JP6340304B2 - Pattern forming method and electronic device manufacturing method - Google Patents

Description

  The present invention relates to a pattern forming method applicable to a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and other photofabrication lithography processes, a surface treatment agent used therefor, and an electronic The present invention relates to a device manufacturing method and an electronic device. In particular, the present invention relates to a pattern forming method and a surface treatment agent used therefor, an electronic device manufacturing method, and an electronic device, which are suitable for exposure in an ArF exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source.

Since the resist for KrF excimer laser (248 nm), a pattern formation method using chemical amplification has been used to compensate for the sensitivity reduction due to light absorption. For example, in the positive chemical amplification method, first, a photoacid generator contained in an exposed portion is decomposed by light irradiation to generate an acid. Then, in the post-exposure baking (PEB: Post Exposure Bake) process or the like, the alkali-insoluble group contained in the photosensitive composition is changed to an alkali-soluble group by the catalytic action of the generated acid. Thereafter, development is performed using, for example, an alkaline solution. Thereby, an exposed part is removed and a desired pattern is obtained.
In the above method, various alkali developers have been proposed. For example, as this alkaline developer, a 2.38 mass% TMAH (tetramethylammonium hydroxide aqueous solution) aqueous alkaline developer is generally used.

To reduce the size of semiconductor elements, the exposure light source has become shorter and the projection lens has a higher numerical aperture (high NA). Currently, an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. ing. As a technique for further increasing the resolving power, a method of filling a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”) between the projection lens and the sample (that is, an immersion method) has been proposed. In addition, EUV lithography in which exposure is performed with ultraviolet light having a shorter wavelength (13.5 nm) has also been proposed.
However, in reality, it is extremely difficult to find an appropriate combination of a resist composition, a developing solution, a rinsing solution, and the like necessary for forming a pattern with a comprehensively good performance. It has been demanded.

  In recent years, a pattern forming method using a developer containing an organic solvent is being developed (see, for example, Patent Documents 1 and 2).

Japanese Patent No. 4554665 JP 2008-310314 A

  However, a pattern forming method capable of forming a pattern having excellent pattern survivability at the time of double development with excellent roughness performance is not described in the above-mentioned document, and there is room for further improvement.

  The present invention solves the above-mentioned problems, and a pattern forming method capable of forming a pattern having excellent pattern survivability during multiple development (typically double development) with excellent roughness performance, and a surface treatment agent used therefor An object of the present invention is to provide an electronic device manufacturing method and an electronic device.

The present invention is as follows.
<1>
(1) forming a first actinic ray-sensitive or radiation-sensitive film with a first actinic ray-sensitive or radiation-sensitive resin composition containing a resin that decomposes by the action of an acid to generate a polar group;
(2) a step of exposing the first actinic ray-sensitive or radiation-sensitive film;
(3) developing the first actinic ray-sensitive or radiation-sensitive film using a developer containing an organic solvent to obtain a first development pattern;
(4) A step of causing a surface treatment agent containing a basic compound to act on the first development pattern as a compound that interacts with the polar group of the resin after exposure,
(8) removing the basic compound; and
(5) a step of further developing the first development pattern using an alkali developer to obtain a second development pattern;
The pattern formation method which contains these in this order.
<2>
(1) forming a first actinic ray-sensitive or radiation-sensitive film with a first actinic ray-sensitive or radiation-sensitive resin composition containing a resin that decomposes by the action of an acid to generate a polar group;
(2) a step of exposing the first actinic ray-sensitive or radiation-sensitive film;
(3) developing the first actinic ray-sensitive or radiation-sensitive film using a developer containing an organic solvent to obtain a first development pattern;
(4) A step of causing a surface treatment agent containing a basic compound to act on the first development pattern as a compound that interacts with the polar group of the resin after exposure,
(7) removing the upper portion of the first development pattern; and
(5) a step of further developing the first development pattern using an alkali developer to obtain a second development pattern;
The pattern formation method which contains these in this order.
<3>
Between the process (4) and the process (5), the pattern forming method according to the above <1>, including a process of (7) removing an upper portion of the first development pattern.
<4>
The pattern forming method according to <3>, wherein the step (8) is included after the step (7).
<5>
The pattern formation method according to <3>, which includes the step (7) after the step (8).
<6>
The pattern forming method according to any one of <2> to <5>, wherein the step (7) is a step (7 ′) of etching the first development pattern.
<7>
Between the step (1) and the step (2), (6 ′) the first actinic ray sensitive or radiation sensitive resin composition on the first actinic ray sensitive or radiation sensitive film. The second actinic ray-sensitive or radiation-sensitive film is formed by the second actinic ray-sensitive or radiation-sensitive resin composition containing a resin that is decomposed by the action of an acid and generates a polar group. The pattern formation method of any one of said <1>-<6> including the process to perform.
<8>
The resin in the first actinic ray-sensitive or radiation-sensitive resin composition contains a lactone structure, and the resin in the second actinic ray-sensitive or radiation-sensitive resin composition does not contain a lactone structure, The pattern forming method according to <7> above.
<9>
The pattern formation according to any one of the above items <1> to <8>, including a step of (10) heating the first development pattern between the step (4) and the step (5). Method.
<10>
The pattern forming method according to any one of <1> to <9>, wherein the surface treatment agent contains a resin having a repeating unit having a basic functional group as the basic compound.
<11>
The pattern forming method according to any one of <1> to <10>, wherein the basic compound is a compound having a primary or secondary amino group.
<12>
The pattern forming method according to any one of <1> to <11>, wherein the basic compound is soluble in the alkaline developer.
<13>
The pattern forming method according to any one of <1> to <12>, wherein the surface treatment agent contains a solvent, and the solvent is a ketone solvent or an ester solvent.
< 14 >
<1> to < 13 >, wherein the surface treatment agent contains a solvent, and the step (4) includes a step of bringing the surface treatment agent into contact with the surface of the first development pattern. Pattern forming method.
< 15 >
The pattern forming method according to any one of <1> to < 14 >, wherein the step (4) includes a step of bringing the vapor of the surface treatment agent into contact with the surface of the first development pattern.
< 16 >
The pattern forming method according to any one of <1> to < 15 >, wherein the exposure is immersion exposure.
< 17 >
The manufacturing method of an electronic device containing the pattern formation method of any one of said <1>-< 16 >.
The present invention relates to the items described in <1> to < 17 > above, but other items are also described for reference.
[1]
(1) forming a first actinic ray-sensitive or radiation-sensitive film with a first actinic ray-sensitive or radiation-sensitive resin composition containing a resin that decomposes by the action of an acid to generate a polar group;
(2) a step of exposing the first actinic ray-sensitive or radiation-sensitive film;
(3) developing the first actinic ray-sensitive or radiation-sensitive film using a developer containing an organic solvent to obtain a first development pattern;
(4) a step of causing a surface treatment agent containing a compound that interacts with a polar group of the resin after exposure to act on the first development pattern;
(5) a step of further developing the first development pattern using an alkali developer to obtain a second development pattern;
The pattern formation method which contains these in this order.
[2]
Between the step (1) and the step (2), (6 ′) the first actinic ray sensitive or radiation sensitive resin composition on the first actinic ray sensitive or radiation sensitive film. The second actinic ray-sensitive or radiation-sensitive film is formed by the second actinic ray-sensitive or radiation-sensitive resin composition containing a resin that is decomposed by the action of an acid and generates a polar group. The pattern formation method as described in said [1] including the process to perform.
[3]
The resin in the first actinic ray-sensitive or radiation-sensitive resin composition contains a lactone structure, and the resin in the second actinic ray-sensitive or radiation-sensitive resin composition does not contain a lactone structure, The pattern forming method according to [2] above.
[4]
The pattern according to any one of the above [1] to [3], which includes a step (7) of removing an upper portion of the first development pattern between the step (4) and the step (5). Forming method.
[5]
Between the step (4) and the step (5), (8) including a step of removing a compound that is provided on the first development pattern and interacts with a polar group of the resin after exposure. The pattern forming method according to any one of [1] to [3] above.
[6]
Between the step (4) and the step (5), (7) a step of removing an upper part of the first development pattern, and (8) the post-exposure provided on the first development pattern. The pattern formation method of any one of said [1]-[3] including the process of removing the compound which interacts with the polar group which resin has.
[7]
The pattern forming method according to the above [6], which includes the step (8) after the step (7).
[8]
The pattern forming method according to the above [6], which includes the step (7) after the step (8).
[9]
The pattern forming method according to any one of [4] and [6] to [8], wherein the step (7) is a step (7 ′) of etching the first development pattern.
[10]
The pattern formation according to any one of the above [1] to [9], including a step of (10) heating the first development pattern between the step (4) and the step (5). Method.
[11]
The pattern forming method according to any one of [1] to [10], wherein the surface treatment agent contains a basic compound as a compound that interacts with the polar group.
[12]
The pattern forming method according to [11] above, wherein the surface treatment agent contains a resin having a repeating unit having a basic functional group as the basic compound.
[13]
The pattern forming method according to [11] or [12] above, wherein the basic compound is a compound having a primary or secondary amino group.
[14]
The pattern forming method according to any one of [1] to [13], wherein the compound that interacts with the polar group is soluble in the alkaline developer.
[15]
The said surface treating agent contains a solvent, The said process (4) includes the process of making the said surface treating agent contact the surface of said 1st image development pattern, Any one of said [1]-[14]. Pattern forming method.
[16]
The pattern forming method according to any one of the above [1] to [15], wherein the step (4) includes a step of bringing the surface treatment agent into contact with the surface of the first development pattern.
[17]
The pattern forming method according to any one of [1] to [16], wherein the exposure is immersion exposure.
[18]
The manufacturing method of an electronic device containing the pattern formation method of any one of said [1]-[17].
[19]
The electronic device manufactured by the manufacturing method of the electronic device as described in said [18].
[20]
The surface treating agent used for the pattern formation method of any one of said [1]-[17].

  According to the present invention, a pattern forming method capable of forming a pattern having excellent pattern survivability during multiple development (typically double development) with excellent roughness performance, a surface treatment agent used therefor, and an electron A device manufacturing method and an electronic device can be provided.

1A to 1F are schematic cross-sectional views illustrating a pattern forming method according to a first embodiment of the present invention. FIGS. 2A to 2F are schematic cross-sectional views illustrating a pattern forming method according to a modification of the first embodiment of the present invention. 3A to 3F are schematic cross-sectional views for explaining a pattern forming method according to the second embodiment of the present invention. 4A to 4F are schematic cross-sectional views illustrating a pattern forming method according to a modification of the second embodiment of the present invention. 5A to 5E are schematic cross-sectional views illustrating a pattern forming method according to a reference example.

Hereinafter, modes for carrying out the present invention will be described.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “active light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.

<Pattern formation method>
The pattern forming method of the present invention comprises:
(1) forming a first actinic ray-sensitive or radiation-sensitive film with a first actinic ray-sensitive or radiation-sensitive resin composition containing a resin that decomposes by the action of an acid to generate a polar group;
(2) a step of exposing the first actinic ray-sensitive or radiation-sensitive film;
(3) developing the first actinic ray-sensitive or radiation-sensitive film using a developer containing an organic solvent to obtain a first development pattern;
(4) a step of causing a surface treatment agent containing a compound that interacts with a polar group of the resin after exposure to act on the first development pattern;
(5) A step of further developing the first development pattern using an alkali developer to obtain a second development pattern is included in this order.

First, a pattern forming method according to the first embodiment of the present invention will be described.
1A to 1F are schematic cross-sectional views illustrating a pattern forming method according to a first embodiment of the present invention.

When the exposure in the step (2) is a pattern exposure of a line-and-space optical image, as shown in FIG. 1A, the first actinic ray sensitive or radiation sensitive formed on the substrate 10 is used. A low photosensitive portion 11, an intermediate photosensitive portion 12, and a high photosensitive portion 13 are formed on the film. Here, the high photosensitive portion 13, the intermediate photosensitive portion 12, and the low photosensitive portion 11 mean areas having a relationship in which the exposure amount increases in this order, and the low photosensitive portion is not exposed at all. It can also include regions (ie, the exposure dose is zero).
Next, by developing the first actinic ray-sensitive or radiation-sensitive film using a developer containing an organic solvent, the low photosensitive portion 11 is removed as shown in FIG. A first development pattern 101 as a pattern is formed.

Next, a surface treatment agent is allowed to act on the first development pattern 101. As a result, as shown in FIG. 1C, the surface treatment agent and the cured layer 14 formed by the interaction between the upper portion of the intermediate photosensitive portion 12 and the high photosensitive portion 13, and the surface treatment agent film 15. Is formed.
Next, as shown in FIG. 1 (d), the upper portion 14a of the cured layer 14 is removed together with the surface treatment agent film 15, and then exists between the cured layers 14 and 14 as shown in FIG. 1 (e). The remaining surface treatment agent film 15 is removed, and the first development pattern 102 to which the surface treatment agent is applied is formed. Note that if the step (5) can be performed, it is not always necessary to remove the upper portion 14a of the hardened layer 14, and therefore the removal of the upper portion 14a of the hardened layer 14 is a step that is appropriately performed as necessary.

  Next, by further developing the first development pattern 102 using an alkaline developer, the highly photosensitive portion 13 is removed as shown in FIG. 1F, and the second development pattern as a positive pattern is obtained. 103 is formed.

  FIGS. 2A to 2F are schematic cross-sectional views illustrating a pattern forming method according to a modification of the first embodiment of the present invention.

  The steps referring to FIGS. 2A to 2C are the same as the steps referring to FIGS. 1A to 1C. Thereafter, in this modified example, as shown in FIG. 2D, the surface treatment agent film 15 is removed, and then, as shown in FIG. 2E, the upper portion 14a of the cured layer 14 is removed, A first development pattern 102 on which the surface treatment agent is applied is formed.

  The process referring to FIG. 2F is the same as the process referring to FIG.

  From the viewpoint that when the upper portion 14a of the hardened layer 14 is removed, the hardened layer 14 is less likely to be damaged from the side surface, the pattern forming method according to the first embodiment of the present invention is the first embodiment of the present invention. Although it is preferable to the pattern forming method according to the modification of the embodiment, the specific method and the conditions of the step of removing the upper portion 14a of the hardened layer 14 (for example, the type of etching gas, the type of substrate, and the like in the etching step) Depending on other conditions, the pattern forming method according to the modification of the first embodiment of the present invention can be sufficiently employed.

Next, a pattern forming method according to the second embodiment of the present invention will be described.
3A to 3F are schematic cross-sectional views for explaining a pattern forming method according to the second embodiment of the present invention.
In the second embodiment of the present invention, a first actinic ray-sensitive or radiation-sensitive film is formed on a substrate, and a protective film is formed on the first actinic-ray-sensitive or radiation-sensitive film. It is a form.
In this embodiment, when the exposure in the step (2) is a pattern exposure of a line-and-space optical image, the first actinic ray formed on the substrate 10 as shown in FIG. The low photosensitive portion 21, the intermediate photosensitive portion 22, and the high photosensitive portion 23 are formed on the photosensitive or radiation sensitive film. Here, the high photosensitive part 23, the intermediate photosensitive part 22, and the low photosensitive part 21 mean areas where the exposure amount increases in this order, and the low photosensitive part is not exposed at all. It can also include regions (ie, the exposure dose is zero).
Further, the protective film 51 formed on the first actinic ray-sensitive or radiation-sensitive film is preferably a second actinic ray-sensitive film different from the first actinic ray-sensitive or radiation-sensitive film. Or a radiation sensitive film (more specifically, the first actinic ray sensitive or radiation sensitive resin composition forming the first actinic ray sensitive or radiation sensitive film is decomposed by the action of an acid. And a second actinic ray-sensitive or radiation-sensitive film formed from a second actinic ray-sensitive or radiation-sensitive resin composition containing a resin that generates a polar group). The region 51a located above the low photosensitive portion 21 is also a low photosensitive portion with a low exposure amount.

  Next, by developing the two-layer actinic ray-sensitive or radiation-sensitive film using a developer containing an organic solvent, as shown in FIG. 51a is removed, and a first development pattern 201 as a negative pattern is formed.

Next, a surface treatment agent is allowed to act on the first development pattern 201. Thereby, as shown in FIG. 3C, a hardened layer 24 and a surface treatment agent film 25 formed by the interaction of the surface treatment agent and the intermediate photosensitive portion 22 are formed.
Next, as shown in FIG. 3 (d), the protective film 51 is removed together with the surface treatment agent film 25, and then, as shown in FIG. 3 (e), the remaining surface existing between the hardened layers 24, 24. The treatment agent film 25 is removed, and the first development pattern 202 to which the surface treatment agent is applied is formed.

  Next, by further developing the first development pattern 202 using an alkaline developer, the highly photosensitive portion 23 is removed as shown in FIG. 3F, and the second development pattern as a positive pattern is obtained. 203 is formed.

  4A to 4F are schematic cross-sectional views for explaining a pattern forming method according to a modification of the first embodiment of the present invention.

  The steps referring to FIGS. 4A to 4C are the same as the steps referring to FIGS. 3A to 3C. Thereafter, in this modification, the surface treatment agent film 25 is removed as shown in FIG. 4D, and then the protective film 51 is removed as shown in FIG. A first development pattern 202 on which is applied is formed.

  The process referring to FIG. 4F is the same as the above process referring to FIG.

  From the viewpoint that when the protective film 51 is removed, the cured layer 24 is not easily damaged from the side surface, the pattern forming method according to the second embodiment of the present invention is a modification of the second embodiment of the present invention. Although preferable to the pattern forming method according to the example, it depends on a specific method of the step of removing the protective film 51 and its conditions (for example, the type of etching gas, the type of substrate, and other conditions in the etching step). The pattern forming method according to the modification of the second embodiment of the present invention can be sufficiently employed.

  According to the pattern forming methods according to the first and second embodiments of the present invention and the modifications thereof, a pattern having excellent pattern survivability at the time of multiple development (typically double development) has roughness performance. It can be formed in an excellent state. The reason is not clear, but is estimated as follows, for example.

In the pattern forming method of the present invention, between step (3) and step (5), (4) a surface containing a compound that interacts with the polar group of the resin after exposure with respect to the first development pattern A step of applying a treatment agent.
Here, the first development patterns 101 and 201 used in the step (4) have space portions 101S and 201S formed by removing the low photosensitive portions 11 and 21, respectively. Thereby, in the step (4), the surface treatment agent that has entered the space portions 101S and 201S (see FIGS. 1B, 2B, 3B, and 4B) is transferred to the intermediate photosensitive portion. By acting from the side walls of the intermediate photosensitive portions 12 and 22, the polar group of the resin contained in the intermediate photosensitive portions 12 and 22 interacts with the surface treatment agent. As a result, the cured layers 14 and 24 in which the intermediate photosensitive portions 12 and 22 are cured are formed, and the pattern survivability and roughness performance during multiple development (typically double development) are considered to be excellent.

Next, a pattern forming method according to a reference example will be described.
5A to 5E are schematic cross-sectional views illustrating a pattern forming method according to a reference example.
Also in the pattern forming method according to the reference example, line and space optical image pattern exposure is performed as in the pattern forming methods according to the first and second embodiments of the present invention.
As a result, as shown in FIG. 5A, the low photosensitive portion 31, the intermediate photosensitive portion 32, and the high photosensitive portion 33 are formed on the actinic ray-sensitive or radiation-sensitive film formed on the substrate 10. Here, the high photosensitive portion 33, the intermediate photosensitive portion 32, and the low photosensitive portion 31 mean areas having a relationship in which the exposure amount increases in this order, and the low photosensitive portion is not exposed at all. It can also include regions (ie, the exposure dose is zero).
Next, the actinic ray-sensitive or radiation-sensitive film is developed using an alkaline developer, whereby the highly photosensitive portion 33 is removed as shown in FIG. 5B, and the first development as a positive pattern is performed. A pattern 301 is formed.

Next, a surface treatment agent is allowed to act on the first development pattern 301. As a result, as shown in FIG. 5C, a hardened layer 34 and a surface treatment agent film 35 formed by the interaction between the surface treatment agent and the intermediate photosensitive portion 32 are formed.
Next, as shown in FIG. 5D, the surface treating agent film 35 is removed.

  Next, by further developing the first development pattern 301 using an alkaline developer, the low photosensitive portion 31 is removed as shown in FIG. 5E, and the second development pattern 303 as a negative pattern is obtained. Is formed.

Similar to the pattern forming methods according to the first and second embodiments of the present invention and the modifications thereof, in the pattern forming method according to the reference example, the surface treatment agent is added to the space portion 301S (see FIG. 5B). The first and second embodiments of the present invention are intruded and act from the side wall side of the intermediate photosensitive portion 32 to cause an interaction between the polar group of the resin contained in the intermediate photosensitive portion 32 and the surface treatment agent. It can be expected that the same effects as those of the form and the pattern formation according to these modified examples are exhibited.
However, in the pattern forming method according to the reference example, the removal of the highly photosensitive portion 33 is performed with an alkali developer as described above. As a result, during development, the alkali developer that has entered the space portion 301S acts from the side wall side of the intermediate photosensitive portion 32 to neutralize some of the polar groups of the resin contained in the intermediate photosensitive portion 32. Tend to occur.
On the other hand, in the pattern forming methods according to the first and second embodiments of the present invention and the modifications thereof, the low photosensitive portions 11 and 21 are removed by a developer containing an organic solvent as described above. Therefore, the polar group of the resin contained in the intermediate photosensitive portions 12 and 22 is not easily deactivated by the developer. Therefore, the pattern formation method according to the first and second embodiments of the present invention and these modified examples has a tendency to more reliably form the hardened layers 14 and 24 than the pattern formation method according to the reference example. Therefore, it is more advantageous in terms of manifesting the effects of the present invention.

  Hereinafter, each process included in the pattern forming method of the present invention will be described in detail.

(1) A step of forming a first actinic ray-sensitive or radiation-sensitive film from a first actinic ray-sensitive or radiation-sensitive resin composition containing a resin that decomposes by the action of an acid to generate a polar group The first actinic ray-sensitive or radiation-sensitive film in (1) is formed from the first actinic ray-sensitive or radiation-sensitive resin composition in step (1), and more specifically. A film formed by applying a first actinic ray-sensitive or radiation-sensitive resin composition to a substrate is preferable. In the pattern forming method of the present invention, the step of forming a film of the first actinic ray-sensitive or radiation-sensitive resin composition on the substrate can be performed by a generally known method.

  Details of the first actinic ray-sensitive or radiation-sensitive resin composition will be described later.

In the present invention, the substrate on which the film is formed is not particularly limited, and silicon, SiN, inorganic substrates such as SiO ₂ and SiN, coated inorganic substrates such as SOG, semiconductor manufacturing processes such as IC, liquid crystal, thermal head For example, a substrate generally used in a circuit board manufacturing process such as the photolithographic lithography process can be used.

  A substrate coated with an antireflection film in advance may be used. As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, as an organic antireflection film, ARC series such as DUV30 series manufactured by Brewer Science, DUV-40 series, AR-2, AR-3, AR-5 manufactured by Shipley, ARC29A manufactured by Nissan Chemical Co., etc. Commercially available organic antireflection films can also be used.

The formation of the first actinic ray-sensitive or radiation-sensitive film is preferably performed by applying the first actinic ray-sensitive or radiation-sensitive resin composition on the substrate, and a conventionally known spin coating method A spray method, a roller coating method, a flow coating method, a doctor coating method, a dipping method, or the like can be used. Preferably, the coating film is formed by applying the first actinic ray-sensitive or radiation-sensitive composition by spin coating.
The thickness of the coating film is preferably 10 to 200 nm, and more preferably 20 to 150 nm.

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

(2) Step of exposing the first actinic ray-sensitive or radiation-sensitive film Although there is no limitation on the wavelength of the light source used in the exposure method of the present invention, infrared light, visible light, ultraviolet light, far ultraviolet light, pole Examples include ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light having a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm). , ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc., preferably KrF excimer laser, ArF excimer laser, EUV or electron beam, ArF excimer laser It is more preferable.

In the exposure process of the present invention, an immersion exposure method can be applied. The immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a modified illumination method.
When performing immersion exposure, (1) after forming the film on the substrate, before the exposure step and / or (2) after exposing the film via the immersion liquid, Prior to the heating step, a step of washing the surface of the membrane with an aqueous chemical may be performed.

The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the film. In the case of an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.
When water is used, an additive (liquid) that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens element.

As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained.
On the other hand, when an opaque substance or impurities whose refractive index is significantly different from that of water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. Therefore, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.

  The electrical resistance of the water used as the immersion liquid is preferably 18.3 MΩcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.

Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

  The receding contact angle of the actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is 70 ° or more at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%. It is suitable for exposure through an immersion medium, preferably 75 ° or more, and more preferably 75 to 85 °.

  If the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited. In order to realize a preferable receding contact angle, it is preferable to include a hydrophobic resin (HR) described later in the actinic ray-sensitive or radiation-sensitive composition. Alternatively, the receding contact angle may be improved by forming a coating layer (so-called “topcoat”) of a hydrophobic resin composition on the actinic ray-sensitive or radiation-sensitive film.

  In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. The contact angle of the immersion liquid with respect to the actinic ray-sensitive or radiation-sensitive film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

(3) Step of developing the first actinic ray-sensitive or radiation-sensitive film using a developer containing an organic solvent (hereinafter also referred to as “organic developer”) to obtain a first development pattern Organic development As the liquid, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents can be used.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate (also known as 3-methylbutyl acetate), amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, Examples thereof include butyl lactate, propyl lactate, and methyl 2-hydroxyisobutyrate.
Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.
Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.

Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents and ester solvents, and in particular, butyl acetate or ketone as the ester solvent. A developer containing methyl amyl ketone (2-heptanone) as a system solvent is preferred.

A plurality of solvents may be mixed, or may be used by mixing with a solvent other than those described above or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent 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, with respect to the total amount of the developer.

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

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in the specifications of US Pat. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

Further, the organic developer may contain a basic compound as necessary. Examples of the basic compound include the below-described basic compound that may be contained in the actinic ray-sensitive or radiation-sensitive resin composition described below, and particularly <0021> to <0063 in JP2013-11833A, for example. >, Nitrogen-containing basic compounds such as nitrogen-containing compounds described later, which are preferably contained in the surface-treating agent described later, and the like.
However, in order to fully achieve the effects of the present invention, the basic compound content as a whole developer is preferably less than 10% by mass, and more preferably substantially free of basic compounds. .
As the solvent in the organic developer, it is preferable to use a solvent having a reduced peroxide content.
In order to suppress the generation of peroxide, the solvent may contain a stabilizer (for example, an antioxidant).
The peroxide content in the solvent is preferably 2.0 mmol% or less, more preferably 1.0 mmol% or less, still more preferably 0.5 mmol% or less, and organic development. It is particularly preferred that the solvent in the liquid contains substantially no peroxide.

Examples of the developing method include the same methods as the developing method in step (3) described above.
When the above various development methods include a step of discharging the developer from the developing nozzle of the developing device toward the actinic ray-sensitive or radiation-sensitive film or the first development pattern, the discharge pressure (discharge) of the discharged developer the flow rate per unit area of the developer) is to be, as an example, preferably 2mL / sec / mm ² or less, more preferably 1.5mL / sec / mm ² or less, more preferably 1mL / sec / mm ² or less is there. There is no particular lower limit on the flow rate, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput. Details of this are described in JP 2010-232550 A, in particular paragraphs 0022 to 0029.
Moreover, you may implement the process of stopping image development, after substituting with another solvent after the process developed using the developing solution containing an organic solvent.

  It is preferable that the pattern formation method of this invention includes the rinse process wash | cleaned using a rinse liquid after a process (3). The rinsing liquid is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. As the rinsing liquid, a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. It is preferable.

  Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent. A preferred example of the hydrocarbon solvent is undecane.

  In one embodiment of the present invention, after the development step, the step of washing with a rinse liquid containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents. More preferably, the step of washing with a rinsing solution containing an alcohol solvent or an ester solvent is performed, and the step of washing with a rinsing solution containing a monohydric alcohol is particularly preferred. Preferably, a cleaning step is performed using a rinse liquid containing a monohydric alcohol having 5 or more carbon atoms.

  Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols, and specifically, 1-hexanol, 2-hexanol, 4-methyl-2-pen. Tanol (methyl isobutyl carbinol), 1-pentanol, 3-methyl-1-butanol and the like can be used.

A plurality of these components may be mixed, or may be used by mixing with an organic solvent other than the above.
The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.
As the solvent in the rinsing liquid, it is preferable to use a solvent having a reduced peroxide content.
In order to suppress the generation of peroxide, the solvent may contain a stabilizer (for example, an antioxidant).
The content of the peroxide in the solvent is preferably 2.0 mmol% or less, more preferably 1.0 mmol% or less, still more preferably 0.5 mmol% or less, It is particularly preferred that the solvent contains substantially no peroxide.

  The vapor pressure of the rinsing solution used after the step of developing with a developer 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 at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

An appropriate amount of a surfactant can be added to the rinse solution.
In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is washed using the rinse solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually 40 to 160 ° C., preferably 70 to 100 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

(4) A step of causing a surface treatment agent containing a compound that interacts with a polar group of the exposed resin to act on the first development pattern. The surface treatment agent in step (4) preferably contains a solvent. The step (4) is preferably a step of bringing a surface treatment agent into contact with the surface of the first development pattern.

  The polar group of the resin after exposure is not particularly limited as long as it is a polar group of the resin after exposure. However, after exposure, the polarity generated by decomposition of the resin by the action of an acid. It is preferably a group.

  As a method for contacting the surface treatment agent, for example, a method in which the first development pattern is immersed in a tank filled with the surface treatment agent for a predetermined time (dip method), and a surface treatment agent is applied to the surface of the first development pattern by surface tension. Method of developing by standing up and standing for a certain time (paddle method), Method of spraying surface treatment agent on the surface of the first development pattern (spray method), Constant speed on the first development pattern rotating at a constant speed In this method, the surface treatment agent is continuously ejected while scanning the surface treatment agent ejection nozzle (dynamic dispensing method), the surface treatment agent is applied to the first development pattern, and the surface treatment agent film is formed on the pattern. The method of exposing the first development pattern to the vapor of the agent can be applied, and the surface treatment agent film is formed on the pattern by applying the surface treatment agent to the first development pattern. How to it is preferred.

  The detail of the surface treating agent used in the said process (4) is mentioned later.

  The surface treatment agent may be a gas (preferably ammonia) or a solution as long as it contains a compound that interacts with a polar group, but is preferably a solution. In other words, the surface treatment agent preferably contains a solvent. In this case, the step (4) described above preferably includes a step of bringing the surface treatment agent into contact with the surface of the first development pattern. When the surface treatment agent is a solution, the total mass of the compound that interacts with the polar group is not particularly limited, but is 0.1 to 5% by mass with respect to the total amount of the surface treatment agent in terms of more excellent effects of the present invention. The following is preferable, 1 to 5% by mass is more preferable, and 1 to 4% by mass is further preferable. In the present invention, as a compound that interacts with a polar group, only one type of compound may be used, or two or more types of compounds having different chemical structures may be used.

  Further, the surface treatment agent may be a gas as described above. In this case, the step (4) described above may include a step of bringing the surface treatment agent into contact with the surface of the first development pattern. preferable.

  When the surface treatment agent is a solution, the amount used is not particularly limited as long as it can sufficiently interact with the polar group of the exposed resin, but at least the amount that can cover the entire substrate surface is used. It is preferable to use it. The specific amount used depends on the concentration of the surface treatment agent, the viscosity, the thickness of the actinic ray-sensitive or radiation-sensitive film, and the size of the substrate, for example, when the substrate is a wafer having a diameter of 300 mm, The applied amount is appropriately adjusted in the range of 0.1 mL to 100 mL.

  It is also preferable to carry out a heating step (bake after surface treatment) after the step (4). This heating step is usually performed at 40 to 160 ° C., preferably 70 to 100 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

(5) Step of further developing the first development pattern using an alkali developer to obtain the second development pattern According to the pattern forming method of the present invention, the combination of step (3) and step (5), for example, In US Pat. No. 8,227,183B. 1-FIG. 11 and the like, it is possible to obtain a pattern having a half of the spatial frequency of the optical image, or to obtain a pattern that is difficult to obtain by only one development step.
The alkaline developer in the step (5) contains water as a main component. The main component means that the water content exceeds 50% by mass with respect to the total amount of the developer.
As the developer, it is preferable to use an alkaline aqueous solution containing an alkali from the viewpoint of better pattern solubility.
The type of the alkaline aqueous solution is not particularly limited. For example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetra Octylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, tetrabutylammonium hydroxide such as dibutyldipentylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethyl Benzylammonium hydroxide Quaternary ammonium salts such as de, an inorganic alkali, primary amines, secondary amines, tertiary amines, alcohol amines, and the like alkaline aqueous solution containing a cyclic amine. Among these, an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide is preferable.

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

Appropriate amounts of alcohols and surfactants can be added to the alkaline aqueous solution. Specific examples and usage amounts of the surfactant are the same as those of the organic developer described later.
The alkali concentration of the aqueous alkali solution is usually 0.1 to 20% by mass.
The pH of the alkaline aqueous solution is usually 10.0 to 15.0.
Generally, a 2.38% mass aqueous solution of tetramethylammonium hydroxide is used. In addition, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
After the step (5), rinsing may be performed. As a rinsing liquid in the rinsing treatment performed after alkali development, pure water may be used and an appropriate amount of a surfactant may be added. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually 40 to 160 ° C., preferably 70 to 100 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

(6) Step of forming protective film with protective film-forming composition The pattern forming method of the present invention is the same as the above-described second embodiment of the present invention in that the step (1) and the step (2) In the meantime, (6) a step of forming a protective film with the composition for forming a protective film may be included on the first actinic ray-sensitive or radiation-sensitive film. A second photosensitive resin containing a resin which is different from the first active light sensitive or radiation sensitive resin composition and decomposes by the action of an acid to form a polar group on one active light sensitive or radiation sensitive film. It is preferable to include a step of forming a second actinic ray-sensitive or radiation-sensitive film with the actinic ray-sensitive or radiation-sensitive resin composition.
The composition for forming a protective film (particularly, the second actinic ray-sensitive or radiation-sensitive resin composition as a preferred form of the composition for forming a protective film) will be described in detail later.
As a method for forming a protective film on the first actinic ray-sensitive or radiation-sensitive film with the composition for forming a protective film, the first actinic ray-sensitive or sensation described in the above step (1) is used. A method similar to the method for forming the radiation film can be employed.

(7) The process of removing the upper part of the first development pattern The pattern forming method of the present invention comprises (7) the upper part of the first development pattern (the above-mentioned book) between the process (4) and the process (5). The first and second embodiments of the invention and these modifications may include a step of removing the upper portion 14a of the hardened layer 14 and the protective film 51). In this case, (7 ' It is preferable to include a step of etching the first development pattern.

The etching in the step (7 ′) may be dry etching or wet etching, but is preferably dry etching.
As a method of dry etching, JP-A-59-126506, JP-A-59-46628, 58-9108, 58-2809, 57-148706, 61-41102, etc. Mention may be made of the methods as described.

As an etching gas used for dry etching, a mixed gas containing one or more gases (main etching gas) selected from fluorine-based gas, nitrogen, ammonia, and hydrogen and oxygen gas can be preferably exemplified.
When the main etching gas is combined with oxygen gas, the organic film can be processed with anisotropy.

  Furthermore, the mixed gas in the present invention is preferably such that the mixing ratio of main etching gas and oxygen gas (main etching gas / oxygen gas) is 1/1 to 10/1 in terms of flow rate. By being within the above range, the balance between the generation of etching products (deposition film) that is likely to occur on the side wall during etching and the etching can be improved, and the growth of the deposition film on the side wall can be suppressed, and Generation of a damage layer on the outermost surface of the resist can also be suppressed. As a result, the upper part of the first development pattern can be easily removed. Among these, the mixing ratio is preferably 7/1 to 3/1 and more preferably 6/1 to 4/1 in terms of flow rate.

  In addition to the above gas, the mixed gas in the present invention includes other gases such as helium (He), neon (Ne), argon (Ar), krypton (Kr), It is preferable to further include at least one third gas selected from the group of rare gases such as xenon (Xe). In this case, the mixing ratio of the third gas and the main etching gas (third gas / main etching gas) is preferably 1/1 to 1/3 in flow rate ratio. However, when the partial pressure controllability of the etching gas can be maintained, it is not always necessary to mix the third gas.

  The internal pressure of the chamber in the etching is preferably 0.5 to 4.0 Pa, more preferably 1.0 to 4.0 Pa. When the internal pressure of the chamber is within the above range, the rectangularity of the pattern is improved, and adhesion of the deposition film to the side wall generated by etching can be suppressed. The internal pressure of the chamber can be adjusted, for example, by appropriately controlling the flow rate of the etching gas and the degree of decompression of the chamber.

  The flow rate of the mixed gas in the etching is preferably 1500 sccm or less, and more preferably 1200 sccm or less. Here, sscm means a flow rate (mL / min) in a standard state (1 atm (atmospheric pressure: 1013 hPa), 0 ° C.).

  The applied high frequency can be selected from 400 kHz, 60 MHz, 13.56 MHz, 2.45 GHz, etc., preferably 50 to 2000 W, more preferably 100 to 1000 W of RF power.

  In dry etching, the dry etching may be terminated based on an etching processing time calculated in advance, or the end point of the dry etching processing may be detected using an end point detector.

  Further, the etching may include an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The overetching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in etching, from the viewpoint of etching resistance of the upper part of the first development pattern and maintenance of the rectangularity of the pattern to be etched, and 5 to 25% It is more preferable that it is 10 to 15%.

(8) The process of removing the compound which interacts with the polar group which the resin after exposure provided on the 1st image development pattern has The pattern formation method of this invention is the said process (4), the said process (5), (8) A step of removing a compound that is provided on the first development pattern and interacts with the polar group of the exposed resin (the first and second embodiments of the present invention described above and these steps). In a modified example, it may include the removal of the surface treatment agent films 15 and 25).
In the step (8), the method is not particularly limited as long as the compound that interacts with the polar group of the exposed resin can be removed. And the like. Examples of such a solvent include the same solvents as those described later when the surface treatment agent contains a solvent. Examples of the rinsing method include the methods described in the rinsing step that may be performed after the step (3).

  As in the first and second embodiments of the present invention described above and the modifications thereof, the pattern forming method of the present invention includes (7) first step between the step (4) and the step (5). Preferably, the method includes a step of removing an upper portion of one development pattern, and (8) a step of removing a compound provided on the first development pattern and interacting with a polar group of the exposed resin. Even if the mode includes the step (8) after the step (7) (see the first and second embodiments of the present invention described above), the mode includes the step (7) after the step (8) (see above). The modified example of the first embodiment and the modified example of the second embodiment of the present invention may be used, but as described above, the process (8) is included after the process (7). Is more preferable.

(9) Step of heating the first actinic ray-sensitive or radiation-sensitive film The pattern forming method of the present invention includes (9) first step between the step (2) and the step (3). A step of heating the actinic ray-sensitive or radiation-sensitive film may be included.

The heating temperature in the step (9) is preferably 70 ° C to 130 ° C, more preferably 80 ° C to 120 ° C.
The heating time in the step (9) is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and further preferably 30 to 90 seconds.
The heating in the step (9) can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.

(10) Step of heating the first development pattern The pattern forming method of the present invention includes (10) Step of heating the first development pattern between the step (4) and the step (5). It is preferable to contain. By performing the heating, the acid generated from the compound that generates acid upon irradiation with actinic rays or radiation remaining in the intermediate exposure portion in the first development pattern is decomposed by the action of the acid to generate a polar group. It is considered that it reacts with the resin again, and the decomposition of the resin in the intermediate exposure portion is further promoted, and as a result, the pattern remaining property during double development is further improved.

The heating temperature in the step (10) is preferably 30 ° C. or more higher than the heating temperature in the step (9).
The heating temperature in the step (10) is preferably 100 ° C to 160 ° C, more preferably 110 ° C to 150 ° C.
The heating time in the step (10) is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating in the step (10) can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.

Moreover, it is also preferable that the pattern formation method of this invention includes a heating process (Post Bake) after the said process (5).
By this heating process, the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed. This heating step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually for 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

  The organic developer, alkali developer, and / or rinse solution used in the present invention preferably have few impurities such as various fine particles and metal elements. In order to obtain chemicals with few impurities, these chemicals are manufactured in a clean room, and the impurities are reduced by filtering with various filters such as Teflon filters, polyolefin filters, ion exchange filters, etc. It is preferable. As for the metal element, the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn are all preferably 10 ppm or less, and preferably 5 ppm or less. More preferred.

  In addition, the storage container for the developer and the rinsing liquid is not particularly limited, and containers such as polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin that are used for electronic materials can be used as appropriate. In order to reduce impurities eluted from the container, it is also preferable to select a container having a small amount of components eluted from the inner wall of the container into the chemical solution. Examples of such a container include a container whose inner wall is a perfluoro resin (for example, FluoroPure PFA composite drum manufactured by Entegris (wetted inner surface; PFA resin lining), steel drum can manufactured by JFE (wetted inner surface; zinc phosphate coating)) ) And the like.

  Of course, the pattern formed in the present invention is preferably used as an etching mask in a semiconductor manufacturing process. Further, the present invention can also be applied as various other uses, for example, as a guide pattern for self-assembled (DSA) patterning. (See, for example, WO2012 / 046770A and ACS Nano Vol.4 No.8 Pages4815-4823 for the guide pattern of DSA patterning.

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

<Surface treatment agent>
Hereinafter, the surface treatment agent used in the present invention (hereinafter also referred to as “the surface treatment agent of the present invention”) will be described in detail.

The surface treatment agent contains a compound that interacts with the polar group of the exposed resin (hereinafter also referred to as “compound (A)”).
The compound (A) is not particularly limited as long as it interacts with the polar group of the resin after exposure, but at least one chemical bond of ionic bond, hydrogen bond, covalent bond and dipole interaction with the polar group Preferably, the compound can form an ionic bond or a covalent bond. As described above, the interaction between the resin (A) and the surface treatment agent changes the solubility of the resin (A), thereby improving the pattern survivability and roughness performance in double development. The ionic bond is intended for electrostatic interaction between a cation and an anion, and includes salt formation.

As the compound (A), at least one selected from the group consisting of an onium salt compound, a nitrogen-containing compound, and a phosphorus-based compound can be given in that the effect of the present invention is excellent.
The compound (A) may be in the form of a low molecular compound or a polymer compound, but is preferably in the form of a polymer compound.

  Hereinafter, among these compounds, first, the form of the low-molecular compound will be described in detail.

[Low molecular compound]
(Onium salt compound)
As the onium salt compound, a compound having an onium salt structure is intended. The onium salt structure refers to a salt structure generated by a coordinate bond between an organic component and a Lewis base. The onium salt compound mainly forms an interaction with the polar group by an ionic bond. For example, when the polar group is a carboxyl group, a cation in the onium salt compound forms an electrostatic interaction (forms an ionic bond) with the carboxyl-derived carboxyl anion (COO ⁻ ).
The type of onium salt structure is not particularly limited, and examples thereof include structures such as ammonium salts, phosphonium salts, oxonium salts, sulfonium salts, selenonium salts, carbonium salts, diazonium salts, iodonium salts having a cation structure shown below. .
In addition, the cation in the onium salt structure includes those having a positive charge on the hetero atom of the heteroaromatic ring. Examples of such onium salts include pyridinium salts and imidazolium salts.
In the present specification, the above pyridinium salt and imidazolium salt are also included as one embodiment of the ammonium salt.

The onium salt compound may be a polyvalent onium salt compound having two or more onium ion atoms in one molecule from the viewpoint that the effect of the present invention is more excellent. As the polyvalent onium salt compound, a compound in which two or more cations are linked by a covalent bond is preferable.
Examples of the polyvalent onium salt compound include diazonium salts, iodonium salts, sulfonium salts, ammonium salts, and phosphonium salts. Of these, diazonium salts, iodonium salts, sulfonium salts, and ammonium salts are preferable from the viewpoint of more excellent effects of the present invention, and ammonium salts are more preferable from the viewpoint of stability.

The anion (anion) contained in the onium salt compound (onium salt structure) may be any anion as long as it is an anion, but it may be a monovalent ion or a polyvalent ion. .
For example, examples of the monovalent anion include a sulfonate anion, a formate anion, a carboxylate anion, a sulfinate anion, a boron anion, a halide ion, a phenol anion, an alkoxy anion, and a hydroxide ion. Examples of the divalent anion include oxalate ion, phthalate ion, maleate ion, fumarate ion, tartaric acid ion, malate ion, lactate ion, sulfate ion, diglycolate ion, and 2,5-flange. Examples thereof include carboxylate ions.
More specifically, monovalent anions include Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ and CH _3. COO ⁻ , CF ₃ COO ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF _{6 ^{-, TaF 6 -, F (}} HF) n -, (CN) 2 n -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 n -, C 3 F 7 COO -, (CF 3 _{^{SO 2) (CF 3 CO)}} N -, C 9 H 19 COO -, (CH 3) 2 PO 4 -, (C 2 H 5) 2 PO 4 -, C 2 H 5 OSO 3 -, C 6 H 13 _{^{OSO 3 -, C 8 H 17}} OSO 3 -, CH 3 ( _{C 2 H 4) 2 OSO 3} -, C 6 H 4 (CH 3) SO 3 -, (C 2 F 5) 3 PF 3 -, CH 3 CH (OH) COO -, B (C 6 F 5) 4 _{^{-, FSO 3 -, C 6}} H 5 O -, (CF 3) 2 CHO -, (CF 3) 3 CHO -, C 6 H 3 (CH 3) 2 O -, C 2 H 5 OC 6 H 4 COO ^- and the like.
Among them, preferred are sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{— and the} like, more preferably containing a carbon atom. Is an organic anion.

  Below, the specific example of the cation contained in an onium salt structure is illustrated.

  Below, the specific example of the anion contained in an onium salt structure is illustrated.

  Specific examples of the onium salt structure are illustrated below.

A preferred embodiment of the onium salt compound is composed of the onium salt compound represented by the formula (1-1) and the onium salt compound represented by the formula (1-2) in that the effect of the present invention is more excellent. There may be mentioned at least one selected from the group.
In addition, the onium salt compound represented by Formula (1-1) may use only 1 type, or may use 2 or more types together. Moreover, the onium salt compound represented by Formula (1-2) may use only 1 type, or may use 2 or more types together. Moreover, you may use together the onium salt compound represented by Formula (1-1), and the onium salt compound represented by Formula (1-2).

In formula (1-1), M represents a nitrogen atom, a phosphorus atom, a sulfur atom, or an iodine atom. Especially, a nitrogen atom is preferable at the point which the effect of this invention is more excellent.
R each independently represents a hydrogen atom, an aliphatic hydrocarbon group that may contain a hetero atom, an aromatic hydrocarbon group that may contain a hetero atom, or a group in which two or more of these are combined. .
The aliphatic hydrocarbon group may be linear, branched or cyclic. In addition, the number of carbon atoms contained in the aliphatic hydrocarbon group is not particularly limited, but 1 to 15 is preferable and 1 to 5 is more preferable in that the effect of the present invention is more excellent.
Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkene group, an alkyne group, or a group obtained by combining two or more of these.
The aliphatic hydrocarbon group may contain a hetero atom. That is, it may be a heteroatom-containing hydrocarbon group. The type of hetero atom contained is not particularly limited, and examples thereof include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a tellurium atom. For _{example, -Y 1 H, -Y 1 -} , - N (R a) -, - C (= Y 2) -, - CON (R b) -, - C (= Y 3) Y 4 -, - SO _{t -, - SO 2 N (} R c) -, it includes in the manner of a halogen atom, or a group composed of a combination of two or more of these.
Y _{1 to} Y ₄ are each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. Of these, an oxygen atom and a sulfur atom are preferred because they are easier to handle.
Said R _<a> , R _<b> , R _<c> is each independently selected from a hydrogen atom or a C1-C20 hydrocarbon group.
t represents an integer of 1 to 3.

The number of carbon atoms contained in the aromatic hydrocarbon group is not particularly limited, but 6 to 20 is preferable and 6 to 10 is more preferable in that the effect of the present invention is more excellent.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
The aromatic hydrocarbon group may contain a hetero atom. The aspect in which a hetero atom is contained is as described above. In addition, when a hetero atom is contained in an aromatic hydrocarbon group, you may comprise an aromatic heterocyclic group.

  As a preferred embodiment of R, an alkyl group which may contain a heteroatom, an alkene group which may contain a heteroatom, or a cycloalkyl group which may contain a heteroatom from the viewpoint that the effects of the present invention are more excellent. And an aryl group which may contain a hetero atom.

  A plurality of R may be bonded to each other to form a ring. Although the kind of ring formed is not specifically limited, For example, a 5-6 membered ring structure can be mentioned.

Moreover, the ring formed may have aromaticity, for example, the cation of the onium salt compound represented by Formula (1-1) is a pyridinium ring represented by Formula (10) below. There may be. Furthermore, a hetero atom may be contained in a part of the ring formed. For example, the cation of the onium salt compound represented by the formula (1-1) is represented by the following formula (11). It may be an imidazolium ring.
In addition, the definition of R in Formula (10) and Formula (11) is as above-mentioned.
In formula (10) and formula (11), Rv each independently represents a hydrogen atom or an alkyl group. A plurality of Rv may be bonded to each other to form a ring.

X ⁻ represents a monovalent anion. The definition of monovalent anion is as described above.

  In formula (1-1), n represents an integer of 2 to 4. In addition, when M is a nitrogen atom or a phosphorus atom, n represents 4, when M is a sulfur atom, n represents 3, and when M is an iodine atom, n represents 2.

The definitions of M, R and X ⁻ in formula (1-2) are as described above. In formula (1-2), two X ⁻ are included.
L represents a divalent linking group. As the divalent linking group, a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group or a propylene group), substituted or unsubstituted divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms such as a phenylene group.), - O -, - S -, - SO 2 -, - N (R) - (R: alkyl group), -CO-, -NH-, -COO-, -CONH-, or a group in which two or more of these are combined (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.), and the like.
Among these, a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group is preferable in that the effect of the present invention is more excellent.

  In formula (1-2), m represents the integer of 1-3 each independently. In addition, when M is a nitrogen atom or a phosphorus atom, m represents 3, when M is a sulfur atom, m represents 2, and when M is an iodine atom, m represents 1.

(Nitrogen-containing compounds)
A nitrogen-containing compound intends a compound containing a nitrogen atom. In the present specification, the nitrogen-containing compound does not include the onium salt compound. The nitrogen-containing compound mainly forms an interaction between a nitrogen atom in the compound and the polar group. For example, when the polar group is a carboxyl group, it interacts with a nitrogen atom in the nitrogen-containing compound to form a salt.
As said nitrogen-containing compound, the compound represented by following General formula (6) is mentioned, for example.

In the general formula (6), R ⁴ and R ⁵ are each independently a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, a chain hydrocarbon group having 1 to 30 carbon atoms, or a carbon number of 3 It is a group formed by combining 2 or more types of -30 alicyclic hydrocarbon groups, C6-C14 aromatic hydrocarbon groups, or these groups. R ⁶ is a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, an n-valent chain hydrocarbon group having 1 to 30 carbon atoms, an n-valent alicyclic hydrocarbon group having 3 to 30 carbon atoms, An n-valent aromatic hydrocarbon group having 6 to 14 carbon atoms or an n-valent group formed by combining two or more of these groups. n is an integer of 1 or more. However, when n is 2 or more, the plurality of R ⁴ and R ⁵ may be the same or different. Further, any two of R ^{4 to} R ⁶ may be bonded to form a ring structure together with the nitrogen atom to which each is bonded.

Examples of the C1-C30 chain hydrocarbon group represented by R ⁴ and R ⁵ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group and the like.
Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ⁴ and R ⁶ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a norbornyl group.
Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ⁴ and R ⁶ include a phenyl group, a tolyl group, and a naphthyl group.
Examples of the group formed by combining two or more of these groups represented by R ⁴ and R ⁵ include aralkyl groups having 6 to 12 carbon atoms such as benzyl, phenethyl, naphthylmethyl, and naphthylethyl groups. Can be mentioned.

Examples of the n-valent chain hydrocarbon group having 1 to 30 carbon atoms represented by R ⁶ include groups exemplified as the chain hydrocarbon group having 1 to 30 carbon atoms represented by R ⁴ and R ^5. And a group obtained by removing (n-1) hydrogen atoms from the same group.
Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ⁶ include the same groups as those exemplified as the cyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ⁴ and R ^5. And a group obtained by removing (n-1) hydrogen atoms from the group.
Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ⁶ are the same as those exemplified as the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ⁴ and R ⁵ . And a group obtained by removing (n-1) hydrogen atoms from the group.
The group formed by combining two or more of these groups represented by R ⁶ is the same as the group exemplified as a group formed by combining two or more of these groups represented by R ⁴ and R ⁵ , for example. And a group obtained by removing (n-1) hydrogen atoms from the group.

The group represented by R ^{4 to} R ⁶ may be substituted. Specific examples of the substituent include a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a hydroxyl group, a carboxy group, a halogen atom, and an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Moreover, as an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example.

Examples of the compound represented by the above formula (6) include (cyclo) alkylamine compounds, nitrogen-containing heterocyclic compounds, amide group-containing compounds, urea compounds and the like.
Examples of (cyclo) alkylamine compounds include compounds having one nitrogen atom, compounds having two nitrogen atoms, compounds having three or more nitrogen atoms, and the like.
Examples of (cyclo) alkylamine compounds having one nitrogen atom include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, 1-aminodecane, cyclohexylamine and the like. ;
Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, Di (cyclo) alkylamines such as dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri- tri (cyclo) alkylamines such as n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine;
Substituted alkylamines such as triethanolamine;
Aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, N, N-dibutylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2 , 4,6-tri-tert-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropylaniline, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- ( And aromatic amines such as 4-aminophenyl) -2- (4-hydroxyphenyl) propane.

  Examples of the (cyclo) alkylamine compound having two nitrogen atoms include ethylenediamine, tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, and 4,4 ′. -Diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 1,4-bis [ 1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, bis (2-dimethylaminoethyl) ether, bis ( 2-diethylaminoethyl) ether, 1- (2-hydroxyethyl) 2-imidazolidinone, 2-quinoxalinium linoleic, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, and the like.

  Examples of the (cyclo) alkylamine compound having three or more nitrogen atoms include polymers such as polyethyleneimine, polyallylamine, and 2-dimethylaminoethylacrylamide.

  Examples of the nitrogen-containing heterocyclic compound include nitrogen-containing aromatic heterocyclic compounds and nitrogen-containing aliphatic heterocyclic compounds.

As a nitrogen-containing aromatic heterocyclic compound,
For example, imidazoles such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-methyl-1H-imidazole ;
Pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, Examples thereof include pyridines such as quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, and 2,2 ′: 6 ′, 2 ″ -terpyridine.

Examples of the nitrogen-containing aliphatic heterocyclic compound include piperazines such as piperazine and 1- (2-hydroxyethyl) piperazine;
Pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, proline, piperidine, piperidine ethanol, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine , 3- (N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, and the like.

Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, and Nt-butoxy. Carbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, (S)-(- ) -1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl-4-hydroxypiperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonylpyrrolidine Perazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′- Diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N ′, N′-tetra-t-butoxycarbonylhexamethylenediamine, N, N′-di-t-butoxycarbonyl- 1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl-1,9-diaminononane, N, N′-di -T-butoxycarbonyl-1,10-diaminodecane, N, N'-di-t-butoxycarbonyl-1,12-diaminododecane, N, N'-di-t-butyl Nt such as toxoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, etc. A butoxycarbonyl group-containing amino compound;
Formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamantylamine, isocyanuric Examples include acid tris (2-hydroxyethyl).

  Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea and the like. Is mentioned.

  Of these, (cyclo) alkylamine compounds and nitrogen-containing aliphatic heterocyclic compounds are preferable, and 1-aminodecane, di-n-octylamine, tri-n-octylamine, tetramethylethylenediamine, N, N-dibutylaniline, Proline is more preferred.

As a preferred embodiment of the nitrogen-containing compound, a nitrogen-containing compound containing a plurality (two or more) of nitrogen atoms (multivalent nitrogen-containing compound) is preferable. In particular, an embodiment including three or more is preferable, and an embodiment including four or more is more preferable.
Moreover, as another suitable aspect of a nitrogen-containing compound, the compound represented by Formula (3) is mentioned at the point which the effect of this invention is more excellent.

In Formula (3), A represents a single bond or an n-valent organic group.
n represents an integer of 2 or more.
Specific examples of A include a single bond, a group represented by the following formula (1A), a group represented by the following formula (1B),

—NH—, —NR _W —, —O—, —S—, carbonyl group, alkylene group, alkenylene group, alkynylene group, cycloalkylene group, aromatic group, heterocyclic group, and combinations of two or more thereof A preferred example is an n-valent organic group consisting of a group. Here, in the above formulas, R _W represents an organic group, preferably an alkyl group, an alkylcarbonyl group, an alkylsulfonyl group. Further, in the above combination, heteroatoms are not linked to each other.
Of these, an aliphatic hydrocarbon group (an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group), a group represented by the above formula (1B), —NH—, and —NR _W — are preferable.

Here, the alkylene group, alkenylene group, and alkynylene group preferably have 1 to 40 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 2 to 12 carbon atoms. The alkylene group may be linear or branched and may have a substituent. Here, the cycloalkylene group preferably has 3 to 40 carbon atoms, more preferably 3 to 20 carbon atoms, and still more preferably 5 to 12 carbon atoms. The cycloalkylene group may be monocyclic or polycyclic, and may have a substituent on the ring.
The aromatic group may be monocyclic or polycyclic, and includes non-benzene aromatic groups. Monocyclic aromatic groups include benzene, pyrrole, furan, thiophene, and indole residues. Polycyclic aromatic groups include naphthalene, anthracene, tetracene, and benzofuran. Examples include benzothiophene residues and the like. The aromatic group may have a substituent.

  The n-valent organic group may have a substituent, and the kind thereof is not particularly limited, but an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, an alkenyl group, an alkenyloxy group Alkenylcarbonyl group, alkenylcarbonyloxy group, alkenyloxycarbonyl group, alkynyl group, alkynyleneoxy group, alkynylenecarbonyl group, alkynylenecarbonyloxy group, alkynyleneoxycarbonyl group, aralkyl group, aralkyloxy group, aralkylcarbonyl group Aralkylcarbonyloxy group, aralkyloxycarbonyl group, hydroxyl group, amide group, carboxyl group, cyano group, fluorine atom and the like can be mentioned as examples.

B represents a single bond, an alkylene group, a cycloalkylene group, or an aromatic group, and the alkylene group, the cycloalkylene group, and the aromatic group may have a substituent. Here, the explanation of the alkylene group, cycloalkylene group, and aromatic group is the same as described above.
However, A and B are not both single bonds.

R _z each independently represents a hydrogen atom, an aliphatic hydrocarbon group that may contain a heteroatom, or an aromatic hydrocarbon group that may contain a heteroatom.
Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. The number of carbon atoms contained in the aliphatic hydrocarbon group is not particularly limited, but 1 to 20 is preferable and 1 to 10 is more preferable in that the effect of the present invention is more excellent.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
The aliphatic hydrocarbon group and the aromatic hydrocarbon group may contain a hetero atom. The definition and preferred embodiment of the heteroatom are the same as the definition of the heteroatom described in the above formula (1-1).
In addition, aliphatic hydrocarbon groups and aromatic hydrocarbon groups include substituents (for example, hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups and other functional groups, alkoxy groups, halogens, Atoms) may be included.
n preferably represents an integer of 2 to 8, more preferably an integer of 3 to 8.
In addition, it is preferable that the compound represented by the said Formula (3) has three or more nitrogen atoms. In this embodiment, when n is 2, A contains at least one nitrogen atom. That A contains a nitrogen atom includes, for example, at least one selected from the group consisting of the group represented by the above formula (1B), —NH—, and —NR _W —.

  Below, the compound represented by Formula (3) is illustrated.

(Phosphorus compounds)
A phosphorus compound is a compound containing -P <(phosphorus atom). The phosphorus compound does not include an onium salt compound. The phosphorus compound mainly forms an interaction between a phosphorus atom in the compound and the polar group. For example, when the polar group is a carboxyl group, it interacts with the phosphorus atom in the phosphorus compound to form a salt.
The phosphorus compound only needs to include at least one phosphorus atom, and may include a plurality (two or more).
The molecular weight of the phosphorus compound is not particularly limited, but is preferably 70 to 500, more preferably 70 to 300, from the viewpoint that the effect of the present invention is more excellent.

  A preferred embodiment of the phosphorus compound is selected from the group consisting of the compound represented by the following formula (4-1) and the compound represented by the formula (4-2) in that the effect of the present invention is more excellent. The phosphorus compound is preferable.

In the formula (4-1) and formula (4-2), R _W are each independently an aliphatic contain a hetero atom hydrocarbon group, an aromatic may contain a hetero atom hydrocarbon group Or represents a group selected from the group consisting of groups obtained by combining two or more of these.
The aliphatic hydrocarbon group may be linear, branched or cyclic. In addition, the number of carbon atoms contained in the aliphatic hydrocarbon group is not particularly limited, but 1 to 15 is preferable and 1 to 5 is more preferable in that the effect of the present invention is more excellent.
Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkene group, an alkyne group, or a group obtained by combining two or more of these.
The number of carbon atoms contained in the aromatic hydrocarbon group is not particularly limited, but 6 to 20 is preferable and 6 to 10 is more preferable in that the effect of the present invention is more excellent.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
The aliphatic hydrocarbon group and the aromatic hydrocarbon group may contain a hetero atom. The definition and preferred embodiment of the heteroatom are the same as the definition of the heteroatom described in the above formula (1-1). In addition, it is preferable that an oxygen atom is contained as a hetero atom, and it is preferable that it is contained in the aspect of -O-.

L _W represents a divalent linking group. As the divalent linking group, a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group or a propylene group), substituted or unsubstituted divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, for example, an arylene group.), - O -, - S -, - SO 2 -, - N (R) - (R: alkyl group), -CO-, -NH-, -COO-, -CONH-, or a group in which two or more of these are combined (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.), and the like.
Among these, a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group is preferable in that the effect of the present invention is more excellent.

  Below, the specific example of a phosphorus compound is illustrated.

As described above, the compound (A) may be in the form of a low molecular compound or a polymer compound, but from the viewpoint of performing multipoint interaction with a polar group, the compound (A) is in the form of a polymer compound. Preferably there is.
Hereinafter, among the onium salt compound, the nitrogen-containing compound, and the phosphorus compound, the form of the polymer compound will be described in detail.

(Onium salt compound)
Among the onium salt compounds, the polymer compound includes a polymer having an onium salt. The polymer having an onium salt intends a polymer having an onium salt structure in a side chain or main chain. In particular, a polymer having a repeating unit having an onium salt structure is preferable.
The definition of the onium salt structure is as described above, and the definitions of the cation and the anion are also synonymous.

  A preferred embodiment of the polymer having an onium salt includes a polymer having a repeating unit represented by the formula (5-1) in that the effect of the present invention is more excellent.

In formula (5-1), R _p represents a hydrogen atom or an alkyl group. The number of carbon atoms contained in the alkyl group is not particularly limited, but 1 to 20 is preferable and 1 to 10 is more preferable in that the effect of the present invention is more excellent.
L _p represents a divalent linking group. Definition of the divalent linking group represented by L _p is the same as the definition of L, represented by the above formula (1-2).
Among these, L _p is an alkylene group, an arylene group, —COO—, or a group in which two or more of these are combined (—arylene group—alkylene group—, —COO—) in that the effect of the present invention is more excellent. Alkylene group- etc.) is preferable, and an alkylene group is more preferable.

A _p represents a group having an onium salt structure, specifically, by removing one hydrogen atom from an onium salt represented by any one of formulas (1-1) and (1-2) remaining It is preferable to represent a group. The residue refers to a group having a structure in which one hydrogen atom is extracted from any position in the structural formula showing an onium salt and can be bonded to L _p . Usually, one of the hydrogen atoms in R is withdrawn and becomes a group having a structure capable of binding to the above L _p .
The definition of each group in Formula (1-1) and Formula (1-2) is as described above.

  The content of the repeating unit represented by the above formula (5-1) in the polymer is not particularly limited, but is 30 to 100 mol% with respect to all the repeating units in the polymer in that the effect of the present invention is more excellent. Is preferable, and 50 to 100 mol% is more preferable.

  Although the weight average molecular weight of the said polymer is not restrict | limited in particular, 1000-30000 are preferable and 1000-10000 are more preferable at the point which the effect of this invention is more excellent.

  The weight average molecular weight and dispersity (weight average molecular weight / number average molecular weight) of the polymer are defined as polystyrene converted values by GPC measurement. In the present specification, the weight average molecular weight and the degree of dispersion are, for example, HLC-8120 (manufactured by Tosoh Corporation) and TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm) as a column. ) Can be determined by using THF (tetrahydrofuran) as the eluent.

  As a suitable aspect of the repeating unit represented by Formula (5-1), the repeating unit represented by Formula (5-2) is mentioned.

In formula (5-2), the definitions of R, R _p , L _p and X ⁻ are as described above.

  Furthermore, as a suitable aspect of the repeating unit represented by Formula (5-2), the repeating unit represented by Formula (5-3)-Formula (5-5) is mentioned.

In formula (5-3), the definitions of R, R _p , and X ⁻ are as described above.
In formula (5-4), the definitions of R, R _p , and X ⁻ are as described above.
A represents -O-, -NH-, or -NR-. The definition of R is the same as the definition of R in the above formula (1-1).
B represents an alkylene group.
In formula (5-5), the definitions of R, R _p , and X ⁻ are as described above.

(Nitrogen-containing compounds)
Among the nitrogen-containing compounds, the polymer compound is preferably a polymer having an amino group in that the effect of the present invention is more excellent. In the present specification, the “amino group” is a concept including a primary amino group, a secondary amino group, and a tertiary amino group. The secondary amino group also includes cyclic secondary amino groups such as pyrrolidino group, piperidino group, piperazino group, hexahydrotriazino group and the like.
The amino group may be contained in either the main chain or the side chain of the polymer.
Specific examples of the side chain when the amino group is contained in a part of the side chain are shown below. In addition, * represents the connection part with a polymer and / or an oligomer residue.

  Examples of the polymer having an amino group include polyallylamine, polyethyleneimine, polyvinylpyridine, polyvinylimidazole, polypyrimidine, polytriazole, polyquinoline, polyindole, polypurine, polyvinylpyrrolidone, and polybenzimidazole.

  As a suitable aspect of the polymer which has an amino group, the polymer which has a repeating unit represented by Formula (2) is mentioned.

In formula (2), R ¹ represents a hydrogen atom or an alkyl group. The number of carbon atoms contained in the alkyl group is not particularly limited, but 1 to 4 is preferable and 1 to 2 is more preferable in that the effect of the present invention is more excellent.
R ² and R ³ are each independently a hydrogen atom, an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, or an aromatic group that may contain a hetero atom. Represents.
The number of carbon atoms contained in the alkyl group and cycloalkyl group is not particularly limited, but is preferably 1-20, and more preferably 1-10.
Examples of the aromatic group include aromatic hydrocarbons and aromatic heterocyclic groups.
The alkyl group, cycloalkyl group and aromatic group may contain a hetero atom. The definition and preferred embodiment of the heteroatom are the same as the definition of the heteroatom described in the above formula (1-1).
In addition, the alkyl group, cycloalkyl group, and aromatic group include substituents (eg, hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group functional group, alkoxy group, halogen Atoms) may be included.

L _a represents a divalent linking group. Definition of the divalent linking group represented by L _a is the same definition of L represented by the aforementioned formula (1-2).
Among them, as La, in which the effect of the present invention is more excellent, as L _a , an alkylene group, an arylene group, —COO—, and a group in which two or more of these are combined (-arylene group-alkylene group—, —COO— Alkylene group- etc.) is preferable, and an alkylene group is more preferable.

Incidentally, the group represented by the above R ¹ to R ^3, and, in the divalent linking group represented by L _a, substituent group (e.g., hydroxyl, etc.) may be further substituted.

  Below, the repeating unit represented by Formula (2) is illustrated.

The content of the repeating unit represented by the above formula (2) in the polymer is not particularly limited, but is preferably 40 to 100 mol% with respect to all the repeating units in the polymer in that the effect of the present invention is more excellent. 70 to 100 mol% is more preferable.
In addition, other repeating units other than the repeating unit represented by Formula (2) may be contained in the polymer.

  Although the weight average molecular weight of the polymer which has an amino group is not restrict | limited in particular, 1000-30000 are preferable and 1000-10000 are more preferable at the point which the effect of this invention is more excellent.

The surface treatment agent preferably contains a basic compound as the compound (A). In the present invention, the basic compound is a polar group contained in the resin in the actinic ray-sensitive or radiation-sensitive resin composition, for example, a —COOH site, more specifically, a repeating unit corresponding to a methacrylic acid structure. , A compound that forms a salt by an acid-base interaction, and specifically includes the above-mentioned nitrogen-containing compounds.
It is preferable that a surface treating agent contains resin which has a repeating unit which has a basic functional group as a basic compound. The basic compound is preferably a compound having a primary or secondary amino group. As a result, the compound (A) can form a covalent bond or an ionic bond with the polar group (preferably other functional group in the resin) of the resin after exposure, and the side wall of the first development pattern (of the present invention described above) can be formed. In the first and second embodiments and these modified examples, the cured layers 14 and 24) can be further cured, so that the effect of the present invention can be further improved. From this viewpoint, in the compound represented by the above formula (6), at least one of R ⁴ and R ⁵ is preferably a hydrogen atom, and in the compound represented by the above formula (3), two At least one of Rz is preferably a hydrogen atom, and in the polymer having a repeating unit represented by the above formula (2), at least one of R ² and R ³ is preferably a hydrogen atom.

  The compound (A) is preferably soluble in the alkali developer in the step (5), and examples thereof include water-soluble low molecular weight compounds and resins. Specific examples include triethylamine, ethylenediamine, Preferred examples include N, N′-dimethylethylenediamine, ammonia, poly (aminoethyl methacrylate), polyallylamine and the like.

When the surface treating agent contains a solvent, specific examples and preferred examples of the solvent include water, those in the developer mentioned in the above step (3), and rinse that may be carried out after the above step (3). In the aforementioned rinsing liquid mentioned in the process, the film dissolution rate at 23 ° C. when the first actinic ray-sensitive or radiation-sensitive film is in contact with the unexposed film as the solvent is 0.1 nm / It is particularly preferable to use a solvent that is s or less.
Specifically, an alcohol solvent or an ether solvent is preferable. Specifically, an alkyl group having 3 or more carbon atoms (preferably having 5 to 10 carbon atoms), a cycloalkyl group (preferably having 5 to 10 carbon atoms), and an aralkyl group (preferably having 7 to 10 carbon atoms are preferable). ) And / or dialkyl ethers. Water is also applicable as a solvent.
The film dissolution rate represents the amount of decrease in film thickness per unit time when the solution is brought into contact with the first actinic ray-sensitive or radiation-sensitive film. The film dissolution rate was measured on the developer at room temperature (23 ° C.) measured using a QCM (quartz crystal microbalance) sensor after the first actinic ray-sensitive or radiation-sensitive film was formed on the substrate. On the other hand, it is the average dissolution rate (thickness reduction rate) when the membrane is immersed for 1000 seconds.
The solvent in the surface treatment agent is preferably a ketone solvent or an ester solvent. In this case, it is difficult for the surface treatment agent and the highly photosensitive portion to interact with each other, and a cured layer tends not to be formed on the top of the highly photosensitive portion. For this reason, the step (5) can be easily performed without performing an etching step or the like for the purpose of removing the hardened layer formed on the high photosensitive portion. This is because the ketone solvent or ester solvent easily penetrates into the intermediate photosensitive part, but hardly penetrates into the highly sensitive part with high polarity. This is thought to be because it easily penetrates selectively only to the part.
As the solvent in the surface treatment agent, it is preferable to use a solvent having a reduced peroxide content, thereby improving the storage stability of the surface treatment agent.
In order to suppress the generation of peroxide, the solvent may contain a stabilizer (for example, an antioxidant).
The content of the peroxide in the solvent is preferably 2.0 mmol% or less, more preferably 1.0 mmol% or less, still more preferably 0.5 mmol% or less, and the solvent is contained in excess. It is particularly preferable that the oxide is not substantially contained.

<First actinic ray-sensitive or radiation-sensitive resin composition>
The first actinic ray-sensitive or radiation-sensitive resin composition contains a resin that decomposes by the action of an acid to generate a polar group.
In one embodiment, the first actinic ray-sensitive or radiation-sensitive resin composition is at least one of a compound that generates an acid upon irradiation with actinic rays or radiation, a hydrophobic resin, a basic compound, and a surfactant. May further be contained.
Hereinafter, each of these components will be described.

[Resin that decomposes by the action of acid to produce polar groups]
A resin that decomposes by the action of an acid to generate a polar group (hereinafter also referred to as “resin (A)”) is a resin that changes its polarity by the action of an acid, and has a solubility in an organic solvent developer by the action of an acid. Is a resin whose solubility in an alkaline developer is increased.
Resin (A) is a group (hereinafter also referred to as “acid-decomposable group”) that decomposes by the action of an acid to generate a polar group in the main chain or side chain of the resin, or both of the main chain and side chain. It is preferable to have.
The acid-decomposable group preferably has a structure protected by a group capable of decomposing and leaving a polar group by the action of an acid.

  The polar group is not particularly limited as long as it is a group that is hardly soluble or insoluble in a developer containing an organic solvent, but a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group. , Sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkyl Sulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group and other acidic groups (2.38 mass% tetra, conventionally used as a resist developer) Methylan Group dissociates in onium hydroxide aqueous solution), or alcoholic hydroxyl group.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group). An aliphatic alcohol substituted with a functional group (for example, a fluorinated alcohol group (such as a hexafluoroisopropanol group)) is excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa of 12 or more and 20 or less.
Preferred polar groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.
A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
Examples of the group capable of leaving by the action of 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 the like.

In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The alkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms.
The cycloalkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The number of carbon atoms is preferably 3-20.
The aryl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms.
The aralkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms.
The alkenyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms.
The ring formed by combining R ₃₆ and R ₃₇ is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferable.
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.

[Repeating unit having acid-decomposable group]
The resin (A) preferably has a repeating unit having an acid-decomposable group.
In one embodiment, the resin (A) contains, as a repeating unit having an acid-decomposable group, a repeating unit (AI) that is decomposed by an acid to generate a carboxyl group (hereinafter also referred to as “repeating unit (AI)”). It is preferable to have a repeating unit represented by the following general formula (aI) or (aI ′).

In general formulas (aI) and (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 represents an alkyl group or a cycloalkyl group. Two of Rx _{1 to} Rx ₃ may combine to form a ring structure. The ring structure may contain a hetero atom such as an oxygen atom in the ring.
Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and a phenylene group. In the formula, Rt represents an alkylene group or a cycloalkylene group.

T in the general formula (aI) is preferably a single bond or a —COO—Rt— group, more preferably a —COO—Rt— group, from the viewpoint of insolubilization of the resist with respect to the organic solvent developer. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.
T in the general formula (aI ′) is preferably a single bond.

The alkyl group of _Xa1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
The alkyl group for _Xa1 preferably has 1 to 4 carbon atoms, and is preferably a methyl group.
X _a1 is preferably a hydrogen atom or a methyl group.
The alkyl group for Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched.
Examples of the cycloalkyl group of Rx ₁ , Rx ₂ and Rx ₃ include polycyclic rings such as a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group. Are preferred.
The ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ includes a monocyclic cycloalkane ring such as cyclopentyl ring and cyclohexyl ring, norbornane ring, tetracyclodecane ring, tetracyclododecane ring, adamantane ring A polycyclic cycloalkyl group such as is preferable. A monocyclic cycloalkane ring having 5 or 6 carbon atoms is particularly preferable.
Rx ₁ , Rx ₂ and Rx ₃ are preferably each independently an alkyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a cycloalkyl group (3 to 8 carbon atoms), a halogen atom, an alkoxy group (carbon). Number 1-4), a carboxyl group, an alkoxycarbonyl group (carbon number 2-6) etc. are mentioned, and carbon number 8 or less is preferable. Among these, from the viewpoint of further improving the dissolution contrast with respect to a developer containing an organic solvent before and after acid decomposition, a substituent having no hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom is more preferable ( For example, it is more preferable that it is not an alkyl group substituted with a hydroxyl group, etc.), a group consisting of only a hydrogen atom and a carbon atom is more preferable, and a linear or branched alkyl group or a cycloalkyl group is particularly preferable. preferable.

Specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited to these specific examples.
In specific examples, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb are each an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, sec -Butyl group, t-butyl group, etc.). Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Z represents a substituent, and when a plurality of Zs are present, the plurality of Zs may be the same as or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and preferred examples of the substituent that each group such as Rx _{1 to} Rx ₃ may have.

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

In one embodiment, the resin (A) preferably contains, as a repeating unit having an acid-decomposable group, a repeating unit having a total of 4 to 9 carbon atoms at the site decomposed by the acid. More preferably, in the above-described general formula (aI), the —C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) moiety has 4 to 9 carbon atoms.
More preferably, in the general formula (aI), all of Rx ₁ , Rx ₂ and Rx ₃ are methyl groups or ethyl groups, or an aspect represented by the following general formula (aII).

In general formula (aII),
R ₃₁ represents a hydrogen atom or an alkyl group.
R ₃₂ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a sec-butyl group.
R ₃₃ represents an atomic group necessary for forming a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which R ₃₂ is bonded. In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom.
Here, the total number of carbon atoms of R ₃₂ and R ₃₃ is 8 or less.

The alkyl group for R ₃₁ may have a substituent, and examples of the substituent include a fluorine atom and a hydroxyl group.
R ₃₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₃₂ is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl group.

The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably a 3- to 8-membered ring, and more preferably a 5- or 6-membered ring.
In the monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom, examples of the hetero atom that can form the ring include an oxygen atom and a sulfur atom. Examples of the group having a hetero atom include a carbonyl group and the like. Can be mentioned. However, the group having a hetero atom is preferably not an ester group (ester bond).
The monocyclic alicyclic hydrocarbon structure formed by R ₃₃ together with the carbon atom is preferably formed only from the carbon atom and the hydrogen atom.
In another embodiment, the resin (A) is a repeating unit having an acid-decomposable group and a repeating unit having an acid-decomposing site containing 10 to 20 carbon atoms and a polycyclic structure. Unit (aIII) may be included.
As the repeating unit (aIII) having 10 to 20 carbon atoms in the acid decomposition site and containing a polycyclic structure in the acid decomposition site, Rx ₁ , Rx ₂ and Rx in the above general formula (aI) can be used. _In an embodiment in which one of ₃ is a group having an adamantane skeleton and the remaining two are linear or branched alkyl groups, or in general formula (aI), _{two of} Rx ₁ , Rx ₂ and Rx ₃ are bonded An embodiment in which an adamantane structure is formed and the remaining one is a linear or branched alkyl group is preferred.

  Moreover, resin (A) may have a repeating unit which decomposes | disassembles by the effect | action of an acid and produces an alcoholic hydroxyl group as represented below as a repeating unit which has an acid-decomposable group.

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

One type of repeating unit having an acid-decomposable group that can be contained in the resin (A) may be used, or two or more types may be used in combination.
When the resin (A) contains a repeating unit having two or more kinds of acid-decomposable groups, for example, in the above general formula (aI), all of Rx ₁ , Rx ₂ and Rx ₃ are methyl groups or ethyl groups The repeating unit of the embodiment or the embodiment represented by the general formula (aII) and the repeating unit having 10 to 20 carbon atoms in the acid decomposition site and containing a polycyclic structure in the acid decomposition site ( A combination with a repeating unit represented by aIII) is preferred.

  The total amount of the repeating unit having an acid-decomposable group is preferably from 30 to 80 mol%, more preferably from 40 to 75 mol%, particularly preferably from 45 to 70 mol%, based on all repeating units constituting the resin (A). 50 to 70 mol% is most preferable.

The content of the repeating unit represented by the general formula (aI) is preferably from 30 to 80 mol%, more preferably from 40 to 75 mol%, more preferably from 45 to 70 mol, based on all the repeating units constituting the resin (A). % Is particularly preferable, and 50 to 70 mol% is most preferable.
The proportion of the repeating unit (aIII) in all repeating units having an acid-decomposable group is preferably 3 to 50 mol%, more preferably 5 to 40 mol%, and most preferably 5 to 30 mol%.

  [Repeating unit having lactone structure or sultone structure]

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

  Any lactone structure or sultone structure can be used as long as it has a lactone structure or sultone structure, but a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure is preferable. Other ring structures are condensed in a form that forms a bicyclo structure or spiro structure in a member ring lactone structure, or other rings that form a bicyclo structure or a spiro structure in a 5- to 7-membered ring sultone structure Those having a condensed ring structure are more preferable. A lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3), More preferably, it has a repeating unit having A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), especially A preferred lactone structure is (LC1-4). By using such a specific lactone structure, LER and development defects are improved.

The lactone structure portion or the sultone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. A plurality of substituents (Rb ₂ ) may be bonded to form a ring.

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

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

In the general formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof independently when there are a plurality of R ₀ .
Z is independently a single bond, an ether bond, an ester bond, an amide bond, or a urethane bond when there are a plurality of Zs.

Or urea bond

Represents. Here, each R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
n is the number of repetitions of the structure represented by —R ₀ —Z—, and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, -R ₀ -Z- does not exist and becomes a single bond.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

The alkylene group and cycloalkylene group represented by R ₀ may have a substituent.
Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

The alkyl group for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.
The alkylene group of R ₀ , the cycloalkylene group, and the alkyl group in R ₇ may each be substituted. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a mercapto group, a hydroxyl group, An alkoxy group is mentioned.
R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

A preferred chain alkylene group for R ₀ is a chain alkylene having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. A preferable cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. In order to exhibit the effect of the present invention, a chain alkylene group is more preferable, and a methylene group is particularly preferable.

The monovalent organic group having a lactone structure or a sultone structure represented by R ₈ is not limited as long as it has a lactone structure or a sultone structure. As specific examples, general formulas (LC1-1) to ( LC1-21) and a lactone structure or a sultone structure represented by any one of (SL1-1) to (SL1-3), and among these, a structure represented by (LC1-4) is particularly preferable. preferable. Further, n ₂ in (LC1-1) to (LC1-21) is more preferably 2 or less.
R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or sultone structure, or a monovalent organic group having a lactone structure or sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) having a cyano group as a substituent is more preferable.

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

  In order to enhance the effect of the present invention, it is possible to use two or more kinds of repeating units having a lactone structure or a sultone structure in combination.

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

[Repeating unit having a cyclic carbonate structure]
Moreover, the resin (A) may have a repeating unit having a cyclic carbonate structure.
The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).

In general formula (A-1),
R _A ¹ represents a hydrogen atom or an alkyl group.
R _A ² each independently represents a substituent when n is 2 or more.
A represents a single bond or a divalent linking group.
Z represents an atomic group that forms a monocyclic or polycyclic structure together with a group represented by —O—C (═O) —O— in the formula.
n represents an integer of 0 or more.

General formula (A-1) is demonstrated in detail.
The alkyl group represented by R _A ¹ may have a substituent such as a fluorine atom. R _A ¹ preferably represents a hydrogen atom, a methyl group or a trifluoromethyl group, and more preferably represents a methyl group.

The substituent represented by R _A ² is, for example, an alkyl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, an amino group, or an alkoxycarbonylamino group. Preferably it is a C1-C5 alkyl group, and a C1-C5 linear alkyl group; C3-C5 branched alkyl group etc. can be mentioned. The alkyl group may have a substituent such as a hydroxyl group.

  n is an integer of 0 or more representing the number of substituents. For example, n is preferably 0 to 4, and more preferably 0.

  Examples of the divalent linking group represented by A include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination thereof. As an alkylene group, a C1-C10 alkylene group is preferable and a C1-C5 alkylene group is more preferable.

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

As a monocycle containing -O-C (= O) -O- represented by Z, for example, in the cyclic carbonate represented by the following general formula (a), n _A = 2 to 4 5 to 7-membered ring, and it is preferably a 5- or 6-membered ring _(n a = 2 or 3), more preferably a 5-membered ring _(n a = 2).

Examples of the polycycle containing —O—C (═O) —O— represented by Z include, for example, a cyclic carbonate represented by the following general formula (a) together with one or more other ring structures: Examples include a structure forming a condensed ring and a structure forming a spiro ring. The “other ring structure” that can form a condensed ring or a spiro ring may be an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring. .

In the resin (A), one type of repeating units represented by the general formula (A-1) may be contained alone, or two or more types may be contained.
In the resin (A), the content of the repeating unit having a cyclic carbonate structure (preferably, the repeating unit represented by the general formula (A-1)) is based on the total repeating units constituting the resin (A). 3 to 80 mol%, preferably 3 to 60 mol%, more preferably 3 to 30 mol%, and most preferably 10 to 15 mol%. By setting it as such a content rate, the developability as a resist, low defect property, low LWR, low PEB temperature dependence, a profile, etc. can be improved.

  Although the specific example of the repeating unit represented by general formula (A-1) below is given, this invention is not limited to these.

Incidentally, _R ^{A 1} in the following specific examples are the same meaning as _R ^{A 1} in the general formula (A-1).

[Repeating unit having a hydroxyl group, a cyano group or a carbonyl group]
The resin (A) may have a repeating unit having a hydroxyl group, a cyano group, or a carbonyl group. This improves the substrate adhesion and developer compatibility.

  The repeating unit having a hydroxyl group, a cyano group or a carbonyl group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group, a cyano group or a carbonyl group, and preferably has no acid-decomposable group. .

Further, the repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group, a cyano group or a carbonyl group is preferably different from the repeating unit having an acid-decomposable group (that is, a repeating unit which is stable with respect to an acid). Preferably).
The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group, a cyano group or a carbonyl group is preferably an adamantyl group, a diadamantyl group or a norbornane group.

  More preferably, the repeating unit represented by any of the following general formulas (AIIa) to (AIIe) can be exemplified.

In the formula, R _X represents a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group.

Ab represents a single bond or a divalent linking group.
Examples of the divalent linking group represented by Ab include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination thereof. As an alkylene group, a C1-C10 alkylene group is preferable, A C1-C5 alkylene group is more preferable, For example, a methylene group, ethylene group, a propylene group, etc. are mentioned.
In one embodiment of the present invention, Ab is preferably a single bond or an alkylene group.
Rp represents a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group. A plurality of Rp may be the same or different, but at least one of the plurality of Rp represents a hydroxyl group or a hydroxyalkyl group.

  The resin (A) may or may not contain a repeating unit having a hydroxyl group, a cyano group or a carbonyl group, but the resin (A) contains a repeating unit having a hydroxyl group, a cyano group or a carbonyl group. When contained, the content of the repeating unit having a hydroxyl group, a cyano group, or a carbonyl group is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, more preferably all the repeating units in the resin (A). Preferably it is 5-25 mol%.

  Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.

  In addition, the monomers described in [0011] and thereafter in International Publication 2011/122336, or the corresponding repeating units can be used as appropriate.

[Repeating unit having acid group]
Resin (A) may have a repeating unit having an acid group. Examples of the acid group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, a naphthol structure, and an aliphatic alcohol group (for example, hexafluoroisopropanol group) in which the α-position is substituted with an electron withdrawing group. It is more preferable to have a repeating unit having a carboxyl group. By containing the repeating unit having an acid group, the resolution in the contact hole application is increased. The repeating unit having an acid group includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acid group in the main chain of the resin through a linking group. Either a repeating unit that is bonded, or a polymerization initiator or chain transfer agent having an acid group, is introduced at the end of the polymer chain during polymerization, and the linking group is a monocyclic or polycyclic cyclic hydrocarbon structure. You may have. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

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

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

[Repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability]
The resin (A) in the present invention can further have a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group (for example, the acid group, hydroxyl group, cyano group) and does not exhibit acid decomposability. . As a result, the elution of low molecular components from the resist film to the immersion liquid during immersion exposure can be reduced, and the solubility of the resin can be appropriately adjusted during development using a developer containing an organic solvent. . Examples of such a repeating unit include a repeating unit represented by the general formula (IV).

In general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkenyl having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like, and cycloalkyl groups having 3 to 12 carbon atoms and cyclohexenyl group. Groups. The preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, more preferably a cyclopentyl group or a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.
These alicyclic hydrocarbon groups may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. It is done.

  The resin (A) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. 1-50 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 5-50 mol%.

Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[Repeating unit having an aromatic ring]
When the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, or high-energy light beam having a wavelength of 50 nm or less (for example, EUV), resin (A) preferably has a unit having an aromatic ring, as typified by a hydroxystyrene repeating unit.
The repeating unit having an aromatic ring is not particularly limited, and is also exemplified in the above description of each repeating unit, but a styrene unit, a hydroxystyrene unit, a phenyl (meth) acrylate unit, a hydroxyphenyl (meth) acrylate. Examples include units. More specifically, the resin (A) is a resin having a hydroxystyrene-based repeating unit and a hydroxystyrene-based repeating unit protected by an acid-decomposable group, a repeating unit having the aromatic ring, and (meth) Examples thereof include a resin having a repeating unit in which the carboxylic acid moiety of acrylic acid is protected by an acid-decomposable group. In particular, particularly in the case of EUV exposure, since high sensitivity is generally required, the resin (A) preferably contains a repeating unit containing a protective group that easily undergoes acid decomposition. Specific examples of the repeating unit include -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ) or -C (R ₀₁ ) (R ₀₂ ) ( A compound represented by OR ₃₉ ) (a structure commonly referred to as an acetal type protecting group) is preferred.

  Moreover, the aspect with which the structure corresponding to the acid generator mentioned later was carry | supported may be sufficient as resin (A) in one form. Specifically, as such an embodiment, a structure described in JP2011-248019A (particularly, a structure described in paragraphs 0164 to 0191, a structure included in the resin described in the example in paragraph 0555). And the repeating unit (R) described in paragraphs 0023 to 0210 of JP2013-80002A, and the contents thereof are incorporated in the present specification. Even if the resin (A) has a structure corresponding to the acid generator, the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention is further supported on the resin (A). An acid generator (that is, a compound (B) described later) that is not used may be included.

  Examples of the repeating unit having a structure corresponding to the acid generator include the following repeating units, but are not limited thereto.

Resin (A) used in the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention is, in addition to the above repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, Furthermore, it can have various repeating structural units for the purpose of adjusting the resolution, heat resistance, sensitivity, etc., which are general necessary properties of the first actinic ray-sensitive or radiation-sensitive resin composition.
Examples of such a repeating structural unit include, but are not limited to, repeating structural units corresponding to the following monomers.
Thereby, the performance required for the resin used for the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Fine adjustment such as dry etching resistance can be performed.
As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

In the resin (A) used in the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the content molar ratio of each repeating structural unit is that of the first actinic ray-sensitive or radiation-sensitive resin composition. Adjust dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required performance of first actinic ray-sensitive or radiation-sensitive resin composition, such as resolving power, heat resistance, sensitivity, etc. Therefore, it is set appropriately.
When the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention is for ArF exposure, the first actinic ray-sensitive or radiation-sensitive resin of the present invention from the viewpoint of transparency to ArF light. The resin (A) used in the composition has substantially no aromatic ring (specifically, the ratio of the repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure, preferably not more than mol%, ideally 0 mol%, that is, having no aromatic group.

  The form of the resin (A) in the present invention may be any of random type, block type, comb type, and star type. Resin (A) is compoundable by the radical, cation, or anion polymerization of the unsaturated monomer corresponding to each structure, for example. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.

When the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a hydrophobic resin (HR) described later, the resin (A) is compatible with the hydrophobic resin (HR). From the viewpoint, it does not contain a fluorine atom or a silicon atom (specifically, the ratio of the repeating unit having a fluorine atom or a silicon atom in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, ideal Is preferably 0 mol%.
The resin (A) used in the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably one in which all repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.

  The resin (A) in the present invention can be synthesized according to a conventional method (for example, by a method commonly used in the field of polymer synthesis such as radical polymerization, living radical polymerization, anionic polymerization, and cationic polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the 1st actinic-ray sensitive or radiation sensitive resin composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, polymerization is performed using the same solvent as the solvent used in the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C.

After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied.
For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer. A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.
The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.
The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

  The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

  In addition, after depositing and separating the resin once, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is contacted to precipitate a resin (step a), the resin is separated from the solution (step b), and dissolved again in the solvent to obtain a resin solution A. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).

Further, in order to prevent the resin from aggregating after the preparation of the first actinic ray-sensitive or radiation-sensitive resin composition, for example, a resin synthesized as described in JP-A-2009-037108 May be dissolved in a solvent to obtain a solution, and the solution may be heated at about 30 ° C. to 90 ° C. for about 30 minutes to 4 hours.
By these purification steps, it is preferable to reduce as much as possible unreacted low molecular components (monomers and oligomers).

  The weight average molecular weight of the resin (A) in the present invention is preferably from 6000 to 50000, more preferably from 8000 to 30000, and most preferably from 10000 to 25000 as a polystyrene equivalent value by the GPC method. By setting this molecular weight range, it can be expected that the solubility in an organic developer becomes an appropriate numerical value.

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

  The content of the resin (A) is preferably 30 to 99% by mass, more preferably 60 to 95% by mass, based on the total solid content of the first actinic ray-sensitive or radiation-sensitive resin composition.

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

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

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

[Compound that generates acid upon irradiation with actinic ray or radiation]
The first actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “compound (B)” or “acid generator”). It may contain.
The acid generator may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Further, the form of the low molecular compound and the form incorporated in a part of the polymer may be used in combination.
When the acid generator is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
When the acid generator is incorporated in a part of the polymer, it may be incorporated in a part of the acid-decomposable resin described above or may be incorporated in a resin different from the acid-decomposable resin.
In the present invention, the acid generator is preferably in the form of a low molecular compound.
In one embodiment of the present invention, examples of the acid generator include compounds represented by the following general formula (ZI), (ZII), or (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, at least one of R _{201 to} R ₂₀₃ of the compound represented by the general formula (ZI) is a single bond or at least one of R _{201 to} R ₂₀₃ of another compound represented by the general formula (ZI) It may be a compound having a structure bonded through a linking group.

Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
Examples of Z ⁻ include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion). Etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. 3-30 cycloalkyl groups are mentioned.
The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably carbon) Number 6-20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . About the aryl group and ring structure which each group has, you may have an alkyl group (preferably C1-C15) further as a substituent.

The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.
Examples of the sulfonylimide anion include saccharin anion.
The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
Examples of other Z ⁻ include fluorinated phosphorus (for example, PF ₆ ⁻ ), fluorinated boron (for example, BF ₄ ⁻ ), fluorinated antimony (for example, SbF ₆ ⁻ ), and the like.
Z ^- The at least α-position by an aliphatic sulfonate anion substituted with a fluorine atom, a fluorine atom or a fluorine atom is substituted with a group having a aromatic sulfonate anion of a sulfonic acid, an alkyl group substituted with a fluorine atom Bis (alkylsulfonyl) imide anions and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom are preferred.

In one embodiment of the present invention, the number of fluorine atoms contained in the anion as Z ⁻ is preferably 2 or 3.

  From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

_Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group (preferably having 6 to 15 carbon atoms), a linear or branched alkyl group (preferably having 1 to 10 carbon atoms), and a cycloalkyl group (having 3 carbon atoms). ~ 15 are preferred).
Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.

These aryl groups, alkyl groups and cycloalkyl groups as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may further have a substituent. Examples of the substituent include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

Two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. Examples of the linking group include an alkylene group (preferably having 1 to 3 carbon atoms), —O—, —S—, —CO—, —SO ₂ — and the like, but are not limited thereto.
Preferred structures when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group include paragraphs 0046 and 0047 of JP-A-2004-233661, paragraphs 0040 to 0046 of JP-A-2003-35948, US Compounds exemplified as formulas (I-1) to (I-70) in Patent Publication No. 2003 / 0224288A1, and Formulas (IA-1) to (I) in U.S. Patent Publication No. 2003 / 0077540A1 IA-54) and cation structures such as compounds exemplified as formulas (IB-1) to (IB-24).

  More preferable examples of the compound represented by the general formula (ZI) include compounds represented by the following general formula (ZI-3) or (ZI-4). First, the compound represented by general formula (ZI-3) is demonstrated.

In the general formula (ZI-3),
R ₁ represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group,
R ₂ and R ₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R ₂ and R ₃ may be linked to each other to form a ring,
R ₁ and R ₂ may combine with each other to form a ring,
R _X and R _y each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, or an alkoxycarbonylcycloalkyl group, R _X and R _y may be connected to each other to form a ring, and this ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond.
Z ⁻ represents a non-nucleophilic anion.
The alkyl group as R ₁ is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. Specific examples include branched alkyl groups. The alkyl group of R ₁ may have a substituent.

The cycloalkyl group as R ₁ is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a sulfur atom in the ring. The cycloalkyl group of R ₁ may have a substituent.

The alkoxy group as R ₁ is preferably an alkoxy group having 1 to 20 carbon atoms. The alkoxy group of R ₁ may have a substituent.

The cycloalkoxy group as R ₁ is preferably a C3-C20 cycloalkoxy group. The cycloalkoxy group for R ₁ may have a substituent.

The aryl group as R ₁ is preferably an aryl group having 6 to 14 carbon atoms. The aryl group for R ₁ may have a substituent.

Examples of the alkenyl group as R ₁ include a vinyl group and an allyl group.

R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ₂ and R ₃ may be connected to each other to form a ring. However, at least one of R ₂ and R ₃ represents an alkyl group, a cycloalkyl group, or an aryl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R ₂ and R ₃ include those similar to the specific examples and preferred examples described above for R ₁ . When R ₂ and R ₃ are connected to each other to form a ring, the total number of carbon atoms contributing to the formation of the ring contained in R ₂ and R ₃ is preferably 4 to 7, and 4 or 5 It is particularly preferred that
R ₁ and R ₂ may be connected to each other to form a ring. When R ₁ and R ₂ are connected to each other to form a ring, R ₁ is an aryl group (preferably a phenyl group or a naphthyl group which may have a substituent), and R ₂ has 1 to 4 carbon atoms. An alkylene group (preferably a methylene group or an ethylene group) is preferable, and examples of the preferable substituent include the same substituents that the aryl group as R ₁ may have. As another form in the case where R ₁ and R ₂ are connected to each other to form a ring, it is also preferable that R ₁ is a vinyl group and R ₂ is an alkylene group having 1 to 4 carbon atoms.

The alkyl group represented by R _X and R _y is preferably an alkyl group having 1 to 15 carbon atoms.

The cycloalkyl group represented by R _X and R _y is preferably a cycloalkyl group having 3 to 20 carbon atoms.

The alkenyl group represented by R _X and R _y is preferably 2 to 30 alkenyl groups such as vinyl group, allyl group, and styryl group.

The aryl group represented by R _X and R _y is, for example, an aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

The alkyl group moiety of the 2-oxoalkyl group and alkoxycarbonylalkyl group represented by R _X and R _y, for example, those previously listed as R _X and R _y.
Examples of the cycloalkyl group part of the 2-oxocycloalkyl group and alkoxycarbonylcycloalkyl group represented by R _X and R _y include those enumerated above as R _X and Ry.

Z ^- is, for example, Z in the above general formula (ZI) ^- include those listed as.
The compound represented by the general formula (ZI-3) is preferably a compound represented by the following general formulas (ZI-3a) and (ZI-3b).

In the general formulas (ZI-3a) and (ZI-3b), R ₁ , R ₂ and R ₃ are as defined in the general formula (ZI-3).

Y represents an oxygen atom, a sulfur atom or a nitrogen atom, and is preferably an oxygen atom or a nitrogen atom. m, n, p, and q represent integers, preferably 0 to 3, more preferably 1 to 2, and particularly preferably 1. The alkylene group connecting S ⁺ and Y may have a substituent, and preferred examples of the substituent include an alkyl group.

R ₅ represents a monovalent organic group when Y is a nitrogen atom, and is absent when Y is an oxygen atom or a sulfur atom. R ₅ is preferably a group containing an electron withdrawing group, and particularly preferably a group represented by the following general formulas (ZI-3a-1) to (ZI-3a-4).

In the above (ZI-3a-1) to (ZI-3a-3), R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, preferably an alkyl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R include the same specific examples and preferred examples as those described above for R ₁ in the general formula (ZI-3).

In the above (ZI-3a-1) to (ZI-3a-4), * represents a bond connected to a nitrogen atom as Y in the compound represented by the general formula (ZI-3a).
When Y is a nitrogen atom, R ₅ is particularly preferably a group represented by —SO ₂ —R ₄ . R ₄ represents an alkyl group, a cycloalkyl group or an aryl group, preferably an alkyl group. Specific examples and preferred examples of the alkyl group, cycloalkyl group and aryl group for R ₄ include those similar to the specific examples and preferred examples described above for R ₁ .
Z ^- is, for example, Z in the above general formula (ZI) ^- include those listed as.
Specific examples of the cation moiety of the compound represented by the general formula (ZI-3) are shown below.

  Next, the compound represented by general formula (ZI-4) is demonstrated.

In general formula (ZI-4),
R ₁₃ represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group. These groups may have a substituent.
When there are a plurality of R _{14 s,} each independently represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. Represent. These groups may have a substituent.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring, and the atoms constituting the ring may include heteroatoms such as an oxygen atom, a sulfur atom and a nitrogen atom. These groups may have a substituent.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
Z ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

In General Formula (ZI-4), the alkyl groups represented by R ₁₃ , R _14, and R ₁₅ are linear or branched and preferably have 1 to 10 carbon atoms.

Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group.

The alkoxy group for R ₁₃ and R ₁₄ is linear or branched and preferably has 1 to 10 carbon atoms.

The alkoxycarbonyl group for R ₁₃ and R ₁₄ is linear or branched and preferably has 2 to 11 carbon atoms.

Examples of the group having a cycloalkyl group of R ₁₃ and R ₁₄ include a group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.

The alkyl group of the alkyl group of R _14, include the same specific examples as the alkyl group as R ₁₃ to R ₁₅ described above.

The alkylsulfonyl group and cycloalkylsulfonyl group for R ₁₄ are linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms.

Examples of the substituent that each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Etc.
As a ring structure that two R ₁₅ may be bonded to each other, a 5-membered or 6-membered ring formed by two R ₁₅ together with a sulfur atom in the general formula (ZI-4) is particularly preferable. Includes a 5-membered ring (that is, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. This divalent R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group. Group, alkoxycarbonyloxy group and the like. There may be a plurality of substituents for the ring structure, or they may be bonded to each other to form a ring.

R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, or a divalent group in which two R ¹⁵ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom. A divalent group in which two R ¹⁵ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom is particularly preferable.

The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).
l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.

  Specific examples of the cation structure possessed by the compound represented by the general formula (ZI-3) or (ZI-4) described above include the above-mentioned JP-A-2004-233661, JP-A-2003-35948, In addition to cationic structures such as compounds exemplified in U.S. Patent Application Publication No. 2003 / 0224288A1 and U.S. Patent Application Publication No. 2003 / 0077540A1, for example, paragraphs 0046 and 0047 of JP2011-53360A Cation structures in chemical structures and the like exemplified in 0072-0077 and 0107-0110, cation structures in chemical structures and the like exemplified in paragraphs 0135 to 0137, 0151 and 0196 to 0199 of JP2011-53430, etc. Is mentioned.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ are the same as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI).
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Even the substituent, an aryl group of R ₂₀₁ to R ₂₀₃ in the above compound (ZI), alkyl groups include those which may have a cycloalkyl group.
Z ^- is, for example, Z in the above general formula (ZI) ^- include those listed as.
Next, a preferred structure of the non-nucleophilic anion Z ⁻ will be described.
The non-nucleophilic anion Z ⁻ is preferably a sulfonate anion represented by the general formula (2).

In the general formula (2), Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₇ and R ₈ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R ₇ and R ₈ , R ₇ and R ₈ are the same But it can be different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents an organic group containing a cyclic structure.
x represents an integer of 1 to 20. y represents an integer of 0 to 10. z represents an integer of 0 to 10.

The anion of the general formula (2) will be described in more detail.
Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom as described above, and the alkyl group in the alkyl group substituted with a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms, An alkyl group having 1 to 4 carbon atoms is more preferable. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

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

R ₇ and R ₈ represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom as described above, and the alkyl group preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. As a specific example of the alkyl group substituted with at least one fluorine atom of R ₇ and R ₈ , CF ₃ is preferable.
L represents a divalent linking group, and represents —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, —N (Ri) — (wherein Ri represents a hydrogen atom or alkyl), an alkylene group (preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 10 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), or a plurality of these such divalent linking group formed by combining can be _{mentioned, -COO -, - OCO -,} - CO -, - SO 2 -, - CON (Ri) -, - SO 2 N (Ri) -, - CON (Ri ) - alkylene radical -, - N (Ri) CO- alkylene group -, - is preferably, -COO - - COO- alkylene group - or -OCO- alkylene group, - OCO -, - _SO 2 -, - CON (Ri) - or _-SO 2 N (Ri) - is that Is more preferable. When there are a plurality of L, they may be the same or different.
The alkyl group as Ri is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. Specific examples include straight chain alkyl groups and branched alkyl groups. Examples of the alkyl group having a substituent include a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group, and an ethoxycarbonylmethyl group.

The organic group containing the cyclic structure of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having an aromatic attribute but also aromaticity). For example, a tetrahydropyran ring and a lactone ring structure are also included.
The alicyclic group may be monocyclic or polycyclic. Also preferred are nitrogen atom-containing alicyclic groups such as piperidine group, decahydroquinoline group, decahydroisoquinoline group. Among them, an alicyclic group having a bulky structure of 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, a decahydroquinoline group, and a decahydroisoquinoline group. And diffusibility in the film in the PEB (post-exposure heating) step can be suppressed, which is preferable from the viewpoint of improving exposure latitude.

  Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Of these, naphthalene having low absorbance is preferred from the viewpoint of light absorbance at 193 nm.

  Examples of the heterocyclic group include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, a furan ring, a thiophene ring, and a pyridine ring are preferable.

  The cyclic organic group may have a substituent, and as the substituent, an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), aryl Examples include a group (preferably having 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, a sulfonic acid ester group, and a cyano group.

  Note that the carbon constituting the organic group containing a cyclic structure (carbon contributing to ring formation) may be a carbonyl carbon.

x is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1. y is preferably 0 to 4, more preferably 0 or 1, and still more preferably 0. z is preferably 0 to 8, more preferably 0 to 4, and still more preferably 1.
In one embodiment of the present invention, the number of fluorine atoms contained in the anion represented by the general formula (2) is preferably 2 or 3. Thereby, the effect of the present invention can be further enhanced.

  Specific examples of the sulfonate anion structure represented by the general formula (2) are given below, but the present invention is not limited thereto.

Z ⁻ is also preferably a sulfonate anion represented by the following general formula (B-1).

In the general formula (B-1),
R _b1 each independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group (CF ₃ ).
n represents an integer of 0 to 4.
n is preferably an integer of 0 to 3, and more preferably 0 or 1.
X _b1 represents a single bond, an alkylene group, an ether bond, an ester bond (-OCO- or -COO-), a sulfonate ester bond (-OSO ₂ - or _-SO 3 -), or an combination thereof.
X _b1 is preferably an ester bond (—OCO— or —COO—) or a sulfonate ester bond (—OSO ₂ — or —SO ₃ —), and preferably an ester bond (—OCO— or —COO—). Is more preferable.
R _b2 represents an organic group having 6 or more carbon atoms.

The organic group having 6 or more carbon atoms for R _b2 is preferably a bulky group, and examples thereof include alkyl groups, alicyclic groups, aryl groups, and heterocyclic groups having 6 or more carbon atoms.
The alkyl group having 6 or more carbon atoms for R _b2 may be linear or branched, and is preferably a linear or branched alkyl group having 6 to 20 carbon atoms. Examples thereof include a linear or branched hexyl group, a linear or branched heptyl group, and a linear or branched octyl group. From the viewpoint of bulkiness, a branched alkyl group is preferable.

The alicyclic group having 6 or more carbon atoms for R _b2 may be monocyclic or polycyclic. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is used in a PEB (post-exposure heating) step. From the viewpoints of suppressing diffusibility in the film and improving MEEF (Mask Error Enhancement Factor).

The aryl group having 6 or more carbon atoms for R _b2 may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. Among these, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.

The heterocyclic group having 6 or more carbon atoms for R _b2 may be monocyclic or polycyclic, but polycyclic can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, and a dibenzothiophene ring. Examples of the heterocyclic ring not having aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.

The substituent having 6 or more carbon atoms for R _b2 may further have a substituent. Examples of the further substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), and a cycloalkyl group (monocyclic, polycyclic, or spiro ring). And preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, And sulfonic acid ester groups. The carbon constituting the alicyclic group, aryl group, or heterocyclic group (carbon contributing to ring formation) may be a carbonyl carbon.

  Specific examples of the sulfonate anion structure represented by the general formula (B-1) are shown below, but the present invention is not limited thereto. In addition, what corresponds to the sulfonate anion represented by General formula (2) mentioned above is also contained in the following specific example.

Z ⁻ is also preferably a sulfonate anion represented by the following general formula (AI).

In general formula (AI),
R ₁ is an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, or a heteroaryl group.
R ₂ is a divalent linking group.
Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom.
n ₁ and n ₂ are each independently 0 or 1.

The alkyl group represented by R ₁ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. It is further more preferable, and it is especially preferable that it is a C1-C4 alkyl group.
The alkyl group may have a substituent (preferably a fluorine atom), and the alkyl group having a substituent is an alkyl group having 1 to 5 carbon atoms substituted with at least one fluorine atom. It is preferable that it is a C1-C5 perfluoroalkyl group.

The alkyl group represented by R ₁ is preferably a methyl group, an ethyl group, or a trifluoromethyl group, and more preferably a methyl group or an ethyl group.

The monovalent alicyclic hydrocarbon group represented by R ₁ preferably has 5 or more carbon atoms. The monovalent alicyclic hydrocarbon group preferably has 20 or less carbon atoms, and more preferably 15 or less. The monovalent alicyclic hydrocarbon group may be a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group. A part of —CH ₂ — of the alicyclic hydrocarbon group may be substituted with —O— or —C (═O) —.

  As the monocyclic alicyclic hydrocarbon group, those having 5 to 12 carbon atoms are preferable, and a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are preferable.

  As the polycyclic alicyclic hydrocarbon group, those having 10 to 20 carbon atoms are preferable, and a norbornyl group, an adamantyl group, and a noradamantyl group are preferable.

The aryl group represented by R ₁ preferably has 6 or more carbon atoms. The aryl group preferably has 20 or less carbon atoms, and more preferably 15 or less.

The heteroaryl group represented by R ₁ preferably has 2 or more carbon atoms. The heteroaryl group preferably has 20 or less carbon atoms, more preferably 15 or less.

The aryl group and heteroaryl group may be a monocyclic aryl group or a monocyclic heteroaryl group, or may be a polycyclic aryl group or a polycyclic heteroaryl group.
Examples of the monocyclic aryl group include a phenyl group.
Examples of the polycyclic aryl group include a naphthyl group and an anthracenyl group.
Examples of the monocyclic heteroaryl group include a pyridyl group, a thienyl group, and a furanyl group.
Examples of the polycyclic heteroaryl group include a quinolyl group and an isoquinolyl group.

The monovalent alicyclic hydrocarbon group, aryl group, and heteroaryl group as R ₁ may further have a substituent. Examples of such a further substituent include a hydroxyl group, a halogen atom, Atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), nitro group, cyano group, amide group, sulfonamido group, alkyl group, alkoxy group, alkoxycarbonyl group, acyl group, acyloxy group, carboxy group .
R ₁ is particularly preferably a cyclohexyl group or an adamantyl group.

The divalent linking group represented by R ₂ is not particularly limited, but is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, alkylene. A group (preferably an alkylene group having 1 to 30 carbon atoms), a cycloalkylene group (preferably a cycloalkylene group having 3 to 30 carbon atoms), an alkenylene group (preferably an alkenylene group having 2 to 30 carbon atoms), an arylene group (preferably May be a C6-C30 arylene group), a heteroarylene group (preferably a C2-C30 heteroarylene group), or a group in which two or more of these are combined. The above alkylene group, cycloalkylene group, alkenylene group, arylene group and heteroarylene group may further have a substituent, and specific examples of such a substituent include a monovalent alicyclic ring as R _1. The substituents that the hydrocarbon group, aryl group, and heteroaryl group may further have are the same as those described above.

The divalent linking group represented by R ₂ is preferably an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, or a heteroarylene group, more preferably an alkylene group, and further an alkylene group having 1 to 10 carbon atoms. An alkylene group having 1 to 5 carbon atoms is preferable.

Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Rf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More specifically, Rf is preferably a fluorine atom or CF ₃ .
n ₁ is preferably 1.
n ₂ is preferably 1.
Although the preferable specific example of the sulfonate anion represented by the said general formula (AI) is given to the following, this invention is not limited to these. In addition, what corresponds to the sulfonate anion represented by General formula (2) mentioned above is also contained in the following specific example.

The non-nucleophilic anion Z ⁻ may be a disulfonyl imido acid anion represented by the general formula (2 ′).

In general formula (2 ′),
Xf is as defined in the general formula (2), and preferred examples are also the same. In the general formula (2 ′), two Xf's may be linked to each other to form a ring structure.
Z ^- The disulfonylimide anion of, preferably a bis (alkylsulfonyl) imide anion.
The alkyl group in the bis (alkylsulfonyl) imide anion is preferably an alkyl group having 1 to 5 carbon atoms.
Two alkyl groups in the bis (alkylsulfonyl) imide anion may be linked to each other to form an alkylene group (preferably having 2 to 4 carbon atoms), and may form a ring together with the imide group and the two sulfonyl groups. The ring structure that may be formed by the bis (alkylsulfonyl) imide anion is preferably a 5- to 7-membered ring, and more preferably a 6-membered ring.

These alkyl groups and alkylene groups formed by connecting two alkyl groups to each other can have a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryl Examples thereof include an oxysulfonyl group and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
Examples of the acid generator further include compounds represented by the following general formula (ZV).

一般式（ＺＶ）中、
Ｒ_２０８はアルキル基、シクロアルキル基又はアリール基を表す。
Ａは、アルキレン基、アルケニレン基又はアリーレン基を表す。
Ｒ_２０８のアリール基の具体例としては、上記一般式（ＺＩ）におけるＲ_２０１〜Ｒ_２０３としてのアリール基の具体例と同様のものを挙げることができる。
Ｒ_２０８のアルキル基及びシクロアルキル基の具体例としては、それぞれ、上記一般式（ＺＩ）におけるＲ_２０１〜Ｒ_２０３としてのアルキル基及びシクロアルキル基の具体例と同様のものを挙げることができる。

In general formula (ZV),
R ₂₀₈ represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Specific examples of the aryl group of R ₂₀₈ include the same examples as the specific examples of the aryl group as R _{201 to} R ₂₀₃ in the general formula (ZI).
Specific examples of the alkyl group and cycloalkyl group represented by R ₂₀₈ include the same examples as the specific examples of the alkyl group and cycloalkyl group represented by R _{201 to} R ₂₀₃ in the general formula (ZI).

The alkylene group of A is an alkylene group having 1 to 12 carbon atoms, the alkenylene group of A is an alkenylene group having 2 to 12 carbon atoms, and the arylene group of A is an arylene group having 6 to 10 carbon atoms. , Can be mentioned respectively.
Examples of acid generators are listed below. However, the present invention is not limited to these.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator is preferably 0.1 to 30% by mass, more preferably 1 to 28% by mass, based on the total solid content of the first actinic ray-sensitive or radiation-sensitive resin composition. Preferably it is 3-25 mass%.

[Hydrophobic resin]
The first actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a hydrophobic resin (hereinafter referred to as “hydrophobic resin (HR)” or simply “resin (HR)”), particularly when applied to immersion exposure. May also be included). The hydrophobic resin (HR) is preferably different from the resin (A).

As a result, the hydrophobic resin (HR) is unevenly distributed on the surface layer of the film, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion liquid followability is improved. be able to.
The hydrophobic resin may be included for various purposes even when the composition is not applied to immersion exposure. For example, when the composition is applied to EUV exposure, it is also preferable to use a hydrophobic resin in anticipation of outgas suppression and pattern shape adjustment.
The hydrophobic resin (HR) is preferably designed to be unevenly distributed at the interface as described above. However, unlike the surfactant, the hydrophobic resin (HR) is not necessarily required to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.

Hydrophobic resin (HR) is any one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in side chain portion of resin” from the viewpoint of uneven distribution in the surface layer of the film It is preferable to have the above, and it is more preferable to have two or more.
When the hydrophobic resin (HR) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin (HR) may be contained in the main chain of the resin. , May be contained in the side chain.
When the hydrophobic resin (HR) contains a fluorine atom, the partial structure having a fluorine atom is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. Preferably there is.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and further a fluorine atom It may have a substituent other than.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom. .

  Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). However, at least one of R _{57 to} R ₆₁ , at least one of R _{62 to} R ₆₄ , and at least one of R _{65 to} R ₆₈ are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms).

R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.
Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.

  Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.

Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH _(CF 3) OH and the like, -C _{(CF 3)} 2 OH is preferred.

  The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple | bond with a principal chain through the group selected or the group which combined these 2 or more.

  Hereinafter, although the specific example of the repeating unit which has a fluorine atom is shown, this invention is not limited to this.

In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ . X ₂ represents -F or -CF _3.

The hydrophobic resin (HR) may contain a silicon atom. The partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represent a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, and a urea bond, or a combination of two or more ( Preferably, the total carbon number is 12 or less).
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.
Hereinafter, although the specific example of the repeating unit which has group represented by general formula (CS-1)-(CS-3) is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

Further, as described above, the hydrophobic resin (HR) also preferably includes a CH ₃ partial structure in the side chain portion.
Here, the CH ₃ partial structure possessed by the side chain moiety in the resin (HR) (hereinafter also simply referred to as “side chain CH ₃ partial structure”) has a CH ₃ partial structure possessed by an ethyl group, a propyl group, or the like. It is included.
On the other hand, a methyl group directly bonded to the main chain of the resin (HR) (for example, an α-methyl group of a repeating unit having a methacrylic acid structure) causes the surface uneven distribution of the resin (HR) due to the influence of the main chain. Since the contribution is small, it is not included in the CH ₃ partial structure in the present invention.
More specifically, the resin (HR) includes a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). In the case where R _{11 to} R ₁₄ are CH ₃ “as is”, the CH ₃ is not included in the CH ₃ partial structure of the side chain moiety in the present invention.
Meanwhile, CH ₃ partial structure exists through some atoms from C-C backbone, and those falling under CH ₃ partial structures in the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed that it has “one” CH ₃ partial structure in the present invention.

In the general formula (M),
R < ₁₁ > -R < ₁₄ > represents a side chain part each independently.
Examples of R _{11 to} R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.
Examples of the monovalent organic group for R _{11 to} R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.
The hydrophobic resin (HR) is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and It is more preferable to have at least one repeating unit (x) among repeating units represented by the following general formula (V).
Hereinafter, the repeating unit represented by formula (II) will be described in detail.

In the general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₂ has one or more CH ₃ partial structure represents a stable organic radical to acid. Here, the organic group that is stable to acid is more specifically an organic group that does not have the “group that decomposes by the action of an acid to generate a polar group” described in the resin (A). Is preferred.
The alkyl group of _Xb1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
X _b1 is preferably a hydrogen atom or a methyl group.

Examples of R ₂ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. The above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group may further have an alkyl group as a substituent.
R ₂ is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH ₃ partial structures.

The acid-stable organic group having one or more CH ₃ partial structures as R ₂ preferably has 2 or more and 10 or less CH ₃ partial structures, and more preferably 2 or more and 8 or less.

The alkyl group having one or more CH ₃ partial structures in R ₂ is preferably a branched alkyl group having 3 to 20 carbon atoms.

The cycloalkyl group having one or more CH ₃ partial structures in R ₂ may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. Preferably, they are a norbornyl group, a cyclopentyl group, and a cyclohexyl group.

The alkenyl group having one or more CH ₃ partial structures in R ₂ is preferably a linear or branched alkenyl group having 1 to 20 carbon atoms, and more preferably a branched alkenyl group.

The aryl group having one or more CH ₃ partial structures in R ₂ is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. is there.

The aralkyl group having one or more CH ₃ partial structures in R ₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

Specific examples of the hydrocarbon group having two or more CH ₃ partial structures in R ₂ include isobutyl group, t-butyl group, 2-methyl-3-butyl group, 2,3-dimethyl- 2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2 , 6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, 3,5-dimethylcyclohexyl group, 3,5-ditert-butyl A cyclohexyl group, a 4-isopropylcyclohexyl group, a 4-tbutylcyclohexyl group, and an isobornyl group.

  Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. Note that the present invention is not limited to this.

  The repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

  Hereinafter, the repeating unit represented by formula (V) will be described in detail.

In the general formula (V), X _b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, R ₃ represents an organic group that is stable against an acid having one or more CH ₃ partial structures, n represents an integer of 1 to 5.
The alkyl group of _Xb2 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable.
X _b2 is preferably a hydrogen atom.

Since R ₃ is an organic group that is stable against an acid, more specifically, an organic group that does not have the “group that decomposes by the action of an acid to generate a polar group” described in the resin (A). It is preferable that
R ₃ includes an alkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₃ preferably has 1 or more and 10 or less CH ₃ partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.
The alkyl group having one or more CH ₃ partial structures in R ₃ is preferably a branched alkyl group having 3 to 20 carbon atoms.
Specific examples of the alkyl group having two or more CH ₃ partial structures in R ₃ include isopropyl group, t-butyl group, 2-methyl-3-butyl group, 2-methyl-3-pentyl. Group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl A 3-heptyl group, a 2,3,5,7-tetramethyl-4-heptyl group, and a 2,6-dimethylheptyl group;

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

  Preferred specific examples of the repeating unit represented by the general formula (V) are shown below. Note that the present invention is not limited to this.

  The repeating unit represented by the general formula (V) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

In the case where the resin (HR) contains a CH ₃ partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II) and the general formula The content of at least one repeating unit (x) among the repeating units represented by (V) is preferably 90 mol% or more, and 95 mol% or more with respect to all the repeating units of the resin (C). It is more preferable that The content is usually 100 mol% or less with respect to all repeating units of the resin (C).

  The resin (HR) is a repeating unit represented by the general formula (II), and at least one repeating unit (x) among the repeating units represented by the general formula (V) is all the repeating units of the resin (HR). By containing 90 mol% or more with respect to the unit, the surface free energy of the resin (C) increases. As a result, the resin (HR) is less likely to be unevenly distributed on the surface of the resist film, so that the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved.

In addition, the hydrophobic resin (HR) includes the following (x) to (z) even when (i) contains a fluorine atom and / or a silicon atom, and (ii) contains a CH ₃ partial structure in the side chain portion. ) May have at least one group selected from the group of
(X) an acid group,
(Y) a group having a lactone structure, an acid anhydride group, or an acid imide group,
(Z) A group capable of decomposing by the action of an acid As the acid group (x), a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) ) Methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkyl) A carbonyl) methylene group, a tris (alkylsulfonyl) methylene group, and the like.

Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.
The repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
The content of the repeating unit having an acid group (x) is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, still more preferably 5 to 5 mol% with respect to all repeating units in the hydrophobic resin (HR). 20 mol%.

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

As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.
The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.
Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the acid-decomposable resin (A).
The content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin (HR), It is more preferably 3 to 98 mol%, and further preferably 5 to 95 mol%.

In the hydrophobic resin (HR), examples of the repeating unit having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group listed for the resin (A). The repeating unit having a group (z) that is decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. In the hydrophobic resin (HR), the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol% with respect to all repeating units in the resin (HR). Preferably it is 10-80 mol%, More preferably, it is 20-60 mol%.
The hydrophobic resin (HR) may further have a repeating unit represented by the following general formula (VI).

In general formula (VI):
R _c31 represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a fluorine atom or a silicon atom.

L _c3 represents a single bond or a divalent linking group.
In general formula (VI), the alkyl group represented by R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and these may have a substituent.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.
The divalent linking group of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an ether bond, a phenylene group, or an ester bond (a group represented by —COO—).
The content of the repeating unit represented by the general formula (VI) is preferably 1 to 100 mol%, more preferably 10 to 90 mol%, based on all repeating units in the hydrophobic resin. 30 to 70 mol% is more preferable.

  It is also preferable that the hydrophobic resin (HR) further has a repeating unit represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).
The content of the repeating unit represented by the general formula (CII-AB) is preferably 1 to 100 mol%, and preferably 10 to 90 mol%, based on all repeating units in the hydrophobic resin. More preferably, it is more preferably 30 to 70 mol%.

Specific examples of the repeating unit represented by the general formulas (VI) and (CII-AB) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

  When the hydrophobic resin (HR) has a fluorine atom, the content of the fluorine atom is preferably 5 to 80% by mass with respect to the weight average molecular weight of the hydrophobic resin (HR), and is 10 to 80% by mass. More preferably. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mol% in all the repeating units contained in hydrophobic resin (HR), and it is more preferable that it is 30-100 mol%.

  When the hydrophobic resin (HR) has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass with respect to the weight average molecular weight of the hydrophobic resin (HR), and is 2 to 30% by mass. More preferably. Moreover, it is preferable that it is 10-100 mol% in the repeating unit containing a silicon atom among all the repeating units contained in hydrophobic resin (HR), and it is more preferable that it is 20-100 mol%.

On the other hand, particularly when the resin (HR) includes a CH ₃ partial structure in the side chain portion, it is also preferable that the resin (HR) does not substantially contain a fluorine atom and a silicon atom. In this case, specifically, The content of the repeating unit having a fluorine atom or a silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, more preferably 1 mol based on all repeating units in the resin (HR). % Or less, ideally 0 mol%, that is, no fluorine atom and no silicon atom. Moreover, it is preferable that resin (HR) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom may be 95 mol% or more in all the repeating units of the resin (HR). Preferably, it is 97 mol% or more, more preferably 99 mol% or more, and ideally 100 mol%.

  The weight average molecular weight of the hydrophobic resin (HR) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and even more preferably 2,000 to 15,000. is there.

Moreover, the hydrophobic resin (HR) may be used alone or in combination.
The content of the hydrophobic resin (HR) is preferably 0.01 to 10% by mass with respect to the total solid content in the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention, preferably 0.05 to 8 mass% is more preferable and 0.1-7 mass% is still more preferable.
The hydrophobic resin (HR), like the resin (A), naturally has few impurities such as metals, and the residual monomer and oligomer components are preferably 0.01 to 5% by mass, more preferably. Is more preferably 0.01 to 3% by mass and 0.05 to 1% by mass. Thereby, the 1st actinic-ray sensitive or radiation sensitive resin composition without a temporal change, such as a foreign material in liquid and a sensitivity, is obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

  As the hydrophobic resin (HR), various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.

  The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as described in the resin (A), but in the synthesis of the hydrophobic resin (HR), The reaction concentration is preferably 30 to 50% by mass.

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

[Basic compounds]
The first actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound in order to reduce changes in performance over time from exposure to heating. Although the basic compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(6) can be used.

(1) Basic compound (N)
Preferred examples of the basic compound include compounds (N) having a structure represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
Preferable compound (N) includes guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, and more preferable compound (N) includes imidazole structure, diazabicyclo structure, onium hydroxy group. Compound (N) having an alkyl group structure, an onium 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, etc. be able to.

  Examples of the compound (N) having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. As the compound (N) having a diazabicyclo structure, 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. Examples of the compound (N) having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide. , Tris (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like. As the compound (N) having an onium carboxylate structure, the anion portion of the compound (N) having an onium hydroxide structure is converted to a carboxylate. For example, acetate, adamantane-1-carboxylate, perfluoroalkylcarboxylate Etc. Examples of the compound (N) having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound (N) include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

Preferred examples of the basic compound (N) further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group. Examples of these compounds include compounds (C1-1) to (C3-3) exemplified in paragraph <0066> of US Patent Application Publication No. 2007 / 02245539A1.
The following compounds are also preferable as the basic compound (N).

  As the basic compound (N), in addition to the compounds described above, JP 2011-22560 A <0180> to <0225>, JP 2012-137735 A <0218> to <0219>, International Publication Pamphlet WO 2011 / 158687A1 <0416> to <0438> can also be used. The basic compound (N) may be a basic compound or an ammonium salt compound whose basicity is lowered by irradiation with actinic rays or radiation.

  These basic compounds (N) may be used alone or in combination of two or more.

The first actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain the basic compound (N), but when it is contained, the content of the basic compound (N) is Based on the solid content of the first actinic ray-sensitive or radiation-sensitive resin composition, it is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass.
The ratio of the acid generator and the basic compound (N) used in the first actinic ray-sensitive or radiation-sensitive resin composition is acid generator / basic compound (molar ratio) = 2.5 to 300. It is preferable. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing resolution from being reduced due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (N) (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

(2) Basic compound or ammonium salt compound (F) whose basicity is reduced by irradiation with actinic rays or radiation
The first actinic ray-sensitive or radiation-sensitive resin composition in the present invention is also referred to as a basic compound or an ammonium salt compound (hereinafter referred to as “compound (F)”) whose basicity is lowered by irradiation with actinic rays or radiation. ) Is preferably contained.
The compound (F) is preferably a compound (F-1) having a basic functional group or an ammonium group and a group that generates an acidic functional group upon irradiation with actinic rays or radiation. That is, the compound (F) is a basic compound having a basic functional group and a group capable of generating an acidic functional group upon irradiation with actinic light or radiation, or an acidic functional group upon irradiation with an ammonium group and active light or radiation. An ammonium salt compound having a group to be generated is preferable.
The compound (F) or (F-1) is generated by decomposing upon irradiation with actinic rays or radiation, and the compound with reduced basicity is represented by the following general formula (PA-I), (PA-II) or (PAIII) In particular, from the standpoint that excellent effects regarding LWR, local pattern dimension uniformity and DOF can be achieved at a high level, the compound represented by formula (PA-II) or (PA The compound represented by -III) is preferred.

First, the compound represented by general formula (PA-I) is demonstrated.
_{Q-A 1 - (X)} n -B-R (PA-I)
In general formula (PA-I),
A ₁ represents a single bond or a divalent linking group.
Q represents _-SO 3 H, or -CO ₂ H. Q corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom or -N (Rx)-.
Rx represents a hydrogen atom or a monovalent organic group.
R represents a monovalent organic group having a basic functional group or a monovalent organic group having an ammonium group.

Next, the compound represented by general formula (PA-II) is demonstrated.
_{Q 1 -X 1 -NH-X 2} -Q 2 (PA-II)
In general formula (PA-II),
Q ₁ and Q ₂ each independently represents a monovalent organic group. However, either Q ₁ or Q ₂ has a basic functional group. Q ₁ and Q ₂ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ and X ₂ each independently represent —CO— or —SO ₂ —.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

Next, the compound represented by general formula (PA-III) is demonstrated.
_{Q 1 -X 1 -NH-X 2} -A 2 - (X 3) m -B-Q 3 (PA-III)
In general formula (PA-III),
Q ₁ and Q ₃ each independently represents a monovalent organic group. However, either one of Q ₁ and Q ₃ are a basic functional group. Q ₁ and Q ₃ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ , X ₂ and X ₃ each independently represent —CO— or —SO ₂ —.
A ₂ represents a divalent linking group.
B represents a single bond, an oxygen atom, or —N (Qx) —.
Qx represents a hydrogen atom or a monovalent organic group.
B is, -N (Qx) - when, _{Q 3} and Qx may combine to form a ring.
m represents 0 or 1.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

  Hereinafter, although the specific example of a compound (F) is given, it is not limited to these. In addition to the exemplified compounds, preferred specific examples of the compound (E) include compounds (A-1) to (A-44) of US Patent Application Publication No. 2010/0233629, and US Patent Application Publication No. (A-1)-(A-23) of 2012/0156617 specification, etc. are mentioned.

It is preferable that the molecular weight of a compound (F) is 500-1000.
The first actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not contain the compound (F), but when it is contained, the content of the compound (F) is the first 0.1-20 mass% is preferable on the basis of the solid content of the actinic ray-sensitive or radiation-sensitive resin composition, and more preferably 0.1-10 mass%.

(3) Low molecular weight compound (G) having a nitrogen atom and a group capable of leaving by the action of an acid
The first actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a compound having a nitrogen atom and a group capable of leaving by the action of an acid (hereinafter also referred to as “compound (G)”). May be.
The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.
The molecular weight of the compound (N ″) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
As the compound (G), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.

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

In general formula (d-1),
Rb each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group ( Preferably it represents C1-C10) or an alkoxyalkyl group (preferably C1-C10). Rb may be connected to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are substituted with a functional group such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group, alkoxy group, or halogen atom. It may be. The same applies to the alkoxyalkyl group represented by Rb.
Rb is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
Examples of the ring formed by connecting two Rb to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.
Specific examples of the structure represented by the general formula (d-1) include a structure disclosed in paragraph <0466> of U.S. Patent Application Publication No. 2012 / 0135348A1. It is not limited.

  The compound (G) particularly preferably has a structure represented by the following general formula (6).

In the general formula (6), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.
Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same.
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are described above as the groups in which the alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb may be substituted. It may be substituted with a group similar to the group.
Preferred examples of the Ra alkyl group, cycloalkyl group, aryl group, and aralkyl group (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above groups) include: The same group as the preferable example mentioned above about Rb is mentioned.

  In addition, the heterocyclic ring formed by connecting the Ra to each other preferably has 20 or less carbon atoms. For example, pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3 , 4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7 -Triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2,5-diazabicyclo [2.2.1] Heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, indole, indoline, 1,2, , 4-tetrahydroquinoxaline, perhydroquinoline, groups derived from heterocyclic compounds such as 1,5,9-triazacyclododecane, and groups derived from these heterocyclic compounds are linear or branched alkanes Groups derived from the above, groups derived from cycloalkanes, groups derived from aromatic compounds, groups derived from heterocyclic compounds, hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups, etc. Examples include groups substituted with one or more functional groups or one or more functional groups.

  Specific examples of the particularly preferred compound (G) in the present invention include compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012 / 0135348A1, but are not limited thereto. Absent.

The compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
In the present invention, the low molecular compound (G) can be used singly or in combination of two or more.

  The content of the compound (G) in the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention is 0 based on the total solid content of the first actinic ray-sensitive or radiation-sensitive resin composition. The content is preferably 0.001 to 20% by mass, more preferably 0.001 to 10% by mass, and still more preferably 0.01 to 5% by mass.

(4) Onium salt The first actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain an onium salt as a basic compound. Examples of the onium salt include onium salts represented by the following general formula (6A) or (6B). This onium salt is expected to control the diffusion of the generated acid in the resist system in relation to the acid strength of the photoacid generator usually used in the resist composition.

In general formula (6A),
Ra represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to a carboxylic acid group in the formula are excluded.
X ⁺ represents an onium cation.
In general formula (6B),
Rb represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to the sulfonic acid group in the formula are excluded.
X ⁺ represents an onium cation.

  In the organic group represented by Ra and Rb, the atom directly bonded to the carboxylic acid group or sulfonic acid group in the formula is preferably a carbon atom. However, in this case, in order to make the acid relatively weaker than the acid generated from the above-mentioned photoacid generator, the fluorine atom does not substitute for the carbon atom directly bonded to the sulfonic acid group or 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 C3-C30 heterocyclic group etc. are mentioned. In these groups, some or all of the hydrogen atoms may be substituted.
Examples of the substituent that the alkyl group, cycloalkyl group, aryl group, aralkyl group and heterocyclic group may have include a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.

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

  As the sulfonium cation, for example, an arylsulfonium cation having at least one aryl group is preferable, and a triarylsulfonium cation is more preferable. The aryl group may have a substituent, and the aryl group is preferably a phenyl group.

As examples of the sulfonium cation and the iodonium cation, the aforementioned sulfonium cation structure of the general formula (ZI) and the iodonium structure of the general formula (ZII) in the compound (B) can also be preferably exemplified.
A specific structure of the onium salt represented by the general formula (6A) or (6B) is shown below.

  When the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains an onium salt represented by the general formula (6A) or (6B), the content thereof is the first actinic ray-sensitive property. Or it is 0.01-10 mass% normally on the basis of solid content of a radiation sensitive resin composition, Preferably it is 0.1-5 mass%.

(5) Betaine Compound Further, the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a compound included in the formula (I) of JP2012-189977A, JP2013-6827A. A compound represented by formula (I), a compound represented by formula (I) in JP2013-8020A, a compound represented by formula (I) in JP2012-252124A, and the like A compound having both an onium salt structure and an acid anion structure in one molecule (hereinafter also referred to as a betaine compound) can be preferably used. Examples of the onium salt structure include a sulfonium, iodonium, and ammonium structure, and a sulfonium or iodonium salt structure is preferable. The acid anion structure is preferably a sulfonate anion or a carboxylic acid anion. Examples of this compound include the following.

[solvent]
Examples of the solvent that can be used in preparing the first actinic ray-sensitive or radiation-sensitive resin composition of the present invention include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, and lactate alkyl ester. , Alkoxypropionate alkyl, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkoxyalkoxyacetate, alkyl pyruvate, isobutyric acid An organic solvent such as alkyl (such as methyl 2-hydroxyisobutyrate) can be used.

Specific examples of these solvents include those described in US Patent Application Publication No. 2008/0187860 <0441> to <0455>.
In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.

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

The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate (PGMEA) single solvent or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate (PGMEA). Preferred specific examples of the mixed solvent include a mixed solvent containing PGMEA and a ketone solvent (cyclohexanone, 2-heptanone, etc.), a mixed solvent containing PGMEA and a lactone solvent (γ-butyrolactone, etc.), and a mixed solvent containing PGMEA and PGME. , A mixed solvent containing three types of PGMEA / ketone solvent / lactone solvent, a mixed solvent containing three types of PGMEA / PGME / lactone solvent, a mixed solvent containing three types of PGMEA / PGME / ketone solvent, etc. For example, but not limited to.
As the solvent, it is preferable to use a solvent having a reduced peroxide content, thereby improving the storage stability of the resist composition.
In order to suppress the generation of peroxide, the solvent may contain a stabilizer (for example, an antioxidant). The content of the peroxide in the solvent is preferably 2.0 mmol% or less, more preferably 1.0 mmol% or less, still more preferably 0.5 mmol% or less, and the solvent is contained in excess. It is particularly preferable that the oxide is not substantially contained.

[Surfactant]
The first actinic ray-sensitive or radiation-sensitive resin composition in the present invention may or may not further contain a surfactant, and if it is contained, fluorine and / or silicon surfactant (fluorine-based interface). It is more preferable to contain at least one of an activator, a silicon-based surfactant, a surfactant having both a fluorine atom and a silicon atom).

When the first actinic ray-sensitive or radiation-sensitive resin composition in the present invention contains a surfactant, the adhesiveness and the resolution can be improved with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. A resist pattern with few development defects can be provided.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in <0276> of U.S. Patent Application Publication No. 2008/0248425. For example, Ftop EF301, EF303, (Shin-Akita Kasei Co., Ltd.) )), Florard FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by DIC Corporation), Surflon S-382 SC101, 102, 103, 104, 105, 106, KH-20 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toagosei Chemical Co., Ltd.) ), Surflon S-393 (Seimi Chemical Co., Ltd.), Ftop EF121, EF 22A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 230G, 218G 204D, 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.
In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

As the surfactant corresponding to the above, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC Corporation), acrylate having C ₆ F ₁₃ group (or methacrylate) and (poly (oxyalkylene)) acrylate (copolymer of or methacrylate), and acrylate having a C ₃ F ₇ group (or methacrylate) (poly (oxyethylene) and) acrylate (or methacrylate) (poly ( And a copolymer with oxypropylene)) acrylate (or methacrylate).

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

  These surfactants may be used alone or in several combinations.

When the first actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, the amount of the surfactant used is the total amount of the first actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). ) Is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass.
On the other hand, the surface unevenness of the hydrophobic resin is increased by setting the addition amount of the surfactant to 10 ppm or less with respect to the total amount of the first actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). Thereby, the surface of the resist film can be made more hydrophobic, and the water followability at the time of immersion exposure can be improved.

The first actinic ray-sensitive or radiation-sensitive resin composition of the present invention can be prepared by appropriately mixing the above components. During the preparation, a process of reducing metal impurities in the composition to the ppb level using an ion exchange membrane, a process of filtering impurities such as various particles using an appropriate filter, a deaeration process, etc. Good. Specifics of these steps are described in JP 2012-88574 A, JP 2010-189563 A, JP 2001-12529 A, JP 2001-350266 A, and JP 2002-99076 A. JP-A-5-307263, JP-A-2010-164980, WO2006 / 121162A, JP-A-2010-243866, JP-A-2010-020297, and the like.
The first actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably has a low water content. Specifically, the water content is preferably 2.5% by mass or less, more preferably 1.0% by mass or less, and still more preferably 0.3% by mass or less in the total weight of the composition.

<Composition for protective film formation>
As described above, the pattern forming method of the present invention may include (6) a step of forming a protective film with the protective film forming composition between the step (1) and the step (2). Good.
The composition for forming a protective film is different from the first actinic ray-sensitive or radiation-sensitive resin composition, and is a second actinic ray-sensitive or sensitive material containing a resin that decomposes by the action of an acid to generate a polar group. A radiation resin composition is preferred. That is, in the pattern forming method of the present invention, (6 ′) the action of an acid different from the first actinic ray-sensitive or radiation-sensitive resin composition on the first actinic ray-sensitive or radiation-sensitive film. A step of forming a second actinic ray-sensitive or radiation-sensitive film with a second actinic ray-sensitive or radiation-sensitive resin composition containing a resin that decomposes by the above to generate a polar group preferable. As a result, particularly in the above-described second embodiment of the present invention, the region 51a located above the low photosensitive portion 21 in the protective film 51 can be more easily removed (FIGS. 2A and 2). (See (b)).
The resin in the second actinic ray-sensitive or radiation-sensitive resin composition, each component that the second actinic ray-sensitive or radiation-sensitive resin composition may contain, and these second components The preferred range of the content of the actinic ray-sensitive or radiation-sensitive resin composition with respect to the total solid content is the same as that in the first actinic-ray-sensitive or radiation-sensitive resin composition. However, the second actinic ray-sensitive or radiation-sensitive resin composition is different from the first actinic ray-sensitive or radiation-sensitive resin composition. For example, even if the component contained in the first actinic ray sensitive or radiation sensitive resin composition and the component contained in the second actinic ray sensitive or radiation sensitive resin composition are the same When the concentration of any of the components is different, the first actinic ray-sensitive or radiation-sensitive resin composition and the second actinic ray-sensitive or radiation-sensitive resin composition are different.

When the pattern formation method of the present invention includes the step (6 ′), the resin (A) in the first actinic ray-sensitive or radiation-sensitive resin composition contains a lactone structure, and the second actinic ray. It is preferable that the resin (A) in the light-sensitive or radiation-sensitive resin composition does not contain a lactone structure.
When the pattern forming method of the present invention includes the step (6 ′), the resin (A) in the second actinic ray-sensitive or radiation-sensitive resin composition has substantially a repeating unit having a lactone structure. (Specifically, the content of the repeating unit having a lactone structure is preferably 10 mol with respect to all repeating units in the resin (A) in the second actinic ray-sensitive or radiation-sensitive resin composition). % Or less) is preferable in that it is less susceptible to a nucleophilic reaction from the surface treatment agent and can further exhibit performance as a protective film.

The second actinic ray-sensitive or radiation-sensitive resin composition may or may not contain an acid generator.
When the second actinic ray-sensitive or radiation-sensitive resin composition contains an acid generator, the resin (A) in the second actinic ray-sensitive or radiation-sensitive resin composition is generated from this acid generator. The acid can be decomposed to generate a polar group.
On the other hand, even if the second actinic ray-sensitive or radiation-sensitive resin composition does not contain an acid generator, it is generated from the acid generator in the first actinic ray-sensitive or radiation-sensitive resin composition The second actinic ray-sensitive or radiation-sensitive resin composition by diffusing the generated acid from the first actinic ray-sensitive or radiation-sensitive film to the second actinic ray-sensitive or radiation-sensitive film The resin (A) in can be decomposed by the diffused acid to generate a polar group.

  It is preferable that the first actinic ray-sensitive or radiation-sensitive film and the protective film have little intermix. From this viewpoint, preferred examples of the solvent that the protective film-forming composition may contain include alcohol solvents, ether solvents, and combinations thereof. Specifically, an alkyl group having 3 or more carbon atoms (preferably having 5 to 10 carbon atoms), a cycloalkyl group (preferably having 5 to 10 carbon atoms), and an aralkyl group (preferably having 7 to 10 carbon atoms are preferable). ) And / or dialkyl ethers.

Moreover, the present invention includes the above-mentioned hydrophobic resin (HR) in the first actinic ray-sensitive or radiation-sensitive resin composition in the step (1), and as described above, the hydrophobic resin (HR) ) May be unevenly distributed on the surface of the film to form a film corresponding to the protective film. In this case, the hydrophobic resin (HR) is a resin having substantially no repeating unit having a lactone structure and having a repeating unit that decomposes by the action of an acid to generate a polar group for the reasons described above. Is preferred.
In the present invention, the top coat described in the step (2) may be a film corresponding to the protective film. In this case, for the reasons described above, it is preferable that the top coat includes a resin having substantially no repeating unit having a lactone structure and having a repeating unit that decomposes by the action of an acid to generate a polar group.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.
Synthesis example 1
Under a nitrogen stream, 40 g of a 6/4 (mass ratio) mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether was placed in a three-necked flask and heated to 80 ° C. (solvent 1). Monomers corresponding to the following repeating units are dissolved in a mixed solvent of 6/4 (mass ratio) of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether in a molar ratio of 30/10/60, respectively, and a 22 mass% monomer solution (400 g) was prepared. Furthermore, 8 mol% of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the monomer, and a dissolved solution was added dropwise to the solvent 1 over 6 hours. After completion of dropping, the reaction was further continued at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then poured into 3600 ml of hexane / 400 ml of ethyl acetate, and the precipitated powder was collected by filtration and dried to obtain 74 g of Resin (P-1). The obtained resin (P-1) had a weight average molecular weight of 12,000 and a dispersity (Mw / Mn) of 1.6.
Resins (P-2) to (P-9) and hydrophobicity were prepared in the same manner as in Synthesis Example 1 except that the monomers corresponding to each repeating unit were used so as to have a desired composition ratio (molar ratio). Resins (N-1) to (N-3) were synthesized.

Resist preparation The components shown in Table 4 below were dissolved in the solvent shown in the same table to give a total solid content concentration of 3.5% by mass, and each was filtered through a polyethylene filter having a pore size of 0.05 μm. 1-Ar-14 was prepared.

  Abbreviations in Table 4 are as follows.

〔resin〕
The composition ratio (molar ratio), weight average molecular weight and dispersity of the resins used in the examples are shown below.

[Acid generator]
The structural formula of the acid generator is shown below.

[Basic compounds]
The structural formula of the basic compound is shown below.

[Hydrophobic resin]
The composition ratio (molar ratio), weight average molecular weight and degree of dispersion of the hydrophobic resin used in the examples are shown below.

[Surfactant]
W-1: Megafuck F176 (manufactured by DIC Corporation) (fluorine-based)
W-2: Megafuck R08 (manufactured by DIC Corporation) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based)
W-4: PolyFox PF-6320 (made by OMNOVA) (fluorine-based)

〔solvent〕
A1: Propylene glycol monomethyl ether acetate (PGMEA)
A2: γ-butyrolactone A3: Cyclohexanone B1: Propylene glycol monomethyl ether (PGME)
B2: Ethyl lactate B3: 2-Heptanone B4: Propylene carbonate MIBC: Methyl isobutyl carbinol (4-methyl-2-pentanol)

-Preparation of surface treatment agent The components shown in Table 5 below were mixed, and each was filtered through a polyethylene filter having a pore size of 0.05 m to prepare surface treatment agents S-1 to S-16. In Table 5, MIBC represents methyl isobutyl carbinol. P-14 to P-17 represent the following resins, respectively. The resin (P-17) is a resin used together with N, N-dimethylethylenediamine as the compound (A) in the surface treatment agent (S-9). However, in the resin corresponding to the compound (A), Absent. P-14: Poly (aminoethyl methacrylate), Mw = 15000, Mw / Mn = 1.6
P-15: Poly (4-vinylpyridine), Mw = 60000, Mw / Mn = 2.0
P-16: PAA-08 (manufactured by Nitto Bo Medical Co., Ltd.) (polyallylamine)
P-17: Poly (2-ethylhexyl methacrylate), Mw = 10000, Mw / Mn = 1.5

-Performance evaluation A resist pattern was formed by the following method using the prepared resist composition.

Example 1
An organic antireflection film-forming ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto an 8-inch caliber silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 84 nm. A resist composition Ar-1 (first actinic ray-sensitive or radiation-sensitive resin composition) is applied thereon, baked (PB) at 100 ° C. for 60 seconds, and a resist film having a thickness of 100 nm (first Actinic ray-sensitive or radiation-sensitive film) was formed to obtain a wafer. The obtained wafer was subjected to an exposure mask (6% HTPSM, line / space = 75 nm) using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65). / 75 nm), pattern exposure was performed with an exposure amount at which the line width of the line pattern was 112.5 nm. Thereafter, heating (PEB) was performed at 100 ° C. for 60 seconds, butyl acetate (first developer) was padded for 30 seconds to develop, and then paddled with MIBC (first rinse solution) for 30 seconds for rinsing. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and heated at 100 ° C. for 60 seconds (baked after the first development). Next, surface treatment agent S-1 was applied at a rotation speed of 1500 rpm, baked at 100 ° C. for 60 seconds (baked after the surface treatment), and RF was performed using dry etcher U-621 (manufactured by Hitachi High-Technologies Corporation). Power etching: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate were Ar: 800 mL / min, C ₄ F ₆ : 40 mL / min, O ₂ : 20 mL / min, and dry etching was performed for 30 seconds. . Next, after padding MIBC (surface treatment agent removing solution) for 30 seconds, the wafer was rotated at a rotational speed of 2000 rpm for 30 seconds to obtain a 2.38 mass% aqueous solution of TMAH (tetramethylammonium hydroxide) (second developer). The paddle was developed by paddle for 30 seconds, and then rinsed by paddle with pure water (second rinse solution) for 30 seconds. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and baked (post-baked) at 90 ° C. for 60 seconds to obtain a 1: 1 line and space resist pattern having a line width of 37.5 nm.

(Examples 2, 5, 6, 7, 9)
Except for employing the resist composition, the first developer, the first rinse, the surface treatment agent, the surface treatment remover, the second rinse and the conditions described in Table 6, the same procedure as in Example 1 was performed. Thus, a 1: 1 line and space resist pattern having a line width of 37.5 nm was obtained.

(Example 3)
An organic antireflection film-forming ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto an 8-inch caliber silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 84 nm. A resist composition Ar-3 (first actinic ray-sensitive or radiation-sensitive resin composition) is applied thereon and baked (PB) at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm (first Actinic ray-sensitive or radiation-sensitive film) was formed to obtain a wafer. The obtained wafer was subjected to an exposure mask (6% HTPSM, line / space = 75 nm) using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65). / 75 nm), pattern exposure was performed with an exposure amount at which the line width of the line pattern was 112.5 nm. Thereafter, heating (PEB) was performed at 100 ° C. for 60 seconds, butyl acetate (first developer) was padded for 30 seconds to develop, and then paddled with MIBC (first rinse solution) for 30 seconds for rinsing. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and heated at 100 ° C. for 60 seconds (baked after the first development). Next, the surface treatment agent S-3 was applied at a rotation speed of 1500 rpm, baked at 100 ° C. for 60 seconds (baked after the surface treatment), and RF was performed using a dry etcher U-621 (manufactured by Hitachi High-Technologies Corporation). Power etching: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate were Ar: 800 mL / min, C ₄ F ₆ : 40 mL / min, O ₂ : 20 mL / min, and dry etching was performed for 30 seconds. . Next, a 2.38 mass% TMAH aqueous solution (second developer) was padded for 30 seconds for development, and then paddled with pure water (second rinse solution) for 30 seconds for rinsing. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and baked (post-baked) at 90 ° C. for 60 seconds to obtain a 1: 1 line and space resist pattern having a line width of 37.5 nm.

Example 4
An organic antireflection film-forming ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto an 8-inch caliber silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 84 nm. A resist composition Ar-4 (first actinic ray-sensitive or radiation-sensitive resin composition) is applied thereon, baked (PB) at 100 ° C. for 60 seconds, and a resist film having a thickness of 100 nm (first Actinic ray-sensitive or radiation-sensitive film) was formed to obtain a wafer. The obtained wafer was subjected to an exposure mask (6% HTPSM, line / space = 75 nm) using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65). / 75 nm), pattern exposure was performed with an exposure amount at which the line width of the line pattern was 112.5 nm. Thereafter, heating (PEB) was performed at 100 ° C. for 60 seconds, butyl acetate (first developer) was paddled for 30 seconds and developed, and then paddled with diisoamyl ether (first rinse solution) for 30 seconds for rinsing. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and heated at 100 ° C. for 60 seconds (baked after the first development). Next, the surface treatment agent S-4 was applied at a rotation speed of 1500 rpm, baked at 100 ° C. for 60 seconds (baked after the surface treatment), and RF was performed using a dry etcher U-621 (manufactured by Hitachi High-Technologies Corporation). Power etching: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate were Ar: 800 mL / min, C ₄ F ₆ : 40 mL / min, O ₂ : 20 mL / min, and dry etching was performed for 30 seconds. . Next, after paddle MIBC (surface treatment agent removal solution) for 30 seconds, the wafer is rotated for 30 seconds at a rotational speed of 2000 rpm, and 2.38 mass% TMAH aqueous solution (second developer) is paddle for 30 seconds. Then, paddle was rinsed for 30 seconds with pure water (second rinse solution). Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and baked (post-baked) at 90 ° C. for 60 seconds to obtain a 1: 1 line and space resist pattern having a line width of 37.5 nm.

(Example 8)
A line width of 37 was obtained in the same manner as in Example 4 except that the resist composition, the first developer, the first rinse solution, the surface treatment agent, the surface treatment agent removal solution, and the conditions described in Table 6 were used. A 5 nm 1: 1 line and space resist pattern was obtained.

(Example 10)
An organic antireflection film-forming ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a 12-inch diameter silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. A resist composition Ar-10 (first actinic ray-sensitive or radiation-sensitive resin composition) is applied thereon and baked (PB) at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm (first One actinic ray-sensitive or radiation-sensitive film) was formed to obtain a wafer. The obtained wafer was subjected to an exposure mask (6% HTPSM, XT1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection, manufactured by ASML) using an ArF excimer laser immersion scanner. (Line / space = 65 nm / 65 nm), pattern exposure was performed with an exposure amount at which the line width of the line pattern was 97.5 nm. Ultra pure water was used as the immersion liquid. Thereafter, heating (PEB) is performed at 100 ° C. for 60 seconds, EEP (ethyl 3-ethoxypropionate) (first developer) is paddled for 30 seconds and developed, and then paddled with MIBC (first rinse solution) for 30 seconds. And rinsed. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and heated at 100 ° C. for 60 seconds (baked after the first development). Next, surface treatment agent S-1 was applied at a rotation speed of 1500 rpm, baked at 100 ° C. for 60 seconds (baked after the surface treatment), and RF was performed using dry etcher U-621 (manufactured by Hitachi High-Technologies Corporation). Power etching: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate were Ar: 800 mL / min, C ₄ F ₆ : 40 mL / min, O ₂ : 20 mL / min, and dry etching was performed for 30 seconds. . Next, after paddle MIBC (surface treatment agent removal solution) for 30 seconds, the wafer is rotated for 30 seconds at a rotational speed of 2000 rpm, and 2.38 mass% TMAH aqueous solution (second developer) is paddle for 30 seconds. Then, after rinsing by paddle with pure water (second rinsing liquid) for 30 seconds, the wafer is rotated for 30 seconds at a rotation speed of 2000 rpm, and baking (post-baking) is performed at 90 ° C. for 60 seconds. A 1: 1 line and space resist pattern having a width of 32.5 nm was obtained.

(Examples 11, 16-22)
An organic antireflection film-forming ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto an 8-inch caliber silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 84 nm. A resist composition Ar-11 (first actinic ray-sensitive or radiation-sensitive resin composition) is applied thereon, baked (PB) at 100 ° C. for 60 seconds, and a resist film having a thickness of 100 nm (first Actinic ray-sensitive or radiation-sensitive film) was formed to obtain a wafer. The obtained wafer was subjected to an exposure mask (6% HTPSM, line / space = 75 nm) using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65). / 75 nm), pattern exposure was performed with an exposure amount at which the line width of the line pattern was 112.5 nm. Thereafter, heating (PEB) was performed at 100 ° C. for 60 seconds, the first developer shown in Table 6 was paddled for 30 seconds and developed, and then rinsed by paddling with MIBC (first rinse solution) for 30 seconds. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and heated at 100 ° C. for 60 seconds (baked after the first development). Next, the surface treatment agent shown in Table 6 was applied at a rotation speed of 1500 rpm, baked at 100 ° C. for 60 seconds (baking after surface treatment), and the surface treatment agent removal solution shown in Table 6 was padded for 30 seconds. did. Next, the wafer was rotated at a rotational speed of 2000 rpm for 30 seconds, and the second developer shown in Table 6 was paddled for 30 seconds for development, and then pure water (second rinse solution) was used for Examples 11 and 16-21. ) Paddle for 30 seconds and rinse. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and baked (post-baked) at 90 ° C. for 60 seconds to obtain a 1: 1 line and space resist pattern having a line width of 37.5 nm.

(Example 12)
An organic antireflection film-forming ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto an 8-inch caliber silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 84 nm. A resist composition Ar-12 (first actinic ray-sensitive or radiation-sensitive resin composition) is applied thereon, baked (PB) at 100 ° C. for 60 seconds, and a first resist film (100 nm in thickness) A first actinic ray-sensitive or radiation-sensitive film) was formed. A resist composition Ar-14 (second actinic ray-sensitive or radiation-sensitive resin composition) is further applied thereon and baked (PB) at 100 ° C. for 60 seconds to form a second resist film having a thickness of 100 nm. (Second actinic ray-sensitive or radiation-sensitive film) was formed to obtain a wafer. The obtained wafer was subjected to an exposure mask (6% HTPSM, line / space = 75 nm) using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65). / 75 nm), pattern exposure was performed with an exposure amount at which the line width of the line pattern was 112.5 nm. Thereafter, heating (PEB) was performed at 100 ° C. for 60 seconds, EEP (first developer) was paddled for 30 seconds to develop, and then paddled with MIBC (first rinse) for 30 seconds to rinse. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and heated at 100 ° C. for 60 seconds (baked after the first development). Next, the surface treatment agent S-3 was applied at a rotation speed of 1500 rpm, baked at 100 ° C. for 60 seconds (baked after the surface treatment), and RF was performed using a dry etcher U-621 (manufactured by Hitachi High-Technologies Corporation). Power etching: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate were Ar: 800 mL / min, C ₄ F ₆ : 40 mL / min, O ₂ : 20 mL / min, and dry etching was performed for 30 seconds. . Next, after padding water (surface treatment agent removal solution) for 30 seconds, the wafer is rotated at a rotation speed of 2000 rpm for 30 seconds, and 2.38 mass% TMAH aqueous solution (second developer) is padded for 30 seconds. Then, paddle was rinsed for 30 seconds with pure water (second rinse solution). Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and baked (post-baked) at 90 ° C. for 60 seconds to obtain a 1: 1 line and space resist pattern having a line width of 37.5 nm.

(Example 13)
An organic antireflection film-forming ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto an 8-inch caliber silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 84 nm. A resist composition Ar-13 (first actinic ray-sensitive or radiation-sensitive resin composition) is applied thereon and baked (PB) at 100 ° C. for 60 seconds to form a first resist film having a thickness of 100 nm ( A first actinic ray-sensitive or radiation-sensitive film) was formed. A resist composition Ar-14 (second actinic ray-sensitive or radiation-sensitive resin composition) is further applied thereon and baked (PB) at 100 ° C. for 60 seconds to form a second resist film having a thickness of 100 nm. (Second actinic ray-sensitive or radiation-sensitive film) was formed to obtain a wafer. The obtained wafer was subjected to an exposure mask (6% HTPSM, line / space = 75 nm) using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65). / 75 nm), pattern exposure was performed with an exposure amount at which the line width of the line pattern was 112.5 nm. Thereafter, heating (PEB) was carried out at 100 ° C. for 60 seconds, isoamyl acetate (first developer) was paddled for 30 seconds for development, and then paddled with MIBC (first rinse solution) for 30 seconds for rinsing. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and heated at 100 ° C. for 60 seconds (baked after the first development). Next, the surface treatment agent S-4 was applied at a rotation speed of 1500 rpm, baked at 100 ° C. for 60 seconds (baked after the surface treatment), and MIBC (surface treatment agent removing solution) was padded for 30 seconds. Next, the wafer is rotated at a rotational speed of 2000 rpm for 30 seconds, and a 2.38 mass% TMAH aqueous solution (second developer) is padded for 30 seconds to develop, and then pure water (second rinse solution) is used for 30 seconds. Paddle and rinse. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and baked (post-baked) at 90 ° C. for 60 seconds to obtain a 1: 1 line and space resist pattern having a line width of 37.5 nm.

(Example 14)
An organic antireflection film-forming ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto an 8-inch caliber silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 84 nm. A resist composition Ar-1 (first actinic ray-sensitive or radiation-sensitive resin composition) is applied thereon and baked (PB) at 100 ° C. for 60 seconds to form a first resist film having a thickness of 100 nm ( A first actinic ray-sensitive or radiation-sensitive film) was formed. A resist composition Ar-14 (second actinic ray-sensitive or radiation-sensitive resin composition) is further applied thereon, and baked at 100 ° C. for 60 seconds to form a second resist film having a thickness of 100 nm (second Actinic ray-sensitive or radiation-sensitive film) was formed to obtain a wafer. The obtained wafer was subjected to an exposure mask (6% HTPSM, line / space = 75 nm) using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65). / 75 nm), pattern exposure was performed with an exposure amount at which the line width of the line pattern was 112.5 nm. Thereafter, heating (PEB) was carried out at 100 ° C. for 60 seconds, isoamyl acetate (first developer) was paddled for 30 seconds for development, and then paddled with MIBC (first rinse solution) for 30 seconds for rinsing. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and heated at 100 ° C. for 60 seconds (baked after the first development). Next, the surface treatment agent S-1 was applied at a rotational speed of 1500 rpm, and MIBC (surface treatment agent removing solution) was padded for 30 seconds. Next, the wafer is rotated at a rotational speed of 2000 rpm for 30 seconds, and a 2.38 mass% TMAH aqueous solution (second developer) is padded for 30 seconds to develop, and then pure water (second rinse solution) is used for 30 seconds. Paddle and rinse. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and baked (post-baked) at 90 ° C. for 60 seconds to obtain a 1: 1 line and space resist pattern having a line width of 37.5 nm.

(Example 15)
An organic antireflection film-forming ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto an 8-inch caliber silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 84 nm. A resist composition Ar-1 (first actinic ray-sensitive or radiation-sensitive resin composition) is applied thereon, baked (PB) at 100 ° C. for 60 seconds, and a resist film having a thickness of 100 nm (first Actinic ray-sensitive or radiation-sensitive film) was formed to obtain a wafer. The obtained wafer was subjected to an exposure mask (6% HTPSM, line / space = 75 nm) using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65). / 75 nm), pattern exposure was performed with an exposure amount at which the line width of the line pattern was 112.5 nm. Thereafter, heating (PEB) was carried out at 100 ° C. for 60 seconds, isoamyl acetate (first developer) was paddled for 30 seconds for development, and then paddled with MIBC (first rinse solution) for 30 seconds for rinsing. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and heated at 100 ° C. for 60 seconds (baked after the first development). Next, the surface treatment agent S is placed on the pattern by drawing the wafer for 1 hour in a desiccator (at 23 ° C. under 1 atm) together with a bottle containing 100 g of the surface treatment agent S-10 with the opening opened. -10 vapors were contacted. Further, using dry etcher U-621 (manufactured by Hitachi High-Technologies Corporation), RF power: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate are Ar: 800 mL / min, C ₄ F ₆ : 40 mL, respectively. / Min, O ₂ : 20 mL / min, and dry etching was performed for 30 seconds. Next, a 2.38 mass% TMAH aqueous solution (second developer) was padded for 30 seconds for development, and then paddled with pure water (second rinse solution) for 30 seconds for rinsing. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and baked (post-baked) at 90 ° C. for 60 seconds to obtain a 1: 1 line and space resist pattern having a line width of 37.5 nm.

(Comparative Example 1)
An organic antireflection film-forming ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto an 8-inch caliber silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 84 nm. A resist composition Ar-1 (first actinic ray-sensitive or radiation-sensitive resin composition) is applied thereon, baked (PB) at 100 ° C. for 60 seconds, and a resist film having a thickness of 100 nm (first Actinic ray-sensitive or radiation-sensitive film) was formed to obtain a wafer. The obtained wafer was subjected to an exposure mask (6% HTPSM, line / space = 75 nm) using an ArF excimer laser scanner (PAS5500 / 1100, manufactured by ASML, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65). / 75 nm), pattern exposure was performed with an exposure amount at which the line width of the line pattern was 112.5 nm. Thereafter, heating (PEB) was performed at 100 ° C. for 60 seconds, butyl acetate (first developer) was padded for 30 seconds to develop, and then paddled with MIBC (first rinse solution) for 30 seconds for rinsing. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and heated at 100 ° C. for 60 seconds (baked after the first development). Next, 2.38% by mass of TMAH (tetramethylammonium hydroxide) aqueous solution (second developer) was developed by paddle for 30 seconds, and then paddled with pure water (second rinse solution) for 30 seconds to rinse. did. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds and baked (post-baked) at 90 ° C. for 60 seconds to obtain a 1: 1 line and space resist pattern having a line width of 37.5 nm.

  In Table 6, PB means heating before exposure, and PEB means heating after exposure. Further, in the columns of PB, PEB and top coat baking, for example, “100 ° C. 60 s” means heating at 100 ° C. for 60 seconds. Each EEP represents ethyl-3-ethoxypropionate.

-Observation of pattern persistence in double development Using AFM (trade name: Nanoscope 4) manufactured by Veeco, the line pattern in the pattern formation region in the wafer of each example was scanned in the longitudinal direction. Table 7 shows the result of calculating the difference between the average height of the pattern top portion and the average height of the pattern bottom portion. The larger the difference, the better the pattern persistence.

-Line width roughness (LWR) observation The line and space resist pattern obtained in each example was observed using a length-measuring scanning electron microscope (SEM, Hitachi, Ltd. S-9380II). The measurement was performed by measuring 50 dotted line widths in the range of 2 μm in the longitudinal direction at regular intervals and calculating 3σ (nm) from the standard deviation. A smaller value indicates better performance.

  From the results shown in Table 7 above, Examples 1-22 in which the pattern forming method of the present invention was performed were compared with Comparative Example 1 in which the surface treatment process was not performed, and pattern persistence and pattern in double development. It can be seen that it has excellent roughness performance. Moreover, it turns out that Examples 1-14 and 16-22 using the surface treating agent containing a solvent are especially excellent in the pattern survivability and the roughness performance of a pattern in double development.

10 Substrate 11, 21, 31 Low photosensitive area 12, 22, 32 Intermediate photosensitive area 13, 23, 33 High photosensitive area 14, 24, 34 Cured layer 15, 25, 35 Surface treatment agent film 51 Protective film 101, 102, 201 , 202, 301 First development pattern 101S, 201S, 301S Space portion 103, 203, 303 Second development pattern

Claims (17)

(1) forming a first actinic ray-sensitive or radiation-sensitive film with a first actinic ray-sensitive or radiation-sensitive resin composition containing a resin that decomposes by the action of an acid to generate a polar group;
(2) a step of exposing the first actinic ray-sensitive or radiation-sensitive film;
(3) developing the first actinic ray-sensitive or radiation-sensitive film using a developer containing an organic solvent to obtain a first development pattern;
(4) A step of causing a surface treatment agent containing a basic compound to act on the first development pattern as a compound that interacts with the polar group of the resin after exposure,
(8) removing the basic compound; and
(5) a step of further developing the first development pattern using an alkali developer to obtain a second development pattern;
The pattern formation method which contains these in this order. (1) forming a first actinic ray-sensitive or radiation-sensitive film with a first actinic ray-sensitive or radiation-sensitive resin composition containing a resin that decomposes by the action of an acid to generate a polar group;
(2) a step of exposing the first actinic ray-sensitive or radiation-sensitive film;
(3) developing the first actinic ray-sensitive or radiation-sensitive film using a developer containing an organic solvent to obtain a first development pattern;
(4) A step of causing a surface treatment agent containing a basic compound to act on the first development pattern as a compound that interacts with the polar group of the resin after exposure,
(7) removing the upper portion of the first development pattern; and
(5) a step of further developing the first development pattern using an alkali developer to obtain a second development pattern;
The pattern formation method which contains these in this order.   The pattern forming method according to claim 1, further comprising: (7) removing an upper portion of the first development pattern between the step (4) and the step (5).   The pattern formation method of Claim 3 including the said process (8) after the said process (7).   The pattern formation method of Claim 3 including the said process (7) after the said process (8).   The pattern forming method according to claim 2, wherein the step (7) is a step (7 ′) of etching the first development pattern.   Between the step (1) and the step (2), (6 ′) the first actinic ray sensitive or radiation sensitive resin composition on the first actinic ray sensitive or radiation sensitive film. The second actinic ray-sensitive or radiation-sensitive film is formed by the second actinic ray-sensitive or radiation-sensitive resin composition containing a resin that is decomposed by the action of an acid and generates a polar group. The pattern formation method of any one of Claims 1-6 including the process to perform.   The resin in the first actinic ray-sensitive or radiation-sensitive resin composition contains a lactone structure, and the resin in the second actinic ray-sensitive or radiation-sensitive resin composition does not contain a lactone structure, The pattern forming method according to claim 7.   The pattern forming method according to claim 1, comprising a step of (10) heating the first development pattern between the step (4) and the step (5).   The pattern formation method of any one of Claims 1-9 in which the said surface treating agent contains resin which has a repeating unit which has a basic functional group as said basic compound.   The pattern formation method according to claim 1, wherein the basic compound is a compound having a primary or secondary amino group.   The pattern forming method according to claim 1, wherein the basic compound is soluble in the alkaline developer.   The pattern formation method according to claim 1, wherein the surface treatment agent contains a solvent, and the solvent is a ketone solvent or an ester solvent. The pattern formation according to any one of claims 1 to 13 , wherein the surface treatment agent contains a solvent, and the step (4) includes a step of bringing the surface treatment agent into contact with the surface of the first development pattern. Method. It said step (4) comprises the step of contacting the vapor of the surface treatment agent to the surface of the first developed pattern, a pattern forming method according to any one of claims 1-14. The exposure is immersion exposure, the pattern forming method according to any one of claims 1 to 15. Claims including a pattern forming method according to any one of claim 1-16, the method of manufacturing an electronic device.

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