CHEMICALLY AMPLIFIED POSITIVE-TYPE PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE DRY FILM, METHOD FOR PRODUCING PHOTOSENSITIVE DRY FILM, METHOD FOR PRODUCING PATTERNED RESIST FILM, METHOD FOR PRODUCING SUBSTRATE PROVIDED WITH TEMPLATE, AND METHOD FOR PRODUCING A PLATED ARTICLE

Abstract

A chemically amplified positive-type photosensitive resin composition with which a resist pattern having a rectangular cross-sectional shape is easily formed, which has satisfactory sensitivity, and which can suppress decomposition of the acid generating agent; a photosensitive dry film having a photosensitive layer including the photosensitive resin composition; a method for producing the photosensitive dry film; a method for producing a patterned resist film using the positive-type photosensitive resin composition; a method for producing a substrate provided with a template using the positive-type photosensitive resin composition; and a method for producing a plated article using the positive-type photosensitive resin composition. The photosensitive resin composition includes an acid generating agent to generate an acid by irradiation with an active ray or radiation, a resin having alkali solubility that increases under action of an acid, and an acid diffusion suppressing agent, wherein the acid generating agent includes a non-ionic acid generating agent that generates sulfonic acid upon the irradiation, and the acid diffusion suppressing agent includes a compound having a specific structure that is decomposed by the irradiation.

Claims

1. A chemically amplified positive-type photosensitive resin composition comprising an acid generating agent (A) to generate an acid by irradiation with an active ray or radiation, a resin (B) having alkali solubility that increases under action of an acid, and an acid diffusion suppressing agent (C), the acid generating agent (A) comprising a non-ionic acid generating agent to generate sulfonic acid upon the irradiation with active rays or radiation, the acid diffusion suppressing agent (C) comprising a compound decomposed by the irradiation with an active ray or radiation and represented by the following formula (c1): ##STR00092## wherein, in the formula (c1), M.sup.m+ represents an m-valent organic cation, m represents an integer of 1 or more, a ring Z represents a benzene ring, or a benzene ring-fused polycyclic, a number x of the benzene rings as the ring Z is an integer of 1 or more and 4 or less, R.sup.1c represents a substituent, A.sup.− represents —COO.sup.− or —SO.sub.2O.sup.−, n represents an integer of 2 or more and 2x+3 or less, p represents an integer of 0 or more and 2x+3−n or less, and when p is 2 or more, a plurality of R.sup.1cs is identical to or different from each other, and a plurality of R.sup.1cs may be linked to each other to form a ring.

2. The chemically amplified positive-type photosensitive resin composition according to claim 1, wherein in the ring Z, a hydroxy group is bonded to at least one of two carbon atoms adjacent to a carbon atom to which the A.sup.− is bonded.

3. The chemically amplified positive-type photosensitive resin composition according to claim 1, wherein the compound represented by the formula (c1) is a compound represented by the following formula (c2): ##STR00093## wherein in the formula (c2), M.sup.m+, R.sup.1c, A.sup.−, m, n, and p are respectively identical to as M.sup.m+, R.sup.1c, A.sup.−, m, n, and p in the formula (c1), q represents an integer of 0 or more and 3 or less, n, p, and q satisfy a formula n+p≤(q×2)+5.

4. The chemically amplified positive-type photosensitive resin composition according to claim 3, wherein the q is 0 or more and 1 or less.

5. The chemically amplified positive-type photosensitive resin composition according to claim 1, wherein the non-ionic acid generating agent is at least one compound selected from the group consisting of an imide sulfonate compound and an oxime sulfonate compound.

6. The chemically amplified positive-type photosensitive resin composition according to claim 1, further comprising an alkali-soluble resin (D).

7. The chemically amplified positive-type photosensitive resin composition according to claim 6, wherein the alkali-soluble resin (D) comprises at least one resin selected from the group consisting of a novolac resin (D1), a polyhydroxystyrene resin (D2), and an acrylic resin (D3).

8. The chemically amplified positive-type photosensitive resin composition according to claim 1, further comprising a sulfur-containing compound (E) containing a sulfur atom capable of coordinating with a metal.

9. A photosensitive dry film, comprising a base material film and a photosensitive layer formed on a surface of the base material film, the photosensitive layer comprising the chemically amplified positive-type photosensitive resin composition according to claim 1.

10. A method for producing a photosensitive dry film, the method comprising applying the chemically amplified positive-type photosensitive resin composition according to claim 1, on a base material film to form a photosensitive layer.

11. A method for producing a patterned resist film, the method comprising: laminating a photosensitive layer comprising the chemically amplified positive-type photosensitive resin composition according to claim 1, on a substrate; exposing the photosensitive layer through irradiation with an active ray or radiation in a position-selective manner; and developing the photosensitive layer after exposure.

12. A method for producing a substrate provided with a template, the method comprising: laminating a photosensitive layer comprising the chemically amplified positive-type photosensitive resin composition according to claim 1, on a substrate having a metal surface; exposing the photosensitive layer through irradiation with an active ray or radiation in a position-selective manner; and developing the photosensitive layer after exposure to prepare a template for forming a plated article.

13. A method for producing a plated article, the method comprising plating a substrate provided with a template to form a plated article in the template, wherein the substrate is produced by the method for producing a substrate provided with a template according to claim 12.

Description

EXAMPLES

[0343] The present invention will be described in more detail below by way of Examples, but the present invention is not limited to these Examples.

Preparation Example 1

(Synthesis of Mercapto Compound T2)

[0344] In Preparation Example 1, a mercapto compound T2 having the following structure was synthesized as a sulfur-containing compound (E).

##STR00082##

[0345] In a flask, 15.00 g of 7-oxanorborna-5-ene-2,3-dicarboxylic anhydride and 150.00 g of tetrahydrofuran were added, followed by stirring. Then, 7.64 g of thioacetic acid (AcSH) was added in a flask, followed by stirring at room temperature for 3.5 hours. Thereafter, the reaction solution was concentrated to obtain 22.11 g of 5-acetylthio-7-oxanorbornane-2,3-dicarboxylic anhydride. In a flask, 22.11 g of 5-acetylthio-7-oxanorbornane-2,3-dicarboxylic anhydride and 30.11 g of sodium hydroxide aqueous solution having the concentration of 10% by mass were added, and then contents in the flask were stirred at room temperature for 2 hours. Then, hydrochloric acid (80.00 g) having a concentration of 20% by mass was added in the flask to acidify the reaction solution. Thereafter, extraction with 200 g of ethyl acetate was performed four times to obtain an extraction liquid including a mercapto compound T2. The extraction liquid was concentrated to collect residue, and the collected residue was dissolved by adding 25.11 g of tetrahydrofuran (THF). Heptane was added dropwise to the obtained THF solution to precipitate the mercapto compound T2, and the precipitated mercapto compound T2 was collected by filtration. The measurement results of .sup.1H-NMR of the mercapto compound T2 are shown below.

[0346] .sup.1H-NMR (DMSO-d6): δ12.10 (s, 2H), 4.72 (d, 1H), 4.43 (s, 1H), 3.10 (t, 1H), 3.01 (d, 1H), 2.85 (d, 1H), 2.75 (d, 1H), 2.10 (t, 1H), 1.40 (m, 1H)

##STR00083##

Examples 1 to 12, and Comparative Examples 1 to 4

[0347] In Examples 1 to 12, and Comparative Examples 1 to 4, as the acid generating agent (A), the following PAG1 was used.

##STR00084##

[0348] In Examples 1 to 12 and Comparative Examples 1 to 4, the following Resin A1 and Resin A2 were used as the resin having an alkali solubility that increases under action of acid (resin (B)). The number at the lower right of the parentheses in each constituent unit in the following structural formula represents the content (% by mass) of the constituent unit in each resin. Resin A1 has a mass average molecular weight Mw of 42000, and Resin A2 has a mass average molecular weight Mw of 40000.

##STR00085##

[0349] As the acid diffusion suppressing agent (C), the following C1 to C11 were used.

##STR00086## ##STR00087## ##STR00088## ##STR00089##

[0350] As the alkali-soluble resin (D), the following Resin B (polyhydroxystyrene resin) and Resin C (novolac resin (m-cresol single fusion product)) were used. The number at the lower right of the parentheses in each constituent unit in the following structural formula represents the content (% by mass) of the constituent unit in each resin. Resin B has a mass average molecular weight (Mw) of 2500, and dispersivity (Mw/Mn) of 2.4. Resin C has a mass average molecular weight (Mw) of 8000.

##STR00090##

[0351] As the sulfur-containing compound (E), the following sulfur-containing compounds T1 to T3 were used.

##STR00091##

[0352] The acid generating agent (A), the resin (B), the acid diffusion control agent (C), the alkali-soluble resin (D), and the sulfur-containing compound (E) in types and amounts shown in Table 1, and a surfactant (BYK310, manufactured by BYK) were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to obtain photosensitive resin compositions of Examples and Comparative Examples. Note here that the surfactant (BYK310, manufactured by BYK) was added in an amount of 0.05 parts by mass with respect to the total amount of the resin (B) and the alkali-soluble resin (D). The photosensitive resin composition of Examples 1 to 12, and Comparative Examples 1 to 4 was prepared such that the solid content concentration was 35% by mass.

[0353] Using the obtained photosensitive resin composition, shapes and sensitivity were evaluated according to the following methods. The results are shown in Tables 1 and 2.

[0354] [Evaluation of Shape]

[0355] A substrate including a glass substrate having a diameter of 500 mm and a copper layer provided on a surface of the glass substrate by sputtering was prepared, and the photosensitive resin compositions of Examples and Comparative Examples were each applied on the prepared substrate to form a photosensitive layer having a thickness of 5 μm. Then, the photosensitive layer was pre-baked at 120° C. for 4 minutes. After the pre-baking, exposure was carried out with an ultraviolet ray having a wavelength of 365 nm with an exposure amount 1.2 times as large as the minimum exposure amount capable of forming a pattern having a predetermined size using a mask having a line-and-space pattern having a line width of 2 μm and a space width of 2 μm, and exposure apparatus FPA-5510iV (manufactured by Canon Inc.). Then, the substrate was mounted on a hot plate and post-exposure baking (PEB) was carried out at 90° C. for 1.5 minutes. Thereafter, 2.38% by weight aqueous solution of tetramethylammonium hydroxide (developing solution, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was added dropwise to the exposed photosensitive layer, and allowed to stand at 23° C. for 30 seconds. This operation was repeated twice in total. Thereafter, the surface of the resist pattern was washed (rinsed) with running water, and then subjected to blowing with nitrogen to obtain a resist pattern. The cross-sectional shape of this resist pattern was observed under a scanning electron microscope, and the cross-sectional shape of the pattern was evaluated. Specifically, when a width of a surface (bottom) of the resist pattern in contact with the substrate is Wb, and a width of a surface (top) of the resist pattern opposite to the surface in contact with the substrate is Wt, a case where (Wt-Wb)/Wt is within ±10% was evaluated as good, and a case where (Wt-Wb)/Wt is beyond ±10% was evaluated as poor. The results are shown in Table 1.

[Evaluation of Sensitivity]

[0356] A line-and-space pattern having a line width of 2 μm and a space width of 2 μm was formed by adjusting the exposure amount using a mask for forming a line-and-space pattern by the same method as of evaluation of shape. The exposure amount capable of forming a line-and-space pattern having a desired dimension was defined as sensitivity. The results are shown in Table 1.

[Evaluation of Decomposition Property of Acid Generating Agent by Acid Diffusion Suppressing Agent]

[0357] A propylene glycol monomethyl ether acetate (PGMEA) solution by mixing equivalent molar amount of acid diffusion suppressing agents C1 to C12 and PAG1 used in Examples 1 to 12 and Comparative Examples 1 to 4 was prepared, and stored at 40° C. for 24 hours. Note here that the propylene glycol monomethyl ether acetate solution was prepared such that the solid content concentration was 2% by mass. After storage, the decomposition rate of the acid generating agent (PAG1) was calculated by the following formula using .sup.19F-NMR. When a case where the decomposition rate was less than 1% was evaluated as ∘ (good), a case where the decomposition rate was 1% or more and 5% or less was evaluated as A (fair), and a case where the decomposition rate was more than 5% was evaluated as × (poor). In the formula, the integral ratio of an acid state is an integral ratio of F in CF.sub.3SO.sub.3H, and the integral ratio of PAG state is the integral ratio of F in PAG1. The results are shown in the “stability” column of Table 1.

Decomposition rate of acid generating agent (%)=(integral ratio of acid state)/[(integral ratio of PAG state)+(integral ratio of acid state)]×100

TABLE-US-00001 TABLE 1 Acid Resin (B) and Diffusion Sulfur- generating alkali-soluble suppressing containing agent (A) resin (D) agent (C) compound (E) Types/part Types/part Types/part Types/part Sensitivity by mass by mass by mass by mass (J/m.sup.2) Shape Stability Example 1 PAG1/1.0 ResinA1/35 C1/0.46 T1/0.05 800 ◯ ◯ Example 2 ResinB/10 C2/0.47 T3/0.08 900 ◯ ◯ Example 3 ResinC/55 C3/0.47 1000 ◯ Δ Example 4 C4/0.47 900 ◯ ◯ Example 5 C5/0.52 900 ◯ ◯ Example 6 C6/0.53 800 ◯ ◯ Example 7 C7/0.53 900 ◯ ◯ Example 8 C8/0.48 800 ◯ ◯ Example 9 C9/0.50 800 ◯ ◯ Example 10 C10/0.43 1000 ◯ ◯ Example 11 PAG1/0.5 ResinA2/40 C1/0.20 T1/0.01 800 ◯ ◯ Example 12 ResinB/20 C10/0.18 T2/0.05 900 ◯ ◯ ResinC/40 Comparative PAG1/1.0 ResinA1/35 C11/0.14 T1/0.05 1200 X ◯ Example 1 ResinB/10 T3/0.08 Comparative ResinC/55 C12/0.45 1000 ◯ X Example 2 Comparative PAG1/0.5 ResinA2/40 C11/0.06 T1/0.01 1000 X ◯ Example 3 ResinB/20 T2/0.05 Comparative ResinC/40 C12/0.19 1000 ◯ X Example 4

[0358] According to Examples 1 to 12, the positive-type photosensitive resin compositions each including an acid generating agent (A) to generate an acid by irradiation with an active ray or radiation, a resin (B) having alkali solubility that increases under action of acid, and an acid diffusion suppressing agent (C), the acid generating agent (A) including a nonionic acid generating agent to generate sulfonic acid by irradiation with an active ray or radiation, the acid diffusion suppressing agent (C) including a compound represented by the formula (c1), which is to be decomposed by irradiation with an active ray or radiation, had a shape better than and sensitivity equivalent or higher than the positive-type photosensitive resin compositions of Comparative Examples 1 and 3, which did not include the acid diffusion suppressing agent decomposed by irradiation with an active ray or radiation. Then, the decomposition rate of the non-ionic acid generating agent by the acid diffusion suppressing agent (C) was also lower.

[0359] On the other hand, in Comparative Examples 2 and 4, as the acid diffusion suppressing agent (C), when compounds being decomposed by irradiation with an active ray or radiation but being different from the compound represented by the formula (c1) were used, it is seen that the non-ionic acid generating agent to generate sulfonic acid was decomposed.