METHOD FOR MANUFACTURING CHEMICALLY AMPLIFIED PHOTOSENSITIVE COMPOSITION, PREMIX SOLUTION FOR PREPARING CHEMICALLY AMPLIFIED PHOTOSENSITIVE COMPOSITION, CHEMICALLY AMPLIFIED PHOTOSENSITIVE COMPOSITION, METHOD FOR MANUFACTURING PHOTOSENSITIVE DRY FILM, AND METHOD FOR MANUFACTURING PATTERNED RESIST FILM

Abstract

A method for manufacturing a chemically amplified photosensitive composition capable of reducing a foreign matter derived from a sulfur-containing compound. The method includes an acid generating agent which generates an acid by irradiation with an active ray or radiation, a sulfur-containing compound which is a solid at room temperature, a first solvent having a Hansen solubility parameter in which a polar term δp is 10 (MPa.sup.0.5) or more, and a second solvent which is different than the first solvent, the method including preparing a solution of the sulfur-containing compound by dissolving the sulfur-containing compound in the first solvent, and blending the solution of the sulfur-containing compound, the acid generating agent, and the second solvent.

Claims

1. A method for manufacturing a chemically amplified photosensitive composition, the composition comprising: an acid generating agent (A) to generate an acid by irradiation with an active ray or radiation, a sulfur-containing compound (C), the sulfur-containing compound (C) being solid at room temperature, a solvent (S1) having a Hansen solubility parameter in which a polar term δp is 10 (MPa.sup.0.5) or more, and a solvent (S2), the solvent (S2) being a different solvent from the solvent (S1), the method comprising: preparing a solution of the sulfur-containing compound (C) by dissolving the sulfur-containing compound (C) in the solvent (S1), and blending the solution of the sulfur-containing compound (C), the acid generating agent (A), and the solvent (S2).

2. The method for manufacturing a chemically amplified photosensitive composition according to claim 1, wherein the sulfur-containing compound (C) comprises at least one selected from the group consisting of a compound represented by the following formula (c1-1) or (c1-2) or a tautomer thereof and a compound represented by the following formula (c2): ##STR00087## wherein ring A is a monocyclic ring in which the number of ring constituting atoms is 4 or more and 8 or less, or a polycyclic ring in which the number of ring constituting atoms is 5 or more and 20 or less; X.sup.1c is —CR.sup.11cR.sup.12c—, —NR.sup.13c—, —O—, —S—, —Se—, —Te—, ═CR.sup.14c—, or ═N—; X.sup.2c is —CR.sup.11c═ or —N═; R.sup.11c, R.sup.12c, R.sup.13c and R.sup.14c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 or more and 8 or less carbon atoms, an optionally substituted alkenyl group having 1 or more and 8 or less carbon atoms, an optionally substituted alkynyl group having 1 or more and 8 or less carbon atoms, an optionally substituted aromatic group having 4 or more and 20 or less carbon atoms, or a carboxyl group, and ##STR00088## wherein Y.sup.1c and Y.sup.2c are each independently a nitrogen atom or a carbon atom; R.sup.21c and R.sup.22c are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms, an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, and an alicyclic hydrocarbon group having 3 or more and 18 or less carbon atoms; R.sup.23c is a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms, an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, an alicyclic hydrocarbon group having 3 or more and 18 or less carbon atoms, —SR.sup.24c, or —NR.sup.25cR.sup.26c; R.sup.24c, R.sup.25c, and R.sup.26c are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms, an alicyclic hydrocarbon group having 3 or more and 10 or less carbon atoms, an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, or an acyl group having 1 or more and 12 or less carbon atoms; a hydrogen atom of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the acyl group in R.sup.25c and R.sup.26c may be replaced with a hydroxy group; and n and m are each independently 0 or 1; when Y.sup.1c is a nitrogen atom, n is 0; when Y.sup.1c is a carbon atom, n is 1; when Y.sup.2c is a nitrogen atom, m is 0; and when Y.sup.2c is a carbon atom, m is 1.

3. The method for manufacturing a chemically amplified photosensitive composition according to claim 2, wherein, in the formula (c1-1), X.sup.1c is —NR.sup.13c— or ═N— and in the formula (c2), Y.sup.1c and Y.sup.2c are nitrogen atoms.

4. The method for manufacturing a chemically amplified photosensitive composition according to claim 1, wherein the solvent (S1) is γ-butyrolactone, dimethyl sulfoxide, or N-methyl-2-pyrrolidone.

5. The method for manufacturing a chemically amplified photosensitive composition according to claim 1, wherein the chemically amplified photosensitive composition is a positive type.

6. The method for manufacturing a chemically amplified photosensitive composition according to claim 5, wherein the chemically amplified photosensitive composition comprises a resin (B) having an alkali solubility that increases under action of an acid.

7. The method for manufacturing a chemically amplified photosensitive composition according to claim 5, wherein the chemically amplified photosensitive composition further comprises an alkali-soluble resin (D).

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

9. A premix solution for preparing a chemically amplified photosensitive composition, comprising: a sulfur-containing compound (C), the sulfur-containing compound (C) being solid at room temperature, and a solvent (S1) having a Hansen solubility parameter in which a polar term δp is 10 (MPa.sup.0.5) or more, wherein the sulfur-containing compound (C) is dissolved in the solvent (S1).

10. The premix solution for preparing a chemically amplified photosensitive composition according to claim 9, wherein the sulfur-containing compound (C) comprises at least one selected from the group consisting of a compound represented by the following formula (c1-1) or (c1-2) or a tautomer thereof and a compound represented by the following formula (c2): ##STR00089## wherein ring A is a monocyclic ring having the number of ring constituting atoms of 4 or more and 8 or less, or a polycyclic ring having the number of ring constituting atoms of 5 or more and 20 or less; X.sup.1c is —CR.sup.11cR.sup.12c—, —NR.sup.13c—, —O—, —S—, —Se—, —Te—, ═CR.sup.14c—, or ═N—; X.sup.2c is —CR.sup.11c═ or —N═; R.sup.11c, R.sup.12c, R.sup.13c and R.sup.14c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 or more and 8 or less carbon atoms, an optionally substituted alkenyl group having 1 or more and 8 or less carbon atoms, an optionally substituted alkynyl group having 1 or more and 8 or less carbon atoms, an optionally substituted aromatic group having 4 or more and 20 or less carbon atoms, or a carboxyl group, and ##STR00090## wherein Y.sup.1c and Y.sup.2c are each independently a nitrogen atom or a carbon atom; R.sup.21c and R.sup.22c are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms, an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, and an alicyclic hydrocarbon group having 3 or more and 18 or less carbon atoms; R.sup.23c is a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms, an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, an alicyclic hydrocarbon group having 3 or more and 18 or less carbon atoms, —SR.sup.24c, or —NR.sup.25cR.sup.26c; R.sup.24c, R.sup.25c, and R.sup.26c are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms, an alicyclic hydrocarbon group having 3 or more and 10 or less carbon atoms, an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, or an acyl group having 1 or more and 12 or less carbon atoms; a hydrogen atom of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the acyl group in R.sup.25c and R.sup.26c may be replaced with a hydroxy group; and n and m are each independently 0 or 1; when Y.sup.1c is a nitrogen atom, n is 0; when Y.sup.1c is a carbon atom, n is 1; when Y.sup.2c is a nitrogen atom, m is 0; and when Y.sup.2c is a carbon atom, m is 1.

11. The premix solution for manufacturing a chemically amplified photosensitive composition according to claim 10, wherein, in the formula (c1-1), X.sup.1c is —NR.sup.13c— or ═N— and in the formula (c2), Y.sup.1c and Y.sup.2c are nitrogen atoms.

12. The premix solution for manufacturing a chemically amplified photosensitive composition according to claim 9, wherein the solvent (S1) is γ-butyrolactone, dimethyl sulfoxide, or N-methyl-2-pyrrolidone.

13. A chemically amplified photosensitive composition, comprising: an acid generating agent (A) which generates an acid by irradiation with an active ray or radiation, a sulfur-containing compound (C) which is a solid at room temperature, a solvent (S1) having a Hansen solubility parameter in which a polar term δp is 10 (MPa.sup.0.5) or more, and a solvent (S2) that is different than the solvent (S1), wherein the chemically amplified photosensitive composition has a content of the solvent (S1) of greater than 0% by mass and less than 5% by mass, with respect to a total mass of the solvent (S1) and the solvent (S2).

14. The chemically amplified photosensitive composition according to claim 13, wherein the sulfur-containing compound (C) comprises at least one selected from the group consisting of a compound represented by the following formula (c1-1) or (c1-2) or a tautomer thereof and a compound represented by the following formula (c2): ##STR00091## wherein ring A is a monocyclic ring in which the number of ring constituting atoms is 4 or more and 8 or less, or a polycyclic ring in which the number of ring constituting atoms is 5 or more and 20 or less; X.sup.1c is —CR.sup.11cR.sup.12c—, —NR.sup.13c—, —O—, —S—, —Se—, —Te—, ═CR.sup.14c—, or ═N—, X.sup.2c is —CR.sup.11c═ or —N═, R.sup.11c, R.sup.12c, R.sup.13c, and R.sup.14c are each independently a hydrogen atom, an optionally substituted alkyl group having 1 or more and 8 or less carbon atoms, an optionally substituted alkenyl group having 1 or more and 8 or less carbon atoms, an optionally substituted alkynyl group having 1 or more and 8 or less carbon atoms, an optionally substituted aromatic group having 4 or more and 20 or less carbon atoms, or a carboxyl group, and ##STR00092## wherein Y.sup.1c and Y.sup.2c are each independently a nitrogen atom or a carbon atom; R.sup.21c and R.sup.22c are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms, an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, and an alicyclic hydrocarbon group having 3 or more and 18 or less carbon atoms, R.sup.23c is a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms, an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, an alicyclic hydrocarbon group having 3 or more and 18 or less carbon atoms, —SR.sup.24c, or —NR.sup.25cR.sup.26c; R.sup.24c, R.sup.25c, and R.sup.26c are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms, an alicyclic hydrocarbon group having 3 or more and 10 or less carbon atoms, an aromatic hydrocarbon group having 6 or more and 14 or less carbon atoms, or an acyl group having 1 or more and 12 or less carbon atoms; a hydrogen atom of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the acyl group in R.sup.25c and R.sup.26c may be replaced with a hydroxy group; and n and m are each independently 0 or 1; when Y.sup.1c is a nitrogen atom, n is 0; when Y.sup.1c is a carbon atom, n is 1; when Y.sup.2c is a nitrogen atom, m is 0; and when Y.sup.2c is a carbon atom, m is 1.

15. The chemically amplified photosensitive composition according to claim 14, wherein, in the formula (c1-1), X.sup.1c is —NR.sup.13c— or ═N— and in the formula (c2), Y.sup.1c and Y.sup.2c are nitrogen atoms.

16. The chemically amplified photosensitive composition according to claim 13, wherein the solvent (S1) is γ-butyrolactone, dimethyl sulfoxide, or N-methyl-2-pyrrolidone.

17. The chemically amplified photosensitive composition according to claim 13, wherein the chemically amplified photosensitive composition is a positive type.

18. The chemically amplified photosensitive composition according to claim 17, further comprising a resin (B) having an alkali solubility that increases under action of an acid.

19. The chemically amplified photosensitive composition according to claim 17, further comprising an alkali-soluble resin (D).

20. The chemically amplified photosensitive composition according to claim 19, wherein the alkali-soluble resin (D) comprises at least one selected from the group consisting of a novolac resin (D1), a polyhydroxystyrene resin (D2), and an acrylic resin (D3).

21. A method for manufacturing a photosensitive dry film, the method comprising coating a substrate film with the chemically amplified photosensitive composition according to claim 13, to form a photosensitive layer.

22. A method for manufacturing a patterned resist film, the method comprising: laminating a photosensitive layer on a substrate, the layer comprising the chemically amplified photosensitive composition according to claim 13; exposing the photosensitive layer through irradiation with an active ray or radiation in a position-selective manner; and developing the exposed photosensitive layer.

23. The method for manufacturing a patterned resist film according to claim 22, wherein the substrate is a substrate having a metal surface.

Description

EXAMPLES

[0304] The present invention will be described in more detail below by way of Examples, but the present invention is not limited to these Examples.

Examples 1 to 29 and Comparative Examples 1 to 29

[0305] In Examples 1 to 29 and Comparative Examples 1 to 29, as the sulfur-containing compound (C), compounds C1 to C5 of the following formulae were used.

##STR00082##

[0306] In Examples 1 to 29 and Comparative Examples 1 to 29, as the acid generating agent (A), PAG A1 and PAG A4 of the following formulae were used.

##STR00083##

[0307] In Examples 1 to 29 and Comparative Examples 1 to 29, the following Resin A1 to Resin A5 were used as the resin having an alkali solubility that increases under action of an 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 40,000 and dispersivity Mw/Mn) of 2.6. Resin A2 has a mass average molecular weight Mw of 40,000 and dispersivity (Mw/Mn) of 2.6. Resin A3 has a number average molecular weight Mn of 98,000. Resin A4 has a number average molecular weight Mn of 98,000. Resin A5 has a number average molecular weight Mn of 98,000.

##STR00084## ##STR00085##

[0308] In Examples 1 to 29 and Comparative Examples 1 to 29, the following Resin B1 (polyhydroxystyrene resin) and Resin C (novolac resin (m-cresol mono-condensate)) were used as the alkali-soluble resin (D). 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 B1 has a mass average molecular weight (Mw) of 2,500, and dispersivity (Mw/Mn) of 2.4. Resin C has a mass average molecular weight (Mw) of 8,000.

##STR00086##

[0309] As the acid diffusion inhibiting agent (F), the following Amine-1 to Amine-3 were used.

Amine-1: ADK STAB LA-63P (manufactured by ADEKA)
Amine-2: diphenylpyridine
Amine-3: triphenylpyridine

Examples 1 to 27

[0310] A γ-butyrolactone (GBL) solution (premix solution) in which each of the sulfur-containing compounds (C) described in Table 1 and Table 2 was dissolved so that the content of the sulfur-containing compound (C) was 1% by mass, was obtained. Visually, it was confirmed that the sulfur-containing compound (C) was completely dissolved. In addition, each of the acid generating agents (A), the resins (B), the alkali-soluble resins (D), and the acid diffusion inhibiting agents (F) of types and amounts described in Table 1 and Table 2 and 0.05 parts by mass of a surfactant (BYK310, manufactured by Byk Chemie Co., Ltd.) were dissolved in 3-methoxybutyl acetate (MA, δp: 4.1 MPa.sup.0.5, boiling point: 172° C.) so that the solid content was 53% by mass, and then the obtained solution was filtered through a membrane filter having a pore diameter of 1 μm. To each of the solutions after filtration, the γ-butyrolactone solution (premix solution) was added so that the sulfur-containing compound (C) had the values described in Table 1 and Table 2, and the mixture was stirred for 30 minutes and allowed to stand for 4 hours to obtain positive type chemically amplified photosensitive compositions of Examples 1 to 27.

Example 28

[0311] A positive-type chemically amplified photosensitive composition of Example 28 was obtained by carrying out the same procedures as in Example 1, except that dimethyl sulfoxide (DMSO) was used instead of γ-butyrolactone.

Example 29

[0312] A positive chemically amplified photosensitive composition of Example 29 was obtained by carrying out the same procedures as in Example 1, except that N-methyl-2-pyrrolidone (NMP) was used instead of γ-butyrolactone.

Comparative Examples 1 to 27

[0313] Each of the acid generating agents (A), the resins (B), the alkali-soluble resins (D), and the acid diffusion inhibiting agents (F) of types and amounts described in Table 3 and Table 4 and 0.05 parts by mass of a surfactant (BYK310, manufactured by Byk Chemie Co., Ltd.) were dissolved in 3-methoxybutyl acetate (MA) so that the solid content was 53% by mass, and then the obtained solution was filtered through a membrane filter having a pore diameter of 1 μm. To each of the solutions after filtration, the sulfur-containing compound (C) was added so that the sulfur-containing compound (C) had the values described in Table 3 and Table 4, and the mixture was stirred for 30 minutes and allowed to stand for 4 hours to obtain positive-type chemically amplified photosensitive compositions of Comparative Examples 1 to 27.

Comparative Example 28

[0314] A positive-type chemically amplified photosensitive composition of Comparative Example 28 was obtained by carrying out the same procedures as in Example 1, except that methyl ethyl ketone (MEK, δp: 9.0 MPa.sup.0.5, boiling point: 80° C.) was used instead of γ-butyrolactone. The methyl ethyl ketone solution (premix solution) in which the sulfur-containing compound (C) was dissolved so that the content of the sulfur-containing compound (C) was 1% by mass was a suspension in which the sulfur-containing compound (C) was not dissolved, and the obtained positive-type chemically amplified photosensitive composition was also a suspension.

Comparative Example 29

[0315] A positive-type chemically amplified photosensitive composition of Comparative Example 29 was obtained by carrying out the same procedures as in Example 1, except that 3-methoxybutyl acetate (MA) was used instead of γ-butyrolactone. The 3-methoxybutyl acetate solution (premix solution) in which the sulfur-containing compound (C) was dissolved so that the content of the sulfur-containing compound (C) was 1% by mass was a suspension in which the sulfur-containing compound (C) was not dissolved, and the obtained positive-type chemically amplified photosensitive composition was also a suspension.

[0316] The obtained positive-type chemically amplified photosensitive compositions were evaluated according to the following method. The evaluation results are described in Tables 1 to 4.

[Evaluation for Foreign Matter]

[0317] Silicon substrates having a diameter of 8 inches were provided, each of the substrate including a copper layer formed by sputtering on a surface thereof. The chemically amplified photosensitive compositions of Examples and Comparative Examples were each applied on the copper layer of each of the substrates to form a photosensitive layer (coated film of the chemically amplified photosensitive composition) having a thickness of 55 μm. Then, the photosensitive layer was pre-baked at 130° C. for 5 minutes. After the pre-baking, using a mask having a line-and-space pattern having a line width of 2.0 μm and a space width of 2.0 μm, and Canon PLA501F Hardcontact (manufactured by Canon Inc.), pattern exposure was performed with an ultraviolet ray having a wavelength of 365 nm at an exposure dose greater by 1.2 times than the minimum exposure dose capable of forming a pattern having a predetermined size. Subsequently, the substrate was mounted on a hot plate and post-exposure baking (PEB) was performed at 90° C. for 1.5 minutes. Subsequently, an aqueous 2.38% by weight solution of tetramethylammonium hydroxide (TMAH) (developing solution, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was added dropwise to the exposed photosensitive layer, and the photosensitive layer was allowed to stand at 23° C. for 30 seconds. This operation was repeated three times in total. Subsequently, the surface of the resist pattern was washed (rinsed) with running water, and blown with nitrogen to obtain a resist pattern. For the obtained resist pattern (line and space pattern), 50 locations were randomly observed under an optical microscope (magnification: 10×magnification) to confirm the presence or absence of a foreign matter (the sulfur-containing compound (C) remaining without being dissolved). The resist pattern in which 3 or less foreign matters were observed was evaluated as excellent (indicated by bullseye symbol (⊙)), the resist pattern in which 4 or more and 9 or less foreign matters were observed was evaluated as good (indicated by circle symbol (∘)), and the resist pattern in which 10 or more and 19 or less foreign matters were observed was evaluated as poor (indicated by cross symbol (×)), and the resist pattern in which 20 or more foreign matters were observed was evaluated as bad (indicated by double cross symbol (××)). Note that the observed foreign matters had a size of 10 μm or more and 1 mm or less. Furthermore, since filtration was performed before addition of the sulfur-containing compound (C), the foreign matters observed are considered to be only those derived from the sulfur-containing compound (C).

TABLE-US-00001 TABLE 1 Resin (B) and Acid diffusion Acid generating alkali-soluble Sulfur-containing inhibiting agent (A) resin (D) compound (C) agent (F) Solvent Evaluation Type/part(s) Type/part(s) Type/part(s) Type/part(s) (S1) Foreign by mass by mass by mass by mass Type matter Example 1 PAG-A1/0.3 Resin-A1/40 C1/0.1  Amine-1/0.15 GBL ⊙ Example 2 Resin-B1/20 C2/0.1 ⊙ Example 3  Resin-C/40 C3/0.1 ⊙ Example 4 C4/0.1 ⊙ Example 5 C5/0.1 ⊙ Example 6  C1/0.03 ⊙ Example 7  C2/0.03 ⊙ Example 8 C1/0.3 ⊙ Example 9 C2/0.3 ⊙ Example 10 PAG-A2/0.3 C1/0.1 Amine-1/1.5 ⊙ Example 11 C2/0.1 ⊙ Example 12 PAG-A3/1.5 C1/0.1 Amine-2/0.1 ⊙ Example 13 C2/0.1 Amine-3/0.1 ⊙ Example 14 PAG-A4/1.5 C1/0.1 ⊙ Example 15 C2/0.1 ⊙

TABLE-US-00002 TABLE 2 Resin (B) and Acid diffusion Acid generating alkali-soluble Sulfur-containing inhibiting agent (A) resin (D) compound (C) agent (F) Solvent Evaluation Type/part(s) Type/part(s) Type/part(s) Type/part(s) (S1) Foreign by mass by mass by mass by mass Type matter Example 16 PAG-A1/0.3 Resin-A1/40  C1/0.1 Amine-1/1.5 GBL ⊙ Example 17 Resin-B1/20  C2/0.1 ⊙ Resin-C/40 Example 18 Resin-A2/40  C1/0.1 ⊙ Example 19 Resin-B1/20  C2/0.1 ⊙ Resin-C/40 Example 20 Resin-A3/40  C1/0.1 ⊙ Example 21 Resin-B1/20  C2/0.1 ⊙ Resin-C/40 Example 22 Resin-A4/40  C1/0.1 ⊙ Example 23 Resin-B1/20  C2/0.1 ⊙ Resin-C/40 Example 24 Resin-A5/40  C1/0.1 ⊙ Example 25 Resin-B1/20  C2/0.1 ⊙ Resin-C/40 Example 26 PAG-A3/1.5 Resin-A2/100 C1/0.1 Amine-2/0.1 ⊙ Example 27 C2/0.1 Amine-3/0.1 ⊙ Example 28 PAG-A1/0.3 Resin-A1/40  C1/0.1  Amine-1/0.15 DMSO ⊙ Example 29 Resin-B1/20  NMP ⊙ Resin-C/40

TABLE-US-00003 TABLE 3 Acid generating Resin (B) and Sulfur-containing Acid diffusion agent alkali-soluble compound inhibiting agent (A) resin (D) (C) (F) Evaluation Type/part(s) Type/part(s) Type/part(s) Type/part(s) Foreign by mass by mass by mass by mass matter Comparative Example 1 PAG-A1/0.3 Resin-A1/40 C1/0.1 Amine-1/0.15 xx Comparative Example 2 Resin-B1/20 C2/0.1 xx Comparative Example 3 Resin-C/40 C3/0.1 xx Comparative Example 4 C4/0.1 xx Comparative Example 5 C5/0.1 xx Comparative Example 6 C1/0.03 xx Comparative Example 7 C2/0.03 xx Comparative Example 8 C1/0.3 xx Comparative Example 9 C2/0.3 xx Comparative Example 10 PAG-A2/0.3 C1/0.1 Amine-1/1.5 xx Comparative Example 11 C2/0.1 xx Comparative Example 12 PAG-A3/1.5 C1/0.1 Amine-2/0.1 xx Comparative Example 13 C2/0.1 Amine-3/0.1 xx Comparative Example 14 PAG-A4/1.5 C1/0.1 xx Comparative Example 15 C2/0.1 xx

TABLE-US-00004 TABLE 4 Acid generating Resin (B) and Sulfur-containing Acid diffusion agent alkali-soluble compound inhibiting agent (A) resin (D) (C) (F) Evaluation Type/part(s) Type/part(s) Type/part(s) Type/part(s) Foreign by mass by mass by mass by mass matter Comparative Example 16 PAG-A1/0.3 Resin-A1/40 C1/0.1 Amine-1/1.5 xx Comparative Example 17 Resin-B1/20 C2/0.1 xx Resin-C/40 Comparative Example 18 Resin-A2/40 C1/0.1 xx Comparative Example 19 Resin-B1/20 C2/0.1 xx Resin-C/40 Comparative Example 20 Resin-A3/40 C1/0.1 xx Comparative Example 21 Resin-B1/20 C2/0.1 xx Resin-C/40 Comparative Example 22 Resin-A4/40 C1/0.1 xx Comparative Example 23 Resin-B1/20 C2/0.1 xx Resin-C/40 Comparative Example 24 Resin-A5/40 C1/0.1 xx Comparative Example 25 Resin-B1/20 C2/0.1 xx Resin-C/40 Comparative Example 26 PAG-A3/1.5 Resin-A2/100 C1/0.1 Amine-2/0.1 xx Comparative Example 27 C2/0.1 Amine-3/0.1 xx Comparative Example 28 PAG-A1/0.3 Resin-A1/40 C1/0.1 Araine-1/0.15 x Comparative Example 29 Resin-B1/20 x Resin-C/40

[0318] According to Examples 1 to 29, it can be seen that in the resist patterns formed of the chemically amplified photosensitive compositions prepared by dissolving in advance the sulfur-containing compound (C), the sulfur-containing compound (C) being solid at room temperature, in the solvent (S1) having a Hansen solubility parameter in which the polar term δp is 10 (MPa.sup.0.5) or more, and then mixing with other components, fewer foreign matters occurred. Furthermore, it can be seen that the chemically amplified photosensitive compositions of Examples 1 to 29 included fewer foreign matters, since there were fewer foreign matters in the resist patterns formed.

[0319] Contrary to this, it can be seen from Comparative Examples 1 to 29 that, in the resist patterns formed of the chemically amplified photosensitive compositions of Comparative Examples 1 to 27 prepared by adding the sulfur-containing compound (C), the sulfur-containing compound (C) being solid at room temperature, as powder (solid) or in the resist patterns formed of the chemically amplified photosensitive compositions of Comparative Examples 28 and 29 prepared by dissolving in advance the sulfur-containing compound (C) in a solvent having a Hansen solubility parameter in which the polar term δp is less than 10 (MPa.sup.0.5) and then mixing with other components, significant number of foreign matters occurred.