-O-, or represents -O-CO-.
  14. In the substrate processing method according to any one of claims 1 to 13, the resin composition used as the resin composition (a).
  15. Method of manufacturing an electronic device including a substrate processing method according to any one of claims 1 to 13.
PCT/JP2016/065505 2015-05-28 2016-05-25 Substrate processing method, resin composition, and method for producing electronic device WO2016190368A1 (en)

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JPS62276543A (en) * 1986-05-26 1987-12-01 Japan Synthetic Rubber Co Ltd Pattern forming method
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