TW201535475A - Pattern forming method, etching method, method for producing electronic device and electronic device - Google Patents

Abstract

A pattern forming method of the invention forms patterns in which two or more patterns are layout in different areas. And the pattern forming method of the invention forms a first negative pattern in a first area on a substrate, and forms a second negative pattern different from the first negative pattern in a second area different from the first area.

Description

Pattern forming method, etching method, manufacturing method of electronic component, and electronic component

The present invention relates to a pattern forming method, an etching method using the same, a method of manufacturing an electronic component including the same, and an electronic component manufactured by the manufacturing method. More specifically, the present invention relates to a manufacturing process of a circuit board suitable for a semiconductor manufacturing process such as an integrated circuit (IC), a liquid crystal, a thermal head, or the like, and a microelectromechanical system (Micro Electro Manufacturing steps of mechanical systems, MEMS, and the like, and other pattern forming methods of photolithography lithography steps, and etching methods using the same. In particular, the present invention relates to a pattern forming method suitable for exposure of a KrF, an ArF exposure apparatus, and an ArF liquid immersion projection apparatus using a far ultraviolet light having a wavelength of 300 nm or less as a light source, and an etching method using the same, and A method of manufacturing an electronic component including the same, and an electronic component manufactured by the manufacturing method.

In the past, in order to form a high-resolution trench pattern or the like, a negative development process (negatone imaging process) has been proposed, which is a negative type. The development process combines a positive-type chemically amplified resist composition having various properties and a versatility, and a developer containing an organic solvent (for example, see Patent Document 1).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-292975

[Patent Document 2] International Publication No. 2012/157433

In recent years, with the demand for diversification and high functionality of electronic components, it is required to form fine patterns of various shapes by etching or the like. For example, it is required to easily form the following patterns: layout in different regions on the substrate. A hole pattern having a hole pattern and a line pattern, or a resist pattern in which an isolated line pattern and a dense line pattern are mixed.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a pattern forming method, an etching method using the same, a method of manufacturing an electronic component including the same, and an electronic component manufactured by the manufacturing method, the pattern forming method A pattern in which two or more different patterns are arranged in different regions can be easily formed.

The present invention has the following constitution, thereby solving the above problems of the present invention.

[1] A pattern forming method of forming patterns in which two or more different patterns are arranged in different regions, and the pattern forming method includes: (i) sequentially performing the following steps (i-1), the following step (i-2), and the following step (i-3), forming a first negative pattern on the first region on the substrate, (i-1) a step of forming a first film on the substrate using a photosensitive ray-sensitive or radiation-sensitive resin composition (1), wherein the sensitized ray-sensitive or radiation-sensitive resin composition (1) contains (i-2) setting a region other than the first region as a non-exposed portion to the resin which is increased in polarity by an action of an acid and having a reduced solubility in a developing solution containing an organic solvent a step of exposing the first film, (i-3) developing the exposed first film using a developing solution containing an organic solvent, and forming the first negative pattern in the first region; And (iii) sequentially performing the following step (iii-1), the following step (iii-2), and the following step (iii-3) on the substrate different from the first region; a step of forming a second negative pattern different from the first negative pattern in the region, and (iii-1) forming a second on the substrate using the sensitizing ray-sensitive or radiation-sensitive resin composition (2) Membrane step The photosensitive ray-sensitive or radiation-sensitive resin composition (2) contains a resin which is increased in polarity by an action of an acid and which has reduced solubility in a developing solution containing an organic solvent, (iii-2) a step of exposing the second film to a region other than the second region as a non-exposed portion, and (iii-3) developing the exposed second film using a developer containing an organic solvent The step of forming the second negative pattern in the second region.

[2] The pattern forming method according to [1], wherein the heating step (ii) is further included between the step (i) and the step (iii).

[3] The pattern forming method according to [1] or [2], wherein the photosensitive ray-sensitive or radiation-sensitive resin composition (1) and the sensitizing ray-sensitive or radiation-sensitive resin composition ( 2) Different.

[4] The pattern forming method according to [1] or [2] wherein the sensitizing ray-sensitive or radiation-sensitive resin composition (1) and the sensitizing ray-sensitive or radiation-sensitive resin composition ( 2) Same.

[5] An etching method in which a pattern formed by the pattern forming method according to any one of [1] to [4] is used as a mask, and the substrate is subjected to an etching treatment.

[6] A method of producing an electronic component, comprising the pattern forming method according to any one of [1] to [4].

[7] An electronic component produced by the method of producing an electronic component according to [6].

According to the present invention, there can be provided a pattern forming method, an etching method using the same, a method of manufacturing an electronic component including the same, and an electronic component manufactured by the manufacturing method, which can be easily formed in different regions Two or more patterns of different patterns are arranged in the middle.

10‧‧‧Substrate

50‧‧‧1st film

51‧‧‧1st negative pattern

60‧‧‧2nd film

61‧‧‧2nd negative pattern

71‧‧‧3rd negative pattern

A1‧‧‧1st area

A2‧‧‧2nd area

A3‧‧‧3rd area

M1‧‧‧ mask

M2‧‧‧ mask

(a) to (f) in Fig. 1 are diagrams for explaining an embodiment of the present invention, respectively. A schematic cross-sectional view illustrating the method of forming a case.

FIG. 2 is a plan view showing the first negative pattern 51 in the first region A1 formed on the substrate 10.

3 is a plan view showing the first negative pattern 51 in the first region A1 formed on the substrate 10 and the second negative pattern 61 in the second region A2 formed on the substrate 10.

Fig. 4 is a plan view showing another embodiment of the present invention.

Fig. 5 is a plan view showing another embodiment of the present invention.

Fig. 6 is a plan view showing another embodiment of the present invention.

Fig. 7 is a plan view showing still another embodiment of the present invention.

Fig. 8 is a plan view showing still another embodiment of the present invention.

Fig. 9 is a plan view showing still another embodiment of the present invention.

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

In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term "actinic ray" or "radiation" as used in the present specification means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (Extreme Ultraviolet (EUV) light), an X-ray, an electron beam. (Electron Beam, EB) Wait. Further, the term "light" as used in the present invention means actinic ray or radiation.

In addition, the term "exposure" as used in the present specification means not only exposure by far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light, etc. represented by a mercury lamp or a quasi-molecular laser, but also an electron beam or an ion beam. The drawing of the equal particle beam is also included in the exposure.

<Pattern forming method and etching method>

Hereinafter, a pattern forming method of the present invention and an etching method using the same will be described.

First, the pattern forming method of the present invention is formed in a pattern in which different patterns are arranged in two different regions, and the pattern forming method sequentially includes: (i) sequentially performing the following steps (i-1) and Step (i-2) and the following step (i-3), the step of forming a first negative pattern in the first region on the substrate, and (i-1) using a sensitizing ray or a radiation sensitive resin The step of forming a first film on the substrate, wherein the sensitized ray-sensitive or radiation-sensitive resin composition (1) contains an increase in polarity by an action of an acid, and contains an organic solvent. (i-2) a step of exposing the first film to a non-exposed portion by using a region other than the first region as a non-exposure portion, and (i-3) using an organic compound a developing solution of the solvent develops the exposed first film to form the first negative pattern in the first region; and (iii) sequentially performs the following step (iii-1), The following steps (iii-2) and the following Step (iii-3), in the second region different from the first region on the substrate, a step of forming a second negative pattern different from the first negative pattern, (iii-1) a step of forming a second film on the substrate using a photosensitive ray-sensitive or radiation-sensitive resin composition (2), wherein the sensitized ray-sensitive or radiation-sensitive resin composition (2) contains an action by an acid a resin having a reduced polarity and a reduced solubility in a developing solution containing an organic solvent, (iii-2) exposing the second film by setting a region other than the second region as a non-exposed portion In the step (iii-3), the exposed second film is developed using a developing solution containing an organic solvent, and the second negative pattern is formed in the second region.

According to the pattern forming method of the present invention, after the first negative pattern is formed in the first region in the step (i), the second negative pattern is formed in the second region different from the first region in the step (iii). Therefore, for example, it is possible to easily form two hole patterns (first negative pattern) in the first region and two wire patterns (second negative pattern) in the second region. The resist pattern of the different patterns above.

In addition, the first negative pattern and the second negative pattern each include a resist film portion and a gap portion in which the resist film portion is removed to expose the substrate, and the shape and size of the resist film portion and the gap portion are formed. Not limited.

For example, a hole pattern in which a circular hole-shaped hole portion as a gap portion is formed at equal intervals in the column direction and the row direction, a linear line portion having a resist film portion, and a gap portion similar in a line shape are exemplified. Line and gap pattern, the area of the resist film portion is larger than An isolated gap pattern or the like of the area of the linear gap portion.

Therefore, when the angle is changed, the first negative pattern and the second negative pattern are not limited to only the respective resist film portions (for example, one line portion) or the gap portion, and may be referred to as respective resist film portions or gaps. The collection of parts.

However, the first region and the second region are regions different from each other on the substrate, and the first negative pattern formed in the first region does not overlap with the second negative pattern formed in the second region. For example, when both the first negative pattern and the second negative pattern are line and gap patterns, the line portion of the second negative pattern is not formed in the gap portion of the first negative pattern.

Further, a resist film is formed by using a sensitizing ray-sensitive or radiation-sensitive resin composition containing a crosslinking agent, and an unexposed portion is dissolved by an alkali developing solution after exposure to form a negative pattern. In the method, the exposed portion including the crosslinked body is likely to swell due to the alkaline developing solution, and it may be difficult to form a fine pattern.

On the other hand, in the present invention, the photosensitive ray-sensitive or radiation-sensitive resin composition (1) and the photosensitive ray-sensitive or radiation-sensitive resin composition (2) are all polarized by the action of an acid. The resin having a reduced solubility in a developing solution containing an organic solvent (hereinafter also referred to simply as "organic developing solution") is used in the dissolution rate of the exposed portion and the unexposed portion in the organic developing solution. Since the negative pattern is formed by the difference, even a fine pattern can be easily formed.

<Embodiment of the Invention>

Next, a pattern forming method according to an embodiment of the present invention will be described with reference to Figs. 1 to 3 .

(a) to (f) of Fig. 1 are schematic cross-sectional views for explaining a pattern forming method according to an embodiment of the present invention.

FIG. 2 is a plan view showing the first negative pattern 51 in the first region A1 formed on the substrate 10.

3 is a plan view showing the first negative pattern 51 in the first region A1 formed on the substrate 10 and the second negative pattern 61 in the second region A2 formed on the substrate 10.

<Step (i): Formation of the first negative pattern>

In the step (i), first, as shown in (a) to (c) of FIG. 1, the following steps (i-1), the following steps (i-2), and the following steps (i-) are sequentially performed. 3) The first negative pattern 51 having a plurality of holes (gap portions) arranged at equal intervals in the column direction and the row direction, for example, in the first region A1 on the substrate 10.

<Step (i-1): Formation of the first film>

As shown in (a) of FIG. 1, the step (i-1) is a step of forming a resist film (first film 50) on the substrate 10 using the photosensitive ray-sensitive or radiation-sensitive resin composition (1). The photosensitive ray-sensitive or radiation-sensitive resin composition (1) contains a resin which is increased in polarity by an action of an acid and which has reduced solubility in a developing solution containing an organic solvent.

In the step (i-1), the first film 50 may be formed on the entire region of the substrate 10 as shown in FIG. 1(a), or may be formed only in a partial region including the first region A1.

The substrate is not particularly limited, and an inorganic substrate such as ruthenium, SiO ₂ or SiN, a coated inorganic substrate such as spin-on glass (SOG), a semiconductor manufacturing step such as IC, a liquid crystal, and a thermal head can be used. The manufacturing process of the circuit board, and the substrate which is generally used in the lithography step of other photolithography processes. Further, an underlayer film such as an antireflection film may be formed between the first film and the substrate as needed. As the underlayer film, an organic antireflection film, an inorganic antireflection film, and other antireflection films can be appropriately selected. The underlayer film material is available from Brewer Science, Nissan Chemical Industries, Inc., and the like. The underlayer film which is suitable for the process of developing using a developing solution containing an organic solvent is, for example, an underlayer film described in WO2012/039337A.

In the step (i-1), the method of forming the first film using the sensitizing ray-sensitive or radiation-sensitive resin composition (1) is typically performed by a sensitizing ray-sensitive or radiation-sensitive resin composition (1). It is applied to a substrate, and a conventionally known spin coating method, spray method, roll coating method, dipping method, or the like can be used. Preferably, the sensitizing ray or the sensitizing radiation is applied by a spin coating method. Resin composition (1).

Further, the photosensitive ray-sensitive or radiation-sensitive resin composition (1) will be described in detail below.

The film thickness of the first film is preferably from 20 nm to 160 nm, more preferably from 50 nm to 140 nm, and still more preferably from 60 nm to 120 nm.

<Preheating step and post-exposure heating step>

Furthermore, the pattern forming method of the present invention preferably further comprises a pre-heating step (Prebake (PB)) between the step (i-1) and the step (i-2).

In addition, the pattern forming method of the present invention preferably also includes a post-exposure heating step (Post Exposure) between the step (i-2) and the step (i-3). Bake, PEB)).

The heating temperature is preferably 70 ° C to 130 ° C in PB or PEB, and more preferably 80 ° C to 120 ° C.

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

The heating can be performed by a mechanism provided in a general exposure/developer, or by using a hot plate or the like.

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

The pre-heating step and/or the post-exposure heating step may also include multiple heating steps.

<Step (i-2): Exposure of the first film>

As shown in (b) of FIG. 1, step (i-2) is a step of exposing the first film 50 to a region other than the first region A1 (including the second region A2) as a non-exposed portion.

In this case, the sensitizing ray-sensitive or radiation-sensitive resin composition (1) forming the first film 50 has a polarity which is increased by the action of an acid and a decrease in solubility in the organic developing solution, as will be described later. In addition to the resin, a compound which generates an acid by irradiation with actinic rays or radiation is usually contained. Therefore, an acid is generated in the exposed portion (first region A1) of the first film 50, and the polarity is increased by the action of the generated acid, and the solubility in the organic developer is reduced. When the organic developing solution is used for development in the step (i-3) to be described later, the non-exposed portion (second region A2) of the first film 50 is removed in the first region A1 as the exposure portion. Forming the first negative pattern Case 51.

However, the step (i-2) is not a step of setting only the region other than the first region A1 as the non-exposed portion. In other words, in the first film 50 existing in the first region A1, a gap portion (patterning) is formed in the first region A1. Therefore, in the first region A1, a non-exposure is also formed in a portion corresponding to the gap portion. unit.

In the exposure of the step (i-2), the wavelength of the light source used in the exposure apparatus is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, etc., preferably Far-ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 nm to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer thunder Shot (157 nm), X-ray, EUV (13 nm), electron beam, etc., preferably KrF excimer laser, ArF excimer laser, EUV or electron beam.

Step (i-2) may also include multiple exposure steps.

Further, for example, in the case where the light source is a KrF excimer laser, an ArF excimer laser or EUV, it is preferable to irradiate actinic rays or radiation (ie, perform exposure) with a mask.

In this case, as shown in FIG. 1( b ), for example, a hole pattern mask having a plurality of hole portions arranged at equal intervals in the column direction and the row direction as a light shielding portion can be used as the mask pattern. Mask M1.

However, in the present invention, the mask used in the step (i-2) is not limited thereto, and may be appropriately selected depending on the shape of the first negative pattern to be used, etc., for example, a mask or the like may be used: a line portion as a light shielding portion and a gap as a light transmitting portion The line and gap pattern of the portion, and the ratio of the width of the line portion to the width of the gap portion is 1:1.

Further, a liquid immersion exposure method can be applied to the exposure of the step (i-2).

The liquid immersion exposure method is a technique in which a liquid having a high refractive index (hereinafter also referred to as "liquid immersion liquid") is filled between a projection lens and a sample as a technique for improving the resolution. In addition, the liquid immersion exposure can be combined with a super-resolution technique such as a phase shift method or a deformation illumination method.

In the case of performing immersion exposure, (1) after the first film is formed on the substrate, before the step of performing exposure, and/or after (2) after the step of exposing the first film via the liquid immersion liquid, Before the step of heating the first film, the step of washing the surface of the first film with a chemical liquid of a water system is performed.

The liquid immersion liquid is preferably a liquid which is transparent to the exposure wavelength and has a temperature coefficient of the refractive index as small as possible to minimize the distortion of the optical image projected on the first film. Water is preferably used in terms of ease of acquisition, ease of handling, and the like.

In the case of using water, an additive (liquid) which reduces the surface tension of water and increases the interfacial activity can also be added in a small ratio. The additive is preferably an additive which does not dissolve the resist layer on the wafer and which has negligible influence on the optical coating on the lower surface of the lens element.

Such an additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specific examples thereof include methanol, ethanol, and isopropyl alcohol. By adding an alcohol having a refractive index substantially equal to that of water, the following advantages can be obtained: even if the alcohol component in the water is steamed The change in concentration with the hair can also cause the refractive index change of the liquid as a whole to be extremely small.

On the other hand, when a substance which is opaque to light of 193 nm or an impurity which is different in refractive index from water is mixed, distortion of an optical image projected onto the resist is caused, so that water to be used is preferred. It is distilled water. Pure water which has been further filtered by an ion exchange filter or the like can also be used.

In addition, the lithographic performance can be improved by increasing the refractive index of the liquid immersion liquid. From this point of view, it is also possible to add a refractive index-like additive to water, or to use heavy water (D ₂ O) instead of water.

When the first film formed using the photosensitive ray-sensitive or radiation-sensitive resin composition (1) is exposed through a liquid immersion medium, a hydrophobic resin (D) to be described later may be further added as needed. By adding the hydrophobic resin (D), the receding contact angle of the surface is increased. The receding contact angle of the first film is preferably 60 to 90, more preferably 70 or more.

In the immersion exposure step, the liquid immersion liquid must follow the action of causing the exposure head to scan at a high speed on the wafer and form an exposure pattern to move on the wafer, so that the liquid immersion liquid in the dynamic state is on the resist film (first The contact angle of the film becomes important, and the resist is required to have no residual liquid droplets and follow the performance of the high-speed scanning of the exposure head.

A liquid immersion liquid poorly soluble film (hereinafter also referred to as "top coat") may be provided between the first film formed by using the sensitizing ray-sensitive or radiation-sensitive resin composition (1) and the liquid immersion liquid. The film is not directly in contact with the liquid immersion liquid. The functions necessary for the top coat layer include coating suitability to the upper portion of the resist, transparency to radiation, particularly radiation having a wavelength of 193 nm, and poor solubility of the liquid immersion liquid. Top coat is preferred In order not to be mixed with the resist, it can be uniformly applied to the upper layer of the resist.

The top coat layer is preferably an aromatic-free polymer from the viewpoint of transparency at 193 nm.

Specific examples thereof include a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, a ruthenium-containing polymer, and a fluorine-containing polymer. The hydrophobic resin (D) described above is also suitable as a top coat. If the impurities are eluted from the top coat layer into the liquid immersion liquid, the optical lens is contaminated, so that the residual monomer component of the polymer contained in the top coat layer is preferably small.

When the top coat is peeled off, a developer may be used, or a release agent may be separately used. The release agent is preferably a solvent which is less permeable to the first film. In terms of the peeling step and the development processing step of the first film, it is preferable to carry out the peeling using an alkaline developing solution. The top coat layer is preferably acidic from the viewpoint of peeling off with an alkali developer, but may be neutral or alkaline from the viewpoint of non-intermixability with the first film. .

Preferably, there is no difference in refractive index or a difference in refractive index between the top coat layer and the liquid immersion liquid. In this case, the resolution can be improved. In the case where the exposure light source is an ArF excimer laser (wavelength: 193 nm), water is preferably used as the liquid immersion liquid, so the top coat for ArF immersion exposure is preferably close to water (1.44). Further, from the viewpoint of transparency and refractive index, the top coat layer is preferably a film.

The top coat layer is preferably not mixed with the first film and is not mixed with the liquid immersion liquid. From this point of view, in the case where the liquid immersion liquid is water, the solvent used in the top coat layer is preferably a photosensitive ray-sensitive or radiation-sensitive resin composition which is hardly soluble in the present invention. (hereinafter also referred to as "resin composition"), a solvent which is not water-soluble. Further, when the liquid immersion liquid is an organic solvent, the top coat layer may be water-soluble or water-insoluble.

Further, in addition to the normal illumination, the shape of the illumination light source at the time of exposure in the step (i-2) may be, for example, bipolar illumination, quadrupole illumination, ring illumination, special deformation illumination, or the like, and the optimum illumination may be selected according to the desired pattern. Light source shape.

For example, in the case of using a pattern mask containing a hole pattern area, quadrupole illumination can be preferably used, and in the case of using a pattern mask containing a line and gap pattern, dipole illumination can be preferably used. In addition, regardless of which of the hole pattern mask or the line and gap pattern mask, a pattern mask having an area of the light transmitting portion larger than the area of the light shielding portion (for example, a pattern mask formed with an isolated gap pattern) is used. In the case of the case, the usual illumination can be preferably used.

Further, in the present embodiment, since the first negative pattern is a hole pattern, it is preferable to use four-pole illumination in this case.

<Step (i-3): Development of the first film>

As shown in (c) of FIG. 1, step (i-3) develops the exposed first film 50 using a developing solution containing an organic solvent, thereby forming a first negative pattern 51 in the first region A1. A step of.

As described above, in the step (i-2), the solubility of the exposed portion of the first film 50 in the developer containing the organic solvent is reduced. Therefore, in the step (i-3), development is performed using a developing solution containing an organic solvent, and the non-exposed portion of the first film 50 is removed to form the first negative pattern 51.

In the present embodiment, as shown in (c) of FIG. 1 and FIG. 2, a first negative pattern 51 as a hole pattern is formed in the first region A1 on the substrate 10.

In the step (i-3), the developing solution in the step of developing the negative film by using the developing solution containing an organic solvent to form a negative pattern can be a ketone solvent, an ester solvent, an alcohol solvent, or a guanamine. It is a polar solvent such as a solvent or an ether solvent, and a hydrocarbon solvent.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, and 1-hexanone. , 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetamidine acetone, acetone acetone, ionone (ionone), diacetone alcohol, acetyl carbinol, acetophenone, methylnaphthyl ketone, isophorone, and the like.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, and 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, propyl lactate, propyl carbonate, and the like.

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

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

The guanamine-based solvent can be, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphonium triamine, 1 , 3-dimethyl-2-imidazolidinone and the like.

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

The solvent may be mixed in a plurality of types, or may be used in combination with a solvent or water other than the above. In order to fully exert the effects of the present invention, it is preferred that the total moisture content of the developer is less than 10% by mass, and more preferably substantially no moisture.

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

In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and still more preferably 2 kPa or less at 20 °C. By setting the vapor pressure of the organic developing solution to 5 kPa or less, the evaporation of the developing solution on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved, and as a result, the dimensions in the wafer surface are both The uniformity is good.

Specific examples of the vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, and 2 a ketone solvent such as ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone or methyl isobutyl ketone, butyl acetate, pentyl acetate, isoamyl acetate Ester, 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, formic acid Ester ester solvents such as butyl ester, propyl formate, ethyl lactate, butyl lactate, and propyl lactate, n-propanol, isopropanol, n-butanol, second butanol, third butanol, isobutanol, and hexanol An alcohol solvent such as an alcohol, n-heptanol, n-octanol or n-nonanol; a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol; or ethylene glycol monomethyl ether or propylene glycol monomethyl ether; Ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether a glycol ether solvent such as triethylene glycol monoethyl ether or methoxymethylbutanol; an ether solvent such as tetrahydrofuran, phenethyl ether or dibutyl ether; N-methyl-2-pyrrolidone and N,N-di A guanamine solvent such as methyl acetamide or N,N-dimethylformamide; an aromatic hydrocarbon solvent such as toluene or xylene; or an aliphatic hydrocarbon solvent such as octane or decane.

Specific examples of the vapor pressure of 2 kPa or less which is a particularly preferable range include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, and diisobutylene. Ketone solvents such as ketone, cyclohexanone, methylcyclohexanone, phenylacetone, butyl acetate, amyl acetate, cyclohexyl acetate, isobutyl isobutyrate, propylene glycol monomethyl ether acetate, B 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 solvent, n-butanol, second butanol, tert-butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, etc., ethylene glycol, diethylene glycol a glycol solvent such as triethylene glycol, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, A a glycol ether solvent such as oxymethylbutanol, an ether solvent such as phenethyl ether or dibutyl ether, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- A guanamine-based solvent such as dimethylformamide, an aromatic hydrocarbon solvent such as xylene, or an aliphatic hydrocarbon solvent such as octane or decane.

In the organic developer, an appropriate amount of a surfactant may be added as needed.

The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or a lanthanoid surfactant can be used. Examples of the fluorine-based and/or lanthanide-based surfactants include, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and Japan. JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-H08-62834, JP-A No. 8-62834, and JP-A-9-54432 Japanese Patent Laid-Open No. Hei 9-5988, U.S. Patent No. 5,405, 720, U.S. Patent No. 5,360, 692, U.S. Patent No. 5,529, 881, U.S. Patent No. 5,296,330, U.S. Patent No. 5,436,098, U.S. Patent No. 5,576,143 The surfactant described in the specification, the specification of U.S. Patent No. 5,294,511, and the specification of U.S. Patent No. 5,824,451 is preferably a nonionic surfactant. Nonionic The surfactant is not particularly limited, and a fluorine-based surfactant or a quinone-based surfactant is more preferably used.

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

In addition, a state in which a nitrogen-containing compound (amine or the like) is added to an organic developer can be preferably used as in the invention of the patent application of Japanese Patent No. 5,056,974.

<alkali development step>

In addition, the pattern forming method of the present invention may be between step (i-2) and step (i-3) or between step (i-3) and step (iii-1) (in the following step (ii) In the case of the step (i-3) and the step (ii), the step of performing development using an alkaline developer is further included.

In the case where the pattern forming method of the present invention further includes a step of performing development using an alkaline developing solution, the alkaline developing solution may be, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate or sodium metasilicate. Inorganic bases such as ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, and dimethyl An alcoholic amine such as ethanolamine or triethanolamine; a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide; or an aqueous alkaline solution such as a cyclic amine such as pyrrole or piperidine.

Further, an appropriate amount of an alcohol or a surfactant may be added to the alkaline aqueous solution to be used. The surfactants mentioned above may be mentioned. Alkaline display The alkali concentration of the solution is usually from 0.1% by mass to 20% by mass.

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

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

The developing method can be applied, for example, to a method of immersing a substrate in a bath filled with a developing solution for a certain period of time (dipping method), and a method of developing the developing solution by stacking the developing solution on the surface of the substrate and holding it for a certain period of time. Puddle method; a method of spraying a developer onto a substrate surface (spray method); a method of continuously ejecting a developer onto a substrate rotating at a constant speed while scanning a developer discharge nozzle at a constant speed (dynamic dispensing method) )Wait.

In the case where the various developing methods include the step of ejecting the developing solution from the developing nozzle of the developing device to the resist film, the ejection pressure of the ejected developing solution (the flow rate per unit area of the ejected developing solution) is preferably It is 2 mL/sec/mm ² or less, more preferably 1.5 mL/sec/mm ² or less, and still more preferably 1 mL/sec/mm ² or less. The flow rate does not particularly have a lower limit, and is preferably 0.2 mL/sec/mm ² or more in consideration of a throughput.

By setting the discharge pressure of the discharged developing solution to the above range, pattern defects derived from the resist residue after development can be remarkably reduced. This case is described in detail in Japanese Patent Laid-Open Publication No. 2010-232550.

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

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

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

<rinsing step>

The pattern forming method of the present invention is preferably between step (i-3) and step (iii-1) (in the case of performing step (ii) described later, in steps (i-3) and (ii) After the step of performing development using a developing solution containing an organic solvent, a step of washing using an eluent containing an organic solvent (rinsing step) is included.

The eluent used in the rinsing step after the step of performing development using the developing solution containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a usual organic solvent can be used. The eluent is preferably rinsed with at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. liquid.

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

After the step of performing development using a developer containing an organic solvent, it is more preferred to use at least one organic solvent containing a group selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent. a step of washing with an eluent, and preferably a step of washing with an eluent containing an alcohol solvent or an ester solvent, and particularly preferably a step of washing with a eluent containing a monohydric alcohol. It is best to carry out the use of an eluent containing a monohydric alcohol having 5 or more carbon atoms. The steps of cleaning.

Here, the monohydric alcohol used in the elution step may, for example, be a linear, branched or cyclic monohydric alcohol, and specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, Tert-butanol, 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, etc., and particularly preferred monohydric alcohols having a carbon number of 5 or more may be 1-hexanol or 2-hexanol. Alcohol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and the like.

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

The water content in the eluent is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The vapor pressure of the eluent used after the step of performing development using the developing solution containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more at 20 ° C. , 3kPa or less. By setting the vapor pressure of the eluent to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and the swelling due to the penetration of the eluent is suppressed, and the dimensional uniformity in the wafer surface is improved. It is getting better.

In the case where the pattern forming method of the present invention further includes a step of performing development using an alkaline developing solution, it is also preferred to include a step of washing using an eluent (rinsing step). The eluent in this case is pure water, and an appropriate amount of a surfactant may be added and used.

The method of the washing treatment in the rinsing step is not particularly limited, and for example, a method of continuously ejecting the eluent onto a substrate rotating at a constant speed (rotary coating method), and filling the substrate with the eluent can be applied. The method of immersing in the tank for a certain period of time (dipping method), the method of spraying the eluent on the surface of the substrate (spraying method), etc., wherein it is preferable to carry out the cleaning treatment by a spin coating method, and after the cleaning, the substrate is 2000 rpm~ Rotate at 4000 rpm to remove the eluent from the substrate. In addition, it is also preferred to include a heating step (Post Bake) after the rinsing step. The developer and the eluent remaining between the patterns and the inside of the pattern are removed by baking. The heating step after the rinsing step is usually carried out at 40 ° C to 160 ° C, preferably 70 ° C to 95 ° C for usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

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

<Step (ii): Heating step>

The heating step (ii) may also be further carried out between step (i-3) and step (iii-1) which will be described in detail below. Thereby, the solvent resistance of the first negative pattern formed in the step (i-3) can be further improved, and the first negative pattern can be converted into the following: even in the subsequent step (iii-1), the first The liquid containing the sensitized ray-sensitive or radiation-sensitive resin composition (2) is applied to the negative pattern and is not easily damaged.

The temperature in the heating step is preferably 150 ° C or higher, more preferably 170 ° C or higher. This temperature is usually set to 240 ° C or less. Further, the heating time in the heating step is performed in about 30 seconds to 120 seconds. It is considered that by performing the heating step in such a temperature range and time, the decomposition residue of the organic substance or the like is volatilized. It is preferably insoluble in a solvent.

In addition, the first negative pattern 51 contains a resin which is increased in polarity by the action of an acid and has reduced solubility in a developing solution containing an organic solvent, and has sufficient solvent resistance, so that it is not necessary to apply a solidified material ( Freezing material), but it is not excluded in the present invention that a known solidified material is applied to the first negative pattern.

<Step (iii): Formation of the second negative pattern>

Then, in the step (iii), as shown in (d) to (f) of FIG. 1, the following step (iii-1), the following step (iii-2), and the following steps (iii-) are sequentially performed. 3) A second negative pattern 61 different from the first negative pattern 51 is formed in the second region A2 different from the first region A1 on the substrate 10.

<Step (iii-1): Formation of the second film>

As shown in (d) of FIG. 1, the step (iii-1) is a step of forming a resist film (second film 60) on the substrate 10 using the photosensitive ray-sensitive or radiation-sensitive resin composition (2). The photosensitive ray-sensitive or radiation-sensitive resin composition (2) contains a resin which is increased in polarity by an action of an acid and which has reduced solubility in a developing solution containing an organic solvent.

In the step (iii-1), the second film 60 may be formed only in the second region A2 on the substrate 10, or may be formed in the first negative pattern 51 as shown in (d) of FIG. In the gap.

The method of forming a second film using the photosensitive ray-sensitive or radiation-sensitive resin composition (2) in the step (iii-1) and the sensitizing ray-sensitive or radiation-sensitive resin composition in the step (i-1) (1) The method of forming the first film is the same.

The photosensitive ray-sensitive or radiation-sensitive resin composition (2) will be described in detail below.

The preferable range of the film thickness of the second film is also the same as the range described in the preferred range of the film thickness of the first film, but the film thickness of the second film may be the same as or different from the film thickness of the first film.

<Preheating step and post-exposure heating step>

The pattern forming method of the present invention is also preferably between step (iii-1) and step (iii-2), including a pre-heating step (Prebake (PB)).

In addition, the pattern forming method of the present invention is also preferably between step (iii-2) and step (iii-3), including a post-exposure heating step (Post Exposure Bake (PEB)). The heating temperature is preferably 70 ° C to 130 ° C in PB or PEB, and more preferably 80 ° C to 120 ° C.

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

The heating can be performed by a mechanism provided in a general exposure/developer, or by using a heating plate or the like.

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

The pre-heating step and/or the post-exposure heating step may also include multiple heating steps.

<Step (iii-2): Exposure of the second film>

As shown in (e) of FIG. 1, step (iii-2) is a step of exposing the second film 60 to a region other than the second region A2 as a non-exposed portion.

At this time, the sensitized ray-sensitive or radiation-sensitive resin composition of the second film 60 is formed. As described later, the compound (2) contains a compound which generates an acid by irradiation with actinic rays or radiation, in addition to a resin which increases in polarity by an action of an acid and which has a reduced solubility in an organic developing solution. . Therefore, an acid is generated in the exposed portion (second region A2) of the second film 60, and the polarity increases due to the action of the generated acid, and the solubility in the organic developer is reduced. When the development is performed using the organic developing solution in the step (iii-3) described later, the non-exposed portion of the second film 60 (the second film 60 formed in the gap portion of the first negative pattern 51) The second negative pattern 61 is formed in the second region A2 as the exposure portion.

However, the step (iii-2) is not a step of setting only the region other than the second region A2 as the non-exposed portion. In the present invention, the gap portion is formed also in the second film 60 existing in the second region A2. Therefore, in the second region A2, the non-exposed portion is also formed in the portion corresponding to the gap portion.

Similarly to the step (i-2), for example, when the light source is a KrF excimer laser, an ArF excimer laser or EUV, it is preferable to form a mask as shown in (e) of FIG. M2 is used to illuminate actinic rays or radiation (ie, to perform exposure).

The mask pattern of the mask M2 in the step (iii-2) is not particularly limited as long as it is a mask pattern different from the mask M1 used in the step (i-2). In the present embodiment, the use pattern has the following The mask of the pattern (isolated groove pattern) is a mask M2: a pattern having a line portion as a light shielding portion and a gap portion as a light transmission portion, and an area of the light transmission portion larger than an area of the light shielding portion.

However, similarly to the mask used in the step (i-2), the mask of the step (iii-2) is not limited to the mask, and may be shaped according to the shape of the desired second negative pattern. Come to the appropriate choice.

The exposure method in the step (iii-2) can be similarly employed in the method described in the exposure of the step (i-2).

Further, similarly to the step (i-2), the shape of the illumination light source during the exposure of the step (iii-2) includes, for example, normal illumination, dipole illumination, quadrupole illumination, ring illumination, special deformation illumination, and the like. The desired pattern is used to select the optimum illumination source shape.

Further, in the present embodiment, the second negative pattern is an isolated gap pattern. Therefore, in this case, normal illumination is preferred.

<Step (iii-3): Development of the second film>

As shown in (f) of FIG. 1, step (iii-3) is a development of the exposed second film 60 using a developing solution containing an organic solvent, and a second negative pattern 61 is formed in the second region A2. step.

In addition, the developing solution and the developing method described in the organic developing solution in the step (i-3) can be similarly used in the developing solution and the developing method of the organic developing solution in the step (iii-3).

As described above, in the step (iii-2), the solubility of the exposed portion of the second film 60 in the organic developer is reduced. Therefore, in the step (iii-3), development is performed by using an organic developing solution, and the non-exposed portion of the second film 60 is removed to form the second negative pattern 61.

As described above, in the present embodiment, as shown in (f) of FIG. 1 and FIG. 3, the first negative pattern 51 as the hole pattern and the second negative as the isolated gap pattern are formed in different regions on the substrate 10. Pattern 61.

Further, the resist pattern formed by the pattern forming method of the present invention is of course not limited thereto.

<alkali development step>

Furthermore, the pattern forming method of the present invention may further comprise the step of developing using an alkaline developing solution between step (iii-2) and step (iii-3) or after step (iii-3).

In the alkali development step performed between the step (iii-2) and the step (iii-3) or after the step (iii-3), the same alkaline developing solution as the above-described alkaline developing solution can be used. .

Further, in the alkali development step performed between the step (iii-2) and the step (iii-3) or after the step (iii-3), the same alkali development method as the above-described alkali development method may be employed. .

<rinsing step>

Further, the pattern forming method of the present invention is preferably a step of performing cleaning after the step (iii-3), that is, after performing the development using a developing solution containing an organic solvent, using a rinse solution containing an organic solvent. Wash the steps). In the case of the eluent in this case, the following eluent can be similarly used: a step of washing (using a rinse step) using an eluent containing an organic solvent after the step of performing development using a developer containing an organic solvent Description of the eluent.

Further, in the case where the pattern forming method of the present invention has a step of performing development using an alkaline developing solution between steps (iii-2) and (iii-3) or after step (iii-3), Preferably, the step of developing using an alkaline developer After that, it includes the step of washing with the eluent (rinsing step). The eluent in this case is pure water, and an appropriate amount of a surfactant may be added and used.

The method of the washing treatment in the rinsing steps can similarly enumerate the methods described above.

<etching treatment>

Then, a resist pattern (a resist pattern including the first negative pattern 51 and the second negative pattern 61) in which different patterns are arranged in different regions, which are formed as described above, is used as a mask, and the substrate 10 is formed. An etching process is performed. Therefore, in the present embodiment, the substrate 10 that is perforated at the position corresponding to the hole portion of the first negative pattern 51 and the gap portion of the second negative pattern 61 can be obtained (the perforated substrate 10 is not shown). Show).

The method of the etching treatment is not particularly limited, and a known method can be used arbitrarily, and various conditions and the like are appropriately determined depending on the type, use, and the like of the substrate. For example, the etching treatment may be carried out in accordance with "Proc. of SPIE" (Vol. 6924, 692420 (2008)), Japanese Patent Laid-Open No. 2009-267112, and the like.

<Modification>

Further, the first negative pattern and/or the second negative pattern of the present embodiment described above may be formed by patterning the resist film twice or more.

In other words, the step (i) of forming the first negative pattern may also include pattern formation of the step (i-1), the step (i-2), and the step (i-3) in sequence. step.

Similarly, the step (iii) of forming the second negative pattern may also include a plurality of patterns sequentially having the step (iii-1), the step (iii-2), and the step (iii-3). Case formation steps.

In this case, in the plurality of pattern forming steps, the heating step may be further performed between the pattern forming steps twice.

Hereinafter, the modification will be specifically described.

First, step (i-1), step (i-2), and step (i-3) are sequentially performed by the same method as described above to form, for example, a line width and a gap width of 1:3 on the substrate. The line and gap patterns are used as the first negative pattern.

Then, step (i-1), step (i-2), and step (i-3) are sequentially performed, thereby forming, for example, a line and gap pattern having a line width and a gap width of 1:3 as the first negative pattern. .

Specifically, in the subsequent pattern formation, a line portion of the line and gap pattern is formed in the gap portion of the line and gap pattern formed in the previous pattern forming step.

As a result, the line and gap pattern formed in the previous pattern forming step and the line and gap pattern formed in the subsequent pattern forming step are formed on the substrate, for example, the line width and the gap width are 1:1. Negative pattern.

Then, a heating step (so-called solidification step) can also be carried out.

<Other Embodiments>

In the embodiment described above, the hole pattern is formed as the first negative pattern in the step (i), and the line pattern is formed as the second negative pattern in the step (iii), or vice versa. A line pattern is formed in (i), and a hole pattern is formed in the step (iii).

Further, as described above, the first negative pattern and the second negative pattern are not limited to the above-described patterns.

For example, both the first negative pattern and the second negative pattern may be line patterns, or the lines of the first negative pattern and the lines of the second negative pattern may not be parallel, for example, a vertical pattern ( For example, refer to FIG. 5 and FIG. 8 described later).

Further, the pattern may be such that both the first negative pattern and the second negative pattern are hole patterns, and at least one of the arrangement and the pitch of the holes in the first negative pattern and the second negative pattern Not the same pattern.

Further, in the above-described embodiment, half of the rectangular area on the substrate is set as the first area, and the remaining half is set as the second area, but the method of dividing the area is not limited thereto.

4 to 6 are plan views showing other embodiments of the present invention. In FIGS. 4 to 6, in the rectangular region on the substrate 10, the rectangular first region A1 occupies the center, and the second region A2 surrounds the first region A1.

In FIG. 4, a hole pattern (preferably a four-pole illumination) is formed as the first negative pattern 51, and an isolated gap pattern (preferably normal illumination) as a line pattern is formed as the second negative pattern 61.

In FIG. 5, a line and gap pattern (preferably dipole illumination) as a line pattern is formed as the first negative pattern 51, and an isolated gap pattern (preferably normal illumination) as a line pattern is formed as the second negative. Pattern 61. Furthermore, in FIG. 5, the line of the first negative pattern is perpendicular to the line of the second negative pattern and is not parallel.

In FIG. 6, a line and gap pattern (preferably a two-pole illumination) as a line pattern is formed as the first negative pattern 51, and a hole pattern (an isolated gap pattern as a hole portion of the gap portion) is formed (preferably) It is the normal illumination) as the 2nd negative pattern 61.

Further, in the above-described embodiment, the two different patterns are formed in two different regions, but the present invention is not limited thereto, and may be in three or more different regions. Different three or more patterns are formed.

In this case, in the stage of forming the second negative pattern in the step (iii), it is assumed that the first negative pattern is formed in the step (i), and then formed in the step (iii). The second negative pattern can be formed in a pattern in which three different patterns are arranged in three different regions.

Alternatively, it is also conceivable that the pattern forming method of the present invention may further have the same steps as step (i) or step (iii) after step (i) and step (iii).

7 to 9 are plan views showing still another embodiment of the present invention. In FIGS. 7 to 9 , three different patterns are formed in three different regions. Specifically, in the rectangular region on the substrate 10 , the rectangular first region A1 is disposed in the lower left of the figure. The third area A3 occupies the center of the upper half of the figure, and the rest becomes the second area A2.

In FIG. 7, a hole pattern (preferably a four-pole illumination) is formed as the first negative pattern 51, and an isolated gap pattern (preferably normal illumination) as a line pattern is formed as the second negative pattern 61, and is formed as a line pattern. The line and gap pattern (preferably dipole illumination) is used as the third negative pattern 71.

In FIG. 8, a line and gap pattern (preferably a two-pole illumination) as a line pattern is formed as the first negative pattern 51, and a hole pattern (an isolated gap pattern as a hole portion of the gap portion) is formed (preferably Usually illuminated) as the second negative pattern 61, and shaped A line and gap pattern (preferably dipole illumination) as a line pattern is used as the third negative pattern 71. Furthermore, in FIG. 8, the line of the first negative pattern is perpendicular to the line of the third negative pattern and is not parallel.

In FIG. 9, a line and a gap pattern (preferably a two-pole illumination) as a line pattern are formed as the first negative pattern 51, and a hole pattern (an isolated gap pattern as a hole portion of the gap portion) is formed (preferably, usually The illumination is a second negative pattern 61, and an isolated gap pattern (preferably normal illumination) as a line pattern is formed as the third negative pattern 71.

As described above, the pattern forming method and the etching method of the present invention have been described. According to the present invention, patterns in which different patterns are arranged in different regions can be formed on the substrate by etching or the like.

In addition, the pattern obtained by the pattern forming method of the present invention can be applied to a core material of a spacer process as disclosed in Japanese Laid-Open Patent Publication No. Hei No. 3-270227 and Japanese Patent Laid-Open No. Hei No. 2013-164509. Core). Further, it can also be preferably used for guide pattern formation of Directed Self-Assembly (DSA) (for example, see "ACS Nano", Vol. 4, No. 8, page 4815 - 4823 pages). In addition, it can also be applied to various uses.

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

The manufactured electronic components are preferably mounted on electrical and electronic equipment (home appliances, office Automation (Office Automation, OA) / media related equipment, optical equipment and communication equipment, etc.

<Photosensitive ray-sensitive or radiation-sensitive resin composition (1)>

Next, each component of the photosensitive ray-sensitive or radiation-sensitive resin composition (1) (also simply referred to as "resin composition (1)") used in the pattern forming method of the present invention will be described.

The photosensitive ray-sensitive or radiation-sensitive resin composition (1) is typically a resist composition and is a negative resist composition (that is, a resist composition for developing an organic solvent). Further, the sensitized ray-sensitive or radiation-sensitive resin composition (1) is typically a chemically amplified resist composition.

[1] A resin whose polarity is increased by the action of an acid and whose solubility in a developing solution containing an organic solvent is reduced

The resin whose polarity is increased by the action of an acid and which has a reduced solubility in a developing solution containing an organic solvent is exemplified by, for example, a main chain or a side chain of the resin, or both the main chain and the side chain. A resin which decomposes by the action of an acid to generate a polar group (hereinafter also referred to as "acid-decomposable group") (hereinafter also referred to as "acid-decomposable resin" or "resin (A)").

The acid-decomposable group preferably has a structure in which a polar group is protected by a group which is decomposed by decomposition by an action of an acid. Preferable examples of the polar group include a carboxyl group, a phenolic hydroxyl group, and an alcoholic hydroxyl group (so-called alcoholic, which means that it is not acidic as a phenolic hydroxyl group) or a sulfonic acid group.

Preferred groups as the acid-decomposable group are hydrogen atoms of the groups. A group substituted with a group that is desorbed by an acid.

Examples of the group which is desorbed by an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ ) (OR ₃₉ ) and so on.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group (monocyclic or polycyclic), an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may also be bonded to each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group (monocyclic or polycyclic), a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group. Further, in the case of performing the pattern forming method of the present invention by exposure with KrF light or EUV light or electron beam irradiation, it is also preferred to use acid decomposability by protecting a phenolic hydroxyl group by an acid detachment group. base.

The resin (A) preferably contains a repeating unit having an acid-decomposable group.

The repeating unit can be exemplified by the following repeating unit.

In the general formula (aI) and 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 to Rx ₃ each independently represent an alkyl group or a cycloalkyl group. Two of Rx ₁ to Rx ₃ may also be bonded to form a ring structure. Further, the ring structure may contain a hetero atom such as an oxygen atom in the ring.

The divalent linking group of T may, for example, be an alkyl group, a -COO-Rt- group, an -O-Rt- group, a phenylene group or the like. In the formula, Rt represents an alkylene group or a cycloalkyl group.

From the viewpoint of making the resist insoluble in the organic solvent-based developing solution, T in the general formula (aI) is preferably a single bond or a -COO-Rt- group, and more preferably a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH ₂ - group, a -(CH ₂ ) ₂ - group or a -(CH ₂ ) ₃ - group.

T in the formula (aI') is preferably a single bond.

The alkyl group of X _a1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).

The alkyl group of X _a1 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

X _{a1 is} preferably a hydrogen atom or a methyl group.

The alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched.

The cycloalkyl group of Rx ₁ , Rx ₂ and Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, an adamantyl group or the like. Ring cycloalkyl.

The ring structure formed by the two bonds of Rx ₁ , Rx ₂ and Rx ₃ is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring or a cyclohexyl ring; a norbornane ring, a tetracyclodecane ring or a tetracyclic ring; A polycyclic cycloalkyl group such as a dodecane ring or an adamantane ring. More preferably, it is a monocyclic cycloalkane ring having a carbon number of 5 or 6.

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 the groups may have a substituent, and examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a cycloalkyl group (having a carbon number of 3 to 8), a halogen atom, and an alkoxy group (carbon number 1 to 4). ), a carboxyl group, an alkoxycarbonyl group (having a carbon number of 2 to 6), etc., preferably having a carbon number of 8 or less. Among them, from the viewpoint of further improving the dissolution contrast in the developer containing the organic solvent before and after the acid decomposition, it is more preferably a substituent having no hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom (for example, more preferably not The alkyl group substituted by a hydroxyl group, etc.) is preferably a group containing only a hydrogen atom and a carbon atom, and more preferably a linear or branched alkyl group or a cycloalkyl group.

Specific examples of the repeating unit having an acid-decomposable group are listed, but are not limited to these specific examples.

In a specific example, Rx represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH. Z represents a substituent, and when there are a plurality of cases, a plurality of Z may be the same or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and preferred examples of the substituent which each group such as Rx ₁ to Rx ₃ may have.

[Chemical 2]

[Chemical 4]

[Chemical 5]

[Chemistry 7]

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

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[11]

The following specific examples are repeating units having a structure in which an alcoholic hydroxyl group is protected by a group which is decomposed by decomposition by an action of an acid. In a specific example, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH.

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The repeating unit having an acid-decomposable group may be one type or two or more types may be used in combination. When the two types are used in combination, the combination thereof is not particularly limited. For example, it is conceivable that (1) a repeating unit which decomposes by an action of an acid to generate a carboxyl group, and which decomposes by an action of an acid to produce an alcoholic hydroxyl group. a combination of repeating units, (2) a repeating unit which is decomposed by an action of an acid to generate a carboxyl group, a combination of a repeating unit which generates a phenolic hydroxyl group by decomposition of an acid, and (3) by an action of an acid. A combination of two kinds of repeating units (structures are different from each other) which are decomposed to generate a carboxyl group. Among them, a preferred combination of the cases of (3) is cited as a reference.

[Chemistry 13]

The content of the repeating unit having an acid-decomposable group contained in the resin (A) (the total amount of the repeating unit having an acid-decomposable group is not particularly limited), and is not particularly limited with respect to the resin (A). The repeating unit preferably has a lower limit of 15 mol% (% by mole) or more, more preferably 20 mol% or more, and further preferably 25 mol%. More preferably, it is 40 mol% or more. Further, the upper limit is preferably 90 mol% or less, more preferably 75 mol% or less, and still more preferably 65 mol% or less.

The resin (A) may also contain a repeating unit having a lactone structure or a sultone structure.

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

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[Chemistry 16]

Two or more repeating units having a lactone structure or a sultone structure may also be used in combination.

In the case where the resin (A) contains a repeating unit having a lactone structure or a sultone structure, the content of the repeating unit having a lactone structure or a sultone structure is preferable with respect to all the repeating units in the resin (A). It is 5 mol% to 60 mol%, more preferably 5 mol% to 55 mol%, and further preferably 10 mol% to 50 mol%.

Further, the resin (A) may also contain a repeating unit having a cyclic carbonate structure. Specific examples are given below, but the present invention is not limited to these specific examples.

Further, in the following specific examples, R _A ¹ represents a hydrogen atom or an alkyl group (preferably a methyl group).

In the case where the resin (A) contains a repeating unit having a cyclic carbonate structure, the content of the repeating unit having a cyclic carbonate structure is preferably from 5 mol% to 60 mol% based on all the repeating units in the resin (A). More preferably, it is 5 mol% - 55 mol%, and further preferably 10 mol% - 50 mol%.

The resin (A) may also contain a repeating unit having a hydroxyl group or a cyano group.

Specific examples of repeating units having a hydroxyl group or a cyano group are listed below, but the present invention does not Limited to these specific examples.

In the case where the resin (A) contains a repeating unit having a hydroxyl group or a cyano group, the content of the repeating unit having a hydroxyl group or a cyano group is preferably from 3 mol% to 25 mol%, relative to all the repeating units in the resin (A). Preferably, it is 5 mol% to 15 mol%.

The resin (A) may also contain a repeating unit having an acid group.

The resin (A) may contain a repeating unit having an acid group or a repeating unit having an acid group, and in the case of containing a repeating unit having an acid group, having an acid group with respect to all the repeating units in the resin (A) The content of the repeating unit is preferably 25 mol% or less, more preferably 20 mol% or less. Resin (A) contains a repeating single with an acid group In the case of the element, the content of the repeating unit having an acid group in the resin (A) is usually 1 mol% or more.

Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto.

In a specific example, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

The resin (A) may further have the following repeating unit: an alicyclic hydrocarbon structure having no polar group (for example, the acid group, a hydroxyl group, a cyano group) and/or an aromatic ring structure, and no obvious An acid-decomposable repeating unit is shown.

The content of the repeating unit is preferably from 1 mol% to 50 mol%, more preferably from 5 mol% to 50 mol%, even more preferably from 5 mol% to 30 mol%, based on all the repeating units in the resin (A).

Specific examples of the repeating unit having an alicyclic hydrocarbon structure containing no polar group and exhibiting no acid decomposition property are listed below, but the present invention is not limited to these specific examples. In the formula, Ra represents H, CH ₃ , CH ₂ OH or CF ₃ .

The form of the resin (A) of the present invention may be any of a random type, a block type, a comb type, and a star type. The resin (A) can be synthesized, for example, by radical polymerization, cationic polymerization or anionic polymerization of an unsaturated monomer corresponding to each structure. Further, after the polymerization is carried out using an unsaturated monomer corresponding to the precursor of each structure, a polymer reaction is carried out to obtain a target resin.

When the resin composition (1) is used for ArF exposure, it is preferable that the resin (A) used in the resin composition (1) does not substantially have an aromatic ring in terms of transparency to ArF light (specifically In the resin, the ratio of the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, desirably 0 mol%, that is, having no aromatic group, and more preferably the resin (A) has A monocyclic or polycyclic alicyclic hydrocarbon structure.

When the resin composition (1) contains the resin (D) to be described later, the resin (A) preferably has no fluorine atom or ruthenium atom from the viewpoint of compatibility with the resin (D).

The resin (A) used in the resin composition (1) is preferably all repeating single The element is a resin composed of a (meth) acrylate-based repeating unit. In this case, it is possible to use a resin in which all repeating units are methacrylate-based repeating units, all repeating units are acrylate-based repeating units, and all repeating units are derived from methacrylate-based repeating units and acrylate-based repeating units. Any resin of the resin of the unit is preferably an acrylate-based repeating unit of 50 mol% or less of all repeating units.

When the resin composition (1) is irradiated with KrF excimer laser light, electron beam, X-ray, or high-energy light (EUV or the like) having a wavelength of 50 nm or less, the resin (A) may further contain a repeating unit having an aromatic ring. The repeating unit having an aromatic ring is not particularly limited, and is also exemplified in the description relating to each of the repeating units described above, and examples thereof include a styrene unit, a hydroxystyrene unit, and a phenyl (meth) acrylate unit. A hydroxyphenyl (meth) acrylate unit or the like. More specifically, the resin (A) may be a resin containing a hydroxystyrene-based repeating unit and a hydroxystyrene-based repeating unit protected by an acid-decomposable group, and the repeating unit having the aromatic ring and A resin or the like of a repeating unit in which a carboxylic acid moiety of acrylic acid is protected by an acid-decomposable group. Further, in particular, in the case of EUV exposure, high sensitivity is usually required, and therefore the resin (A) is preferably a repeating unit containing a protective group which is susceptible to acid decomposition. Specifically, the repeating unit may be exemplified by -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ) or -C(R ₀₁ ) in the structure illustrated as a group desorbed by an acid as described above. The structure represented by (R ₀₂ ) (OR ₃₉ ) (commonly known as the structure of an acetal type protecting group).

The resin (A) of the present invention can be synthesized and purified in accordance with a usual method (e.g., radical polymerization). For the synthesis method and purification method, for example, refer to paragraphs 0201 to 0202 of JP-A-2008-292975.

The weight average molecular weight of the resin (A) of the present invention is usually 1,000 or more, preferably 7,000 to 200,000, more preferably 7,000 by the polystyrene equivalent value of the Gel Permeation Chromatography (GPC) method. 50,000, and more preferably 7,000 to 40,000,000, and particularly preferably 7,000 to 30,000. When the weight average molecular weight is less than 7,000, the solubility in the organic developer is too high, and it is feared that a precise pattern cannot be formed.

The degree of dispersion (molecular weight distribution, Mw/Mn) is usually 1.0 to 3.0, and a resin preferably in the range of 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0 is used. The resin having a smaller molecular weight distribution is more excellent in resolution and resist shape, and the side wall of the resist pattern is smoother and the roughness is more excellent.

In the resin composition (1), the blending ratio of the resin (A) in the entire composition is preferably 30% by mass to 99% by mass, and more preferably 60% by mass to 95% by mass based on the total solid content.

The resin (A) may be used alone or in combination of two or more.

Specific examples of the resin (A) are listed below (the composition ratio of the repeating unit is a molar ratio), but the present invention is not limited to these specific examples. In the following, a case in which the structure corresponding to the acid generator (B) is carried on the resin (A) will be exemplified below.

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The resin exemplified below is an example of a resin which can be preferably used especially in EUV exposure or electron beam exposure.

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[2] Compounds which generate acid by irradiation with actinic rays or radiation

The resin composition (1) usually contains a compound which generates an acid by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (B)" or "acid generator"). The compound (B) which generates an acid by irradiation with actinic rays or radiation is preferably a compound which generates an organic acid by irradiation with actinic rays or radiation.

The acid generator can be appropriately selected and used: a photoinitiator-polymerized photoinitiator, a photoradical polymerization photoinitiator, a dye-based photodecolorizer, a photochromic agent, or a micro-resist. Knownization of acid by irradiation of actinic rays or radiation And a mixture of such compounds.

For example, a diazonium salt, a sulfonium salt, a sulfonium salt, a sulfonium salt, a quinone sulfinate, an oxime sulfonate, a diazodiazine, a diterpene, an o-nitrobenzyl sulfonate can be mentioned.

A preferred example of the acid generator is listed below.

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The acid generator can be synthesized by a known method, for example, according to JP-A-2007-161707, JP-A-2010-100595, <0200> to <0210>, and International Publication No. 2011/093280. <0051>~<0058>, the method described in <0382>~<0385> of International Publication No. 2008/153110 is synthesized.

The acid generators may be used alone or in combination of two or more.

Based on the total solid content of the resin composition (1), by actinic radiation or The content of the compound which generates an acid by irradiation of the radiation is preferably from 0.1% by mass to 30% by mass, more preferably from 0.5% by mass to 25% by mass, even more preferably from 3% by mass to 20% by mass, more preferably from 3% by mass to 20% by mass. It is 3 mass% to 15 mass%.

Further, depending on the composition of the sensitized ray-sensitive or radiation-sensitive resin, there is also a state (B') in which a structure corresponding to the acid generator is carried on the resin (A). Specifically, the structure described in Japanese Laid-Open Patent Publication No. 2011-248019 (especially the structure described in paragraphs 0164 to 0191, and the structure of the resin described in the example of paragraph 0555), Japan The repeating unit (R) and the like described in paragraph 0023 to paragraph 0210 of JP-A-2013-80002, the contents of which are incorporated herein by reference. Incidentally, even in a state in which the structure corresponding to the acid generator is carried on the resin (A), the sensitizing ray-sensitive or radiation-sensitive resin composition may additionally contain no resin ( Acid generator on A).

The aspect (B') may be exemplified by the following repeating unit, but is not limited thereto.

[Chem. 46]

[3] Solvent

The resin composition (1) usually contains a solvent.

Examples of the solvent which can be used in the preparation of the resin composition (1) include an alkylene glycol monoalkyl ether carboxylate, an alkylene glycol monoalkyl ether, an alkyl lactate, and an alkoxypropane. a base ester, a cyclic lactone (preferably having a carbon number of 4 to 10), a monoketone compound (preferably having a carbon number of 4 to 10), an alkyl carbonate, an alkyl alkoxyacetate, or the like. An organic solvent such as an alkyl pyruvate.

Specific examples of the solvent include the solvents described in the specification of the U.S. Patent Application Publication No. 2008/0187860, <0441> to <0455.

In the present invention, a plurality of organic solvents may also be used in combination.

For example, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent containing no hydroxyl group may be used as the organic solvent. Hydroxyl-containing solvent, no hydroxyl The solvent of the group may be appropriately selected from the above-exemplified compounds, and the solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether, an alkyl lactate or the like, more preferably a propylene glycol monomethyl ether (PGME). , alias 1-methoxy-2-propanol), ethyl lactate. Further, the solvent containing no hydroxyl group is preferably an alkylene glycol monoalkyl ether acetate, an alkyl alkoxy propionate, a ring-containing monoketone compound, a cyclic lactone, an alkyl acetate, or the like. Among these, it is especially preferred to be Propyleneglycol monomethyl ether acetate (PGMEA, alias 1-methoxy-2-ethoxypropane), ethyl ethoxy propionate, 2- Heptone, γ-butyrolactone, cyclohexanone, butyl acetate, preferably propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone.

Further, a solvent having no hydroxyl group in the structure may be used in combination. The combination thereof may be exemplified by PGMEA and cyclohexanone, PGMEA and cyclopentanone, PGMEA and γ-butyrolactone, PGMEA and 2-heptanone.

For example, when two solvents are used, the mixing ratio (mass) is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40.

The solvent preferably contains propylene glycol monomethyl ether acetate, preferably propylene glycol monomethyl ether acetate alone solvent or two or more mixed solvents containing propylene glycol monomethyl ether acetate.

In addition, when a solvent having a relatively high boiling point such as γ-butyrolactone is used in an appropriate amount, it is expected that the hydrophobic resin (D) to be described later is further biased to the surface, and the performance for liquid immersion exposure is improved.

Further, three or more solvents may be used. It is sometimes possible to carry out minor resistance Etch shape adjustment, viscosity adjustment, etc. Combinations include: PGMEA/PGME/γ-butyrolactone, PGMEA/PGME/cyclohexanone, PGMEA/PGME/2-heptanone, PGMEA/cyclohexanone/γ-butyrolactone, PGMEA/γ-butyrolactone /2-heptanone and the like.

[4] Hydrophobic resin (D)

The resin composition (1) may contain a hydrophobic resin (hereinafter also referred to as "hydrophobic resin (D)" or simply "resin (D)") particularly when applied to liquid immersion exposure. Further, the hydrophobic resin (D) is preferably different from the resin (A).

Thereby, the hydrophobic resin (D) is biased toward the surface layer of the film, and when the liquid immersion medium is water, the static/dynamic contact angle with respect to water on the surface of the resist film can be improved, and the liquid immersion liquid followability can be improved.

Further, even when the resin composition (1) is not applied to liquid immersion exposure, the resin composition (1) can contain a hydrophobic resin for various purposes. For example, when the resin composition (1) is applied to EUV exposure, it is preferable to use a hydrophobic resin in order to suppress out gas, adjust a pattern shape, or the like.

The hydrophobic resin (D) is preferably designed to be present at the interface as described above. Unlike the surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and it does not contribute to the polar substance and the non-polarity. The substance is mixed evenly.

The hydrophobic resin (D) preferably has at least one of "fluorine atom", "deuterium atom", and "CH ₃ partial structure contained in a side chain portion of the resin" from the viewpoint of being present in the surface layer of the film. Furthermore, it is preferable to have two or more types.

The standard polystyrene-equivalent weight average molecular weight of the hydrophobic resin (D) is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, and still more preferably 2,000. ~15,000.

Further, the hydrophobic resin (D) may be used alone or in combination of two or more.

The content of the hydrophobic resin (D) in the resin composition (1) is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 8% by mass based on the total solid content in the resin composition (1). %, and further preferably 0.1% by mass to 7% by mass.

The hydrophobic resin (D) is the same as the resin (A), and of course, impurities such as metal are small, and the residual monomer or oligomer component is preferably 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 3% by mass. Further preferably, it is 0.05% by mass to 1% by mass. Thereby, the resin composition (1) which does not change the temporal change of the foreign material, the sensitivity, etc. in liquid is obtained. Further, the molecular weight distribution is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2 in terms of resolution, resist shape, side wall of the resist pattern, roughness, and the like. range.

The hydrophobic resin (D) can be synthesized by various commercial products or by a usual method (for example, radical polymerization). For example, a general synthesis method may be a method in which a monomer type and an initiator are dissolved in a solvent and heated to carry out polymerization, and a monomer polymerization method is carried out in a heating solvent for 1 hour to 10 hours. The dropwise addition polymerization method of the solution of the initiator is preferably a dropping polymerization method.

The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described in the resin (A), and in the synthesis of the hydrophobic resin (D), the reaction concentration is preferred. It is 30% by mass to 50% by mass. More specifically, please refer to the description in the vicinity of paragraphs 0320 to 0329 of Japanese Patent Laid-Open Publication No. 2008-292975.

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

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[5] Basic compounds

The resin composition (1) preferably contains a basic compound.

(1) The resin composition (1) is preferably a basic compound or an ammonium salt compound (hereinafter also referred to as "compound (N)") which is reduced in alkali by irradiation with actinic rays or radiation. ) as a basic compound.

The compound (N) is preferably a compound (N-1) having a basic functional group or an ammonium group and a group which generates an acidic functional group by irradiation with actinic rays or radiation. That is, the compound (N) is preferably a basic compound having a basic functional group and a group which generates an acidic functional group by irradiation with actinic rays or radiation, or an ammonium group and by actinic rays or radiation. An ammonium salt compound that illuminates a group that produces an acidic functional group.

Specific examples of the compound (N) include the following compounds. In addition, except The compounds of (A-1) to (A-44) described in the specification of the U.S. Patent Application Publication No. 2010/0233629, or the disclosure of the specification of U.S. Patent Application Publication No. 2012/0156617 (A) The compound of -1) to (A-23) can also be preferably used in the present invention as the compound (N).

These compounds can be synthesized in accordance with the synthesis examples and the like described in JP-A-2006-330098.

The molecular weight of the compound (N) is preferably from 500 to 1,000.

The resin composition (1) may contain the compound (N) or may not contain the compound (N), and when the compound (N) is contained, the content of the compound (N) based on the solid content of the resin composition (1) It is preferably 0.1% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass.

(2) Resin composition (1) In other forms, in order to reduce self-exposure The change in performance over time from the heating may also include a basic compound (N') different from the compound (N) as a basic compound.

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

In the formula (A'), RA ²⁰⁰ , RA ²⁰¹ and RA ²⁰² may be the same or different and each represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), and a cycloalkyl group (preferably a carbon number of 3~). 20) or an aryl group (carbon number 6 to 20), where RA ²⁰¹ and RA ²⁰² may also be bonded to each other to form a ring. In the formula (E'), RA ²⁰³ , RA ²⁰⁴ , RA ²⁰⁵ and RA ²⁰⁶ may be the same or different and each represents an alkyl group (preferably having a carbon number of 1 to 20).

The alkyl group in the general formula (A') and the general formula (E') may have a substituent, and the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms and a hydroxyl group having 1 to 20 carbon atoms. An alkyl group or a cyanoalkyl group having 1 to 20 carbon atoms.

The alkyl groups in the general formula (A') and the general formula (E') are more preferably unsubstituted.

Preferred examples of the basic compound (N') include hydrazine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc., more preferably Specific examples thereof include a combination of an imidazole structure, a diazabicyclo structure, a cesium hydroxide structure, a ruthenium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure. An alkylamine derivative having a hydroxyl group and/or an ether bond, an aniline derivative having a hydroxyl group and/or an ether bond, or the like.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like. The compound having a diazabicyclo structure may, for example, be 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8- Diazabicyclo[5.4.0]undec-7-ene and the like. The compound having a ruthenium hydroxide structure may, for example, be a triarylphosphonium hydroxide, a benzamidine methylhydrazine hydroxide, a ruthenium hydroxide having a 2-oxoalkyl group, specifically, a triphenylphosphonium hydroxide or a hydroxide three. (Third butylphenyl) hydrazine, bis(t-butylphenyl)phosphonium hydroxide, benzamidine methylthiophene hydroxide, 2-oxopropylthiophene hydroxide, and the like. The compound having a ruthenium carboxylate salt structure is a compound in which the anion portion of the compound having a ruthenium hydroxide structure is a carboxylate salt, and examples thereof include an acetate salt, an adamantane-1-carboxylate, and a perfluoroalkyl carboxylate. . Examples of the compound having a trialkylamine structure include tri(n-butyl)amine, tris(n-octyl)amine and the like. The compound having an aniline structure may, for example, be 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline or N,N-dihexylaniline. The alkylamine derivative having a hydroxyl group and/or an ether bond may, for example, be ethanolamine, diethanolamine, triethanolamine or tris(methoxyethoxyethyl)amine. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

Further, preferred examples of the basic compound include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group. Specific examples thereof include the compound (C1-1) to the compound (C3-3) exemplified in <0066> of the specification of US Patent Application Publication No. 2007/0224539, but are not limited thereto.

(3) The resin composition (1) may contain, as another type of basic compound (N'), a nitrogen-containing organic compound having a group which is desorbed by the action of an acid. Specific examples of the compound are shown below as examples of the compound.

The compound can be synthesized, for example, according to the method described in JP-A-2009-199021.

Further, as the basic compound (N'), a compound having an amine oxide structure can also be used. Specific examples of the compound can be used: triethylamine pyridine-N-oxide, tributylamine-N-oxide, triethanolamine-N-oxide, tris(methoxyethyl)amine-N-oxidation , tris(2-(methoxymethoxy)ethyl)amine = oxide, 2,2',2"-nitrile triethylpropionate-N-oxide, N-2-(2 -Methoxyethoxy)methoxyethylmorpholine-N-oxide, an amine oxide compound exemplified in JP-A-2008-102383.

The molecular weight of the basic compound (N') is preferably from 250 to 2,000, more preferably from 400 to 1,000. The molecular weight of the basic compound is preferably 400 or more, more preferably 500 or more, and more preferably 600 or more from the viewpoint of further reduction in line width roughness (LWR) and uniformity of local pattern size. .

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

The resin composition (1) of the present invention may contain a basic compound (N') or a basic compound (N'), and in the case of a basic compound (N'), a resin composition (1) The amount of the basic compound (N') to be used is usually 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass based on the solid content.

(4) The resin composition (1) may further contain a phosphonium salt represented by the following formula (6A) or (6B) as a basic compound in another embodiment. The onium salt is expected to control the diffusion of acid in the resist system in accordance with the acid strength of the photoacid generator generally used in the resist composition.

In the formula (6A), Ra represents an organic group. Among them, a fluorine atom is substituted for a group which is directly bonded to a carbon atom of a carboxylic acid group in the formula.

X ⁺ represents a phosphonium cation.

In the formula (6B), Rb represents an organic group. Among them, a fluorine atom is substituted for a group which is directly bonded to a carbon atom of a sulfonic acid group in the formula.

X ⁺ represents a phosphonium cation.

The organic group represented by Ra and Rb is preferably a carbon atom directly bonded to a carboxylic acid group or a sulfonic acid group in the formula. Among them, in this case, in order to become a relatively weak acid compared with the acid generated from the photoacid generator, a fluorine atom is not substituted on a carbon atom directly bonded to a sulfonic acid group or a carboxylic acid group.

Examples of the organic group represented by Ra and Rb include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 3 to 30 carbon atoms. Some or all of the hydrogen atoms in the groups may also be substituted.

Examples of the substituent which the alkyl group, the cycloalkyl group, the aryl group, the arylalkyl group and the heterocyclic group may have include a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, an alkylcarbonyl group and the like.

Examples of the phosphonium cation represented by X ⁺ in the general formula (6A) and the general formula (6B) include a phosphonium cation, an ammonium cation, a phosphonium cation, a phosphonium cation, and a diazonium cation. Among them, a phosphonium cation is more preferable.

The phosphonium cation is, for example, preferably an aryl phosphonium cation having at least one aryl group, more preferably a triaryl phosphonium cation. The aryl group may also have a substituent, and the aryl group is preferably a phenyl group.

Examples of the phosphonium cation and the phosphonium cation are also preferably exemplified in the compound (B). The structure of the Ming.

The specific structure of the onium salt represented by the general formula (6A) or the general formula (6B) is shown below.

(5) The resin composition (1) may contain the compound of the formula (I) of JP-A-2012-189977, and the formula (I) of JP-A-2013-6827. The compound represented by the formula (I) of the Japanese Patent Laid-Open Publication No. 2013-8020, and the compound represented by the formula (I) of JP-A-2012-252124 have the same A compound of both a phosphonium salt structure and an acid anion structure (hereinafter also referred to as a betaine compound) is used as a basic compound. The onium salt structure may be an anthracene structure, an anthracene structure or an ammonium structure, and is preferably a phosphonium salt structure or a phosphonium salt structure. Further, the acid anion structure is preferably a sulfonate anion or a carboxylate anion. Examples of the compound thereof include the following compounds.

[60]

[6] surfactants

The resin composition (1) may further contain a surfactant. When the resin composition (1) contains a surfactant, it is preferred to contain a fluorine-based and/or a lanthanoid surfactant (a fluorine-based surfactant, a lanthanoid surfactant, and a fluorine atom and a ruthenium atom). Any one or two or more of the surfactants).

When the resin composition (1) contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, a resist pattern having excellent sensitivity, resolution, adhesion, and development defects can be provided.

Examples of the fluorine-based and/or lanthanoid surfactants include the surfactants described in <0276> of the specification of U.S. Patent Application Publication No. 2008/0248425, for example, Fluorad FC430, Fluorad FC431. , Fluorad FC4430 (made by Sumitomo 3M (share)), Megafac series (made by Di Love (DIC)), Surflon S-382, Surflon SC101, Surflon 102, Surflon 103, Surflon 104, Surflon 105, Surflon 106, Surflon KH -20 (made by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Manufactured by East Asian Synthetic Chemicals Co., Ltd.), Surflon S-393 (made by Seimi Chemical), Eftop EF121, Eftop EF122A, Aifu Eftop EF122B, Eftop RF122C, Eftop EF125M, Eftop EF135M, Eftop EF351, Eftop EF352, Aifutuo (Eftop) Eftop) EF801, Eftop EF802, Eftop EF601 (manufactured by Mitsubishi Materials, Jemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA) , FTX-204G, FTX-208G, FTX-218G, FTX-230G, FTX-204D, FTX-208D, FTX-212D, FTX-218D, FTX-222D (manufactured by Neos). Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a lanthanoid surfactant.

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

The surfactant corresponding to the surfactant may, for example, be a Megafac F178, a Megafac F-470, a Megafac F-473, a Megafac F-475, or a good method. (Megafac) F-476, Megafac F-472 (manufactured by Dixon (DIC) Co., Ltd.), C ₆ F ₁₃ based acrylate (or methacrylate) and (poly(oxygen) () a copolymer of acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₃ F ₇ group and (poly(oxyethyl)) acrylate (or methacrylate) And a copolymer of (poly(oxypropyl)) acrylate (or methacrylate).

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

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

When the resin composition (1) contains a surfactant, the amount of the surfactant used is preferably 0.0001% by mass to 2% by mass, more preferably the total amount of the resin composition (1) (excluding the solvent). It is 0.0005 mass% to 1 mass%.

On the other hand, by setting the amount of the surfactant added to 10 ppm or less with respect to the total amount of the resin composition (1) (excluding the solvent), the surface bias of the hydrophobic resin is improved, whereby the resist can be used. The surface of the membrane is more hydrophobic, which improves the water followability during immersion exposure.

[7]Other additives (G)

The resin composition (1) may also contain a cerium carboxylate salt. The ruthenium carboxylate salt described in the specification of the U.S. Patent Application Publication No. 2008/0187860, <0605> to <0606>, is exemplified.

When the resin composition (1) contains a cerium carboxylate salt, the content of the total solid content of the resin composition (1) is usually 0.1% by mass to 20% by mass. It is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 7% by mass.

Further, the resin composition (1) may contain a so-called acid multiplying agent as needed. The acid multiplying agent is preferably used in the pattern forming method of the present invention by EUV exposure or electron beam irradiation. Specific examples of the acid multiplying agent are not particularly limited, and examples thereof include the following compounds.

In the resin composition (1), if necessary, it may further contain a dye, a plasticizer, A light sensitizer, a light absorbing agent, an alkali-soluble resin, a dissolution inhibitor, and a compound which promotes solubility in a developing solution (for example, a phenol compound having a molecular weight of 1,000 or less, an alicyclic group having a carboxyl group or an aliphatic compound).

<Photosensitive ray-sensitive or radiation-sensitive resin composition (2)>

Next, the photosensitive ray-sensitive or radiation-sensitive resin composition (2) (also simply referred to as "resin composition (2)") used in the pattern forming method of the present invention will be described.

The resin composition (2) contains a resin which is increased in polarity by the action of an acid and which has reduced solubility in a developing solution containing an organic solvent.

The resin which is the same as the resin which is increased in polarity by the action of an acid and which has a reduced solubility in a developing solution containing an organic solvent as described in the resin composition (1), the resin content is relatively The preferred range of the total amount of the resin composition (1) is also the same as the range described in the resin composition (1).

Further, the resin composition (2) may similarly contain the respective components which the resin composition (1) may contain, and the content of each component is preferably in a range from the total amount of the resin composition (2) to the resin composition. The range described in (1) is the same.

The film thickness of the resin composition (1) and the resin composition (2) is preferably from 30 nm to 250 nm, and more preferably from 30 nm to 200 nm, from the viewpoint of improving the resolving power.

The solid content concentration of the resin composition (1) and the resin composition (2) is usually 1.0% by mass to 10% by mass, preferably 2.0% by mass to 5.7% by mass, and more preferably 2.0% by mass to 5.3% by mass. By setting the solid content concentration to the range, The resist solution can be uniformly applied to the substrate.

The solid content concentration refers to the weight percentage of the weight of the other resist component excluding the solvent to the total mass of the resin composition (1) or the resin composition (2).

The resin composition (1) and the resin composition (2) are prepared by dissolving the component in a predetermined organic solvent, preferably in the mixed solvent, filtering the filter, and applying it to a predetermined support (substrate). use. The filter used for the filtration of the filter preferably has a pore size of preferably 0.1 μm or less, more preferably 0.05 μm or less, further preferably 0.03 μm or less, of polytetrafluoroethylene, polyethylene or nylon. filter. When the filter is filtered, for example, it can be circulated and filtered as in the case of Japanese Patent Laid-Open Publication No. 2002-62667, or a plurality of filters can be filtered in series or in parallel. Further, the resin composition (1) and the resin composition (2) may be filtered a plurality of times. Further, the resin composition (1) and the resin composition (2) may be subjected to a degassing treatment or the like before and after filtration of the filter.

The resin composition (1) and the resin composition (2) may be the same as or different from each other.

Further, for the mutual mixing of the two, for example, when the first negative pattern is formed in the step (i-3) and the thermal curing (heating) like the heating step (ii) is performed, the mutual mixing is not easy. It is a problem, but it does not hinder the design of the resist that takes into account the problem of intermixing.

In order to suppress mutual mixing, for example, it is conceivable to select a resin which dissolves the resin of the resin composition (2) but does not dissolve the resin composition (1) as a resin composition (2) The solvent contained. In order to achieve such a design, for example, the solvent contained in the resin composition (2) may be a solvent exemplified as the above-described organic solvent-containing eluent, and an alcohol solvent or an ether solvent may preferably be mentioned. .

[Examples]

Hereinafter, the present invention will be specifically described by way of examples. However, the invention is not limited to the following examples.

<Preparation of sensitized ray-sensitive or radiation-sensitive resin composition>

The components shown in the table were dissolved in a total solid content of 3.8% by mass by the solvent shown in Table 4, and separately filtered by a polyethylene filter having a pore diameter of 0.1 μm to prepare sensitized ray or radiation sensitive. Resin composition Ar-01~ sensitized ray-sensitive or radiation-sensitive resin composition Ar-33.

<Resin (A)>

The resins in Table 4 are as described in Tables 5 and 6 below.

Further, the resin was synthesized as follows.

(Synthesis Example (Synthesis of Resin Pol-02))

102.3 parts by mass of cyclohexanone was heated to 80 ° C under a nitrogen stream. While stirring the solution, 22.2 parts by mass of the monomer represented by the following structural unit (Unit)-1 was added dropwise thereto for 5 hours, and 22.8 parts by mass of the monomer represented by the following structural formula (Unit)-2. 6.6 parts by mass of a monomer represented by the following structural unit (Unit)-3, 189.9 parts by mass of cyclohexanone, and dimethyl 2,2'-azobisisobutyrate [V-601, and Wako Pure Chemical Industries, Ltd. Industrial (manufactured)] 2.40 parts by mass of a mixed solution. After the completion of the dropwise addition, the mixture was further stirred at 80 ° C for 2 hours. After the reaction solution was allowed to stand for cooling, it was reprecipitated by a large amount of hexane/ethyl acetate (mass ratio: 9:1), filtered, and the obtained solid was vacuum-dried to obtain 41.1 parts by mass of the resin Pol-02. .

The weight average molecular weight (Mw: polystyrene conversion) obtained by GPC (carrier: tetrahydrofuran (THF)) of the obtained resin Pol-02 was Mw=9500, and the degree of dispersion was Mw/Mn=1.60. The composition ratio (mol ratio) of the repeating unit of the resin Pol-02 determined by ¹³ C-nuclear magnetic resonance (NMR) was 40/50/10.

The resin Pol-01 and the resin Pol-03 to the resin Pol-22 were synthesized in the same manner as in the synthesis of the resin Pol-02 except that the monomers used were changed in the synthesis of the resin Pol-02. Hereinafter, the composition ratio of the repeating unit of the resin Pol-01 to the resin Pol-22 (Mohr ratio, sequentially from left to right), weight average molecular weight (Mw), The degree of dispersion (Mw/Mn) is shown below.

The acid generators in Table 4 are as follows.

<alkaline compound (N)>

The basic compounds in Table 4 are as follows.

<Hydrophilic resin (D)>

The additive (hydrophobic resin) in Table 4 is as follows.

[化64]

<Surfactant>

The surfactants in Table 4 are as follows.

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

W-2: Megafac R08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd., fluorine and lanthanum)

W-3: Polyoxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd., 矽)

W-4: Troysol S-366 (manufactured by Troy Chemical)

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

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

<solvent>

The solvents in Table 4 are as follows.

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

SL-2: ethyl lactate

SL-3: Propylene Glycol Monomethyl Ether (PGME)

SL-4: cyclohexanone

SL-5: γ-butyrolactone

SL-6: 4-methyl-2-pentanol

<Example 1 to Example 32: Pattern forming method>

As described below, using a tantalum wafer on which an anti-reflection film is formed as a substrate, a hole pattern (first negative pattern) is formed in a partial region (first region) on the substrate, and a region different from the region is formed. An isolated gap pattern (second negative pattern) is formed in the (second region).

(formation of the first film)

First, an anti-reflective film-forming composition ARC29SR (manufactured by Nissan Chemical Co., Ltd.) was applied onto a wafer, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 96 nm. The resin composition (1) shown in the following Table 7 was applied thereon, and the first heating (PAB1) was carried out at 100 ° C for 60 seconds to form a first film having a film thickness of 100 nm.

(1st negative pattern formation)

For the first film, an ArF excimer laser immersion scanner (manufactured by ASML, XT1700i, Numerical Aperture (NA) of 1.20, C-quad 20, XY polarization, σ) was used. Out/in Patterning exposure was 0.981/0.895) with a mask (6% halftone hole pattern, pattern pitch: 90 nm, Critical Dimension: 45 nm). Furthermore, the shape of the illumination source is quadrupole illumination.

At this time, a mask in which a hole pattern is formed only in a portion corresponding to the first region and a portion other than the first region is a mask of the light shielding portion is used.

Then, after performing the second heating (PEB1) at 100 ° C for 60 seconds, organic solvent development was carried out using butyl acetate to obtain a first negative pattern.

(heating of the first negative pattern)

The first negative pattern obtained as described above was subjected to third heating (Post Bake 1) at 200 ° C for 60 seconds.

(formation of the second film)

The resin composition (2) shown in the following Table 7 was applied onto the substrate on which the first negative pattern was formed, and the fourth heating (PAB2) was performed at 100 ° C for 60 seconds to form a second film having a thickness of 100 nm. membrane.

(the second negative pattern is formed)

For the second film, an ArF excimer laser immersion scanner (manufactured by ASML, XT1700i, NA of 0.75, Annular XY polarization, σout/in of 0.97/0.740), and a mask (6) were used. % halftone isolated trench pattern, Critical Dimension: 100 nm) for pattern exposure.

At this time, the following mask is used: an isolated groove pattern is formed in a portion corresponding to the second region by pattern exposure only to the second region, and other than Part of the mask becomes a shade. Furthermore, the shape of the illumination source is the use of normal illumination.

Then, after the fifth heating (PEB2) was carried out at 100 ° C for 60 seconds, organic solvent development was carried out using butyl acetate to obtain a second negative pattern.

The second negative pattern obtained as described above was subjected to a sixth heating (Post Bake 2) at 100 ° C for 60 seconds.

In each of the examples, the second negative pattern was formed and heated, and then observed using a scanning electron microscope (S9380 manufactured by Hitachi, Ltd.). Observed knot It is apparent that, in any of the examples, a resist pattern in which a hole pattern (first negative pattern) and an isolated gap pattern (second negative pattern) are arranged in different regions is formed.

Although the embodiments have been described above, the present invention is not limited to the embodiments, and the pattern formation can be performed, for example, in the following manner.

. In the organic solvent-containing developing solution of each of the examples, a nitrogen-containing basic compound such as trioctylamine or the like is added to carry out negative development.

. In each of the embodiments, the exposure using the ArF excimer laser is replaced with the EUV exposure, and the above-described "reagents which are preferably used especially in EUV exposure or electron beam exposure" are used. The resin (an aromatic group-containing resin) to be described is used as a resin in a photosensitive ray-sensitive or radiation-sensitive resin composition.

10‧‧‧Substrate

50‧‧‧1st film

51‧‧‧1st negative pattern

60‧‧‧2nd film

61‧‧‧2nd negative pattern

A1‧‧‧1st area

A2‧‧‧2nd area

M1‧‧‧ mask

M2‧‧‧ mask

Claims (9)

A pattern forming method of forming patterns of two or more different patterns arranged in different regions, and the pattern forming method comprises: (i) sequentially performing the following step (i-1), following steps (i- 2) and the following step (i-3), the step of forming a first negative pattern in the first region on the substrate, and (i-1) using the sensitizing ray-sensitive or radiation-sensitive resin composition (1) a step of forming a first film on the substrate, wherein the sensitizing ray-sensitive or radiation-sensitive resin composition (1) contains a polarity which is increased by an action of an acid and is dissolved in a developing solution containing an organic solvent (i-2) a step of exposing the first film to a non-exposed portion by setting a region other than the first region, and (i-3) using a developer solution containing an organic solvent. Developing the exposed first film to form the first negative pattern in the first region; and (iii) sequentially performing the following step (iii-1) and following steps (iii) -2) and the following step (iii-3), forming a second region different from the first region on the substrate, different from the first negative pattern a step of forming a negative pattern, (iii-1) a step of forming a second film on the substrate using a sensitizing ray-sensitive or radiation-sensitive resin composition (2), wherein the sensitizing ray or radiation is linear The resin composition (2) contains a resin whose polarity is increased by the action of an acid and which has a reduced solubility in a developing solution containing an organic solvent, and (iii-2) sets a region other than the second region as Non-exposure department a step of exposing the second film, (iii-3) developing the exposed second film using a developing solution containing an organic solvent, and forming the second negative pattern in the second region A step of. The pattern forming method according to claim 1, wherein the step (i) and the step (iii) further comprise a heating step (ii). The pattern forming method according to claim 1, wherein the sensitized ray-sensitive or radiation-sensitive resin composition (1) is different from the sensitized ray-sensitive or radiation-sensitive resin composition (2). The pattern forming method according to claim 2, wherein the sensitized ray-sensitive or radiation-sensitive resin composition (1) is different from the sensitized ray-sensitive or radiation-sensitive resin composition (2). The pattern forming method according to claim 1, wherein the sensitized ray-sensitive or radiation-sensitive resin composition (1) is the same as the sensitized ray-sensitive or radiation-sensitive resin composition (2). The pattern forming method according to claim 2, wherein the sensitized ray-sensitive or radiation-sensitive resin composition (1) is the same as the sensitized ray-sensitive or radiation-sensitive resin composition (2). An etching method of etching a substrate by using a pattern formed by the pattern forming method according to any one of claims 1 to 6 as a mask. A method of producing an electronic component, comprising the pattern forming method according to any one of claims 1 to 6. An electronic component manufactured by the method of manufacturing an electronic component according to claim 8 of the patent application.