Treatment liquid for manufacturing semiconductor and pattern forming method

Abstract

An object of the present invention is to provide a treatment liquid for manufacturing a semiconductor and a pattern forming method, in which the formation of particles including metal atoms can be reduced and an excellent pattern can be formed. A treatment liquid for manufacturing a semiconductor according to an embodiment of the present invention includes: a quaternary ammonium compound represented by Formula (N); at least one additive selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and a chelating agent; and water. The treatment liquid for manufacturing a semiconductor includes one kind or two or more kinds of metal atoms selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, and a total mass of the metal atoms is 1 mass ppt to 1 mass ppm with respect to the sum of a total mass of the additive and the total mass of the metal atoms.

Claims

1. A treatment liquid for manufacturing a semiconductor comprising: a quaternary ammonium compound represented by the following Formula (N); at least one additive selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and a chelating agent; and water, wherein the treatment liquid for manufacturing a semiconductor includes one kind or two or more kinds of metal atoms selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, and a ratio T.sub.1 of a total mass of the metal atoms to the sum of a total mass of the additive and the total mass of the metal atoms as defined by the following formula is in a range from 1 ppt to 1 ppm,
T.sub.1=[total mass of the metal atoms]/([total mass of the additive]+[total mass of the metal atoms]), ##STR00093## in Formula (N), R.sub.N1 to R.sub.N4 each independently represent an alkyl group, a phenyl group, a benzyl group, or a cyclohexyl group, and the alkyl group, the phenyl group, the benzyl group, or the cyclohexyl group may have a substituent.

2. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the ratio T.sub.1 is in a range from 1 ppb to 1 ppm.

3. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein a ratio T.sub.2 of a total mass of particulate metal of the metal atoms measured by a SP-ICP-MS method to the sum of the total mass of the additive and the total mass of the particulate metal as defined by the following formula is in a range from 0.1 ppt to 0.1 ppm,
T.sub.2=[total mass of the particulate metal]/([total mass of the additive]+[total mass of the particulate metal]) .

4. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein a ratio T.sub.2 of a total mass of particulate metal of the metal atoms measured by a SP-ICP-MS method to the sum of the total mass of the additive and the total mass of the particulate metal as defined by the following formula is in a range from 0.1 ppt to 1 ppb,
T.sub.2=[total mass of the particulate metal]/([total mass of the additive]+[total mass of the particulate metal]) .

5. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein a content of the quaternary ammonium compound is 25 mass % or lower and a content of the additive is 1 mass % or lower with respect to the treatment liquid for manufacturing a semiconductor.

6. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein a content of each of the one kind or two or more kinds of metal atoms selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn is 1 mass ppq to 1000 mass ppt with respect to the treatment liquid for manufacturing a semiconductor.

7. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein a content of each of the one kind or two or more kinds of metal atoms selected from the group consisting of Na, K, and Ca is 1 mass ppq to 1000 mass ppt with respect to the treatment liquid for manufacturing a semiconductor.

8. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the treatment liquid for manufacturing a semiconductor comprises at least the nonionic surfactant as the additive and further comprises a peroxide, and a content of the peroxide is 1 mass ppq to 1000 mass ppt with respect to the treatment liquid for manufacturing a semiconductor.

9. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the treatment liquid for manufacturing a semiconductor comprises at least the nonionic surfactant as the additive and further comprises an ester compound, and a content of the ester compound is 1 mass ppq to 1000 mass ppt with respect to the treatment liquid for manufacturing a semiconductor.

10. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the treatment liquid for manufacturing a semiconductor comprises at least the nonionic surfactant as the additive and further comprises an amine compound, and a content of the amine compound is 1 mass ppq to 1000 mass ppt with respect to the treatment liquid for manufacturing a semiconductor.

11. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the treatment liquid for manufacturing a semiconductor comprises at least the nonionic surfactant as the additive, and an HLB of the nonionic surfactant is 8 or higher.

12. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the treatment liquid for manufacturing a semiconductor comprises at least the nonionic surfactant as the additive, and the treatment liquid for manufacturing a semiconductor comprises at least a compound represented by the following Formula (A1) as the nonionic surfactant, ##STR00094## in Formula (A 1), R.sub.a1, R.sub.a2, R.sub.a3 and R.sub.a4 each independently represent an alkyl group, and L.sub.a1 and L.sub.a2 each independently represent a single bond or a divalent linking group.

13. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the treatment liquid for manufacturing a semiconductor comprises at least the anionic surfactant as the additive and further comprises an inorganic salt, and a content of the inorganic salt is 1 mass ppq to 1000 mass ppt with respect to the treatment liquid for manufacturing a semiconductor.

14. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the treatment liquid for manufacturing a semiconductor comprises at least the cationic surfactant as the additive and further comprises an inorganic salt, and a content of the inorganic salt is 1 mass ppq to 1000 mass ppt with respect to the treatment liquid for manufacturing a semiconductor.

15. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the treatment liquid for manufacturing a semiconductor comprises at least a chelating agent represented by the following Formula (K1) or (K2) as the additive, a portion of the chelating agent forms a chelate complex with the one kind or two or more kinds of metal atoms selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, and a content of the chelate complex is 1 mass ppq to 1000 mass ppt with respect to the treatment liquid for manufacturing a semiconductor, ##STR00095## in Formula (K1), R.sup.K1 and R.sup.K2 each independently represent a single bond or an alkylene group, R.sup.K3 represents a divalent organic group, X.sub.1 represents a CH group or a nitrogen atom, Y.sup.K1 and Y.sup.K2 each independently represent a metal-adsorbing group, and A.sub.1 represents a hydrogen atom or a hydrophilic group, and in Formula (K2), R.sup.K4, R.sup.K5, R.sup.K6, and R.sup.K7 each independently represent a single bond or an alkylene group, R.sup.K8 represents a trivalent organic group, X.sub.2 and X.sub.3 each independently represent a CH group or a nitrogen atom, Y.sup.K3, Y.sup.K4, Y.sup.K5, and Y.sup.K5 each independently represent a metal-adsorbing group, and A.sub.2 represents a hydrogen atom or a hydrophilic group.

16. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the treatment liquid for manufacturing a semiconductor comprises two or more additives.

17. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the treatment liquid for manufacturing a semiconductor comprises two or more nonionic surfactants as the additive.

18. The treatment liquid for manufacturing a semiconductor according to claim 17, wherein the treatment liquid for manufacturing a semiconductor comprises at least one nonionic surfactant having an HLB of 12 or higher and at least one nonionic surfactant having an HLB of 10 or lower as the two or more nonionic surfactants.

19. The treatment liquid for manufacturing a semiconductor according to claim 8, wherein a total mass of the nonionic surfactant having an HLB of 12 or higher is 0.5 to 4 with respect to a total mass of the nonionic surfactant having an HLB of 10 or lower.

20. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the treatment liquid for manufacturing a semiconductor comprises at least the nonionic surfactant as the additive, and the treatment liquid for manufacturing a semiconductor comprises at least a compound represented by the following Formula (A1) as the nonionic surfactant, ##STR00096## in Formula (A 1), R.sub.a1, R.sub.a2, R.sub.a3, and R.sub.a4 each independently represent an alkyl group, and L.sub.al and L.sub.a2 each independently represent a single bond or a divalent linking group.

21. The treatment liquid for manufacturing a semiconductor according to claim 20, wherein the treatment liquid for manufacturing a semiconductor comprises at least two nonionic surfactants as the additive, and the at least two nonionic surfactants are the compounds represented by Formula (A1).

22. The treatment liquid for manufacturing a semiconductor according to claim 20, wherein the compound represented by Formula (A1) is a compound represented by the following Formula (A2), ##STR00097## in Formula (A2), R.sub.a1, R.sub.a2, R.sub.a3, and R.sub.a4 each independently represent an alkyl group, m and n each independently represent a positive number of 0.5 to 80, and m+n≥1is satisfied.

23. A pattern forming method comprising: forming a film using an actinic ray-sensitive or radiation-sensitive resin composition or a coloring curable resin composition; exposing the formed film; and treating the exposed film using the treatment liquid for manufacturing a semiconductor according to claim 1.

24. The pattern forming method according to claim 23, wherein the treatment is developing.

25. The pattern forming method according to claim 23, wherein the treatment is developing and rinsing.

26. The pattern forming method according to claim 23, further comprising: cleaning the developed film using a rinsing liquid including an organic solvent or using water.

27. The pattern forming method according to claim 26, wherein the rinsing liquid including an organic solvent is a rinsing liquid including at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent as the organic solvent.

28. The pattern forming method according to claim 26, wherein the rinsing liquid including an organic solvent is a rinsing liquid including at least an alcohol solvent as the organic solvent.

29. The pattern forming method according to claim 26, wherein the rinsing liquid including an organic solvent is a rinsing liquid including a linear, branched, or cyclic monohydric alcohol having 6 to 8 carbon atoms as the organic solvent.

30. The pattern forming method according to claim 26, wherein a moisture content of the rinsing liquid including an organic solvent is 30 mass % or lower.

31. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the ratio T.sub.1 is in a range from 400 ppt to 1 ppm.

32. The treatment liquid for manufacturing a semiconductor according to claim 1, wherein the ratio T.sub.1 is in a range from 35 ppb to 0.105 ppm.

33. A treatment liquid for manufacturing a semiconductor comprising: a quaternary ammonium compound represented by the following Formula (N); at least one additive selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and a chelating agent; and water, wherein the treatment liquid for manufacturing a semiconductor includes one kind or two or more kinds of metal atoms selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, a ratio T.sub.1of a total mass of the metal atoms to the sum of a total mass of the additive and the total mass of the metal atoms as defined by the following formula is in a range from 1 ppt to 1 ppm,
T.sub.1=[total mass of the metal atoms]/([total mass of the additive]+[total mass of the metal atoms]), ##STR00098## in Formula (N), R.sub.N1to R.sub.N4 each independently represent an alkyl group, a phenyl group, a benzyl group, or a cyclohexyl group, and the alkyl group, the phenyl group, the benzyl group, or the cyclohexyl group may have a substituent, a content of each of the one kind or two or more kinds of metal atoms selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn is 1 mass ppq to 500 mass ppt with respect to the treatment liquid for manufacturing a semiconductor, and a content of the additive is 1 mass % or lower with respect to the treatment liquid for manufacturing a semiconductor.

34. The treatment liquid for manufacturing a semiconductor according to claim 33, wherein a content of each of the one kind or two or more kinds of metal atoms selected from the group consisting of Na, K, and Ca is 1 mass ppq to 500 mass ppt with respect to the treatment liquid for manufacturing a semiconductor.

35. A treatment liquid for manufacturing a semiconductor comprising: a quaternary ammonium compound represented by the following Formula (N); at least one additive selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and a chelating agent; and water, wherein the treatment liquid for manufacturing a semiconductor includes one kind or two or more kinds of metal atoms selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn, a ratio T.sub.1 of a total mass of the metal atoms to the sum of a total mass of the additive and the total mass of the metal atoms as defined by the following formula is in a range from 1 ppt to 1 ppm,
T.sub.1=[total mass of the metal atoms]/(total mass of the additive]+[total mass of the metal atoms]) a ratio T.sub.2 of a total mass of particulate metal of the metal atoms measured by a SP-ICP-MS method to the sum of the total mass of the additive and the total mass of the particulate metal as defined by the following formula is in a range from 0.1 ppt to 0.1 ppm,
T.sub.2=[total mass of the particulate metal]/([total mass of the additive]+[total mass of the particulate metal]), where the particulate metal is a nonionic metal component derived from the metal atoms which is not dissolved in the treatment liquid and exists as a solid, and ##STR00099## in Formula (N), R.sub.N1 to R.sub.N4 each independently represent an alkyl group, a phenyl group, a benzyl group, or a cyclohexyl group, and the alkyl group, the phenyl group, the benzyl group, or the cyclohexyl group may have a substituent.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described in detail using Examples, but the scope of the present invention is not limited thereto. Unless specified otherwise, “part(s)” represents “part(s) by mass”.

(2) <A-1. Treatment Liquid for Manufacturing Semiconductor: Examples 1 to 39, Comparative Examples 1 to 15>

(3) [Quaternary Ammonium Compound]

(4) Hereinafter, the following compounds were used as a quaternary ammonium compound. These quaternary ammonium compounds were purified by repeating filter filtration as well as adsorption purification using silicon carbide as described in W02012/043496A.

(5) S-1: tetramethylammonium hydroxide (TMAH)

(6) S-2: dimethyl bis(2-hydroxyethyl)ammonium hydroxide (AH-212)

(7) [Additive]

(8) The following compounds were used as an additive.

(9) AA-1: NEWCOL B4-SN (manufactured by Nippon Nyukazai Co., Ltd.) (anionic surfactant)

(10) AN-1: Surfynol 465 (manufactured by Air Products & Chemicals Ltd.) (nonionic surfactant)

(11) AN-2: DKS NL-15 (manufactured by DKS Co. Ltd.) (nonionic surfactant)

(12) AN-3: NEWCOL 610 (manufactured by Nippon Nyukazai Co., Ltd.) (nonionic surfactant)

(13) AC-1: TEXNOL R2 (manufactured by Nippon Nyukazai Co., Ltd.) (cationic surfactant) AH-1: ethylenediaminetetraacetic acid (chelating agent) AH-2: diethylenetriaminepentaacetic acid (chelating agent)

(14) [Water]

(15) Water was purified using a method described in JP.sub.2007-254168A, and was used for adjusting the treatment liquid for manufacturing a semiconductor after verifying that the metal content in the liquid was lower than 0.001 mass ppt.

(16) <A-2. Preparation of Developer: Examples 1 to 39, Comparative Examples 1 to 15>

(17) Tables 1-1 to 1-3 show ratios of the addition amounts of the quaternary ammonium compounds and the additives with respect to the treatment liquid for manufacturing a semiconductor. 1000 g of each of mixed solutions was prepared according to the ratio shown in Tables 1-1 to 1-3 with respect to water as a balance. The obtained mixed solution was purified by repeating filter filtration to adjust metal atoms. The treatment liquid for manufacturing a semiconductor obtained as described above was used as a developer.

(18) The preparation, filling, storage, and the like of the above-described treatment liquid for manufacturing a semiconductor (developer) were performed in a clean room satisfying ISO Class 2 or lower. In addition, a container to be used was cleaned using the above-described water and/or the treatment liquid for manufacturing a semiconductor according to the present invention.

(19) TABLE-US-00001 TABLE 1-1 A: Additive Quaternary Anionic Cationic Chelating Ammonium Surfactant Nonionic Surfactant Surfactant Agent Compound mass mass mass mass Metal Atom Kind mass % Kind ppm Kind ppm HLB Kind ppm Kind ppm Ratio T.sub.1 Example 1 S-1 2.5 AA-1 200 — 0 — — 0 — 0 0.0000000700 Example 2 S-1 2.5 — 0 AN-1 200 13 — 0 — 0 0.0000000700 Example 3 S-1 2.5 — 0 — 0 — AC-1 200 — 0 0.0000000700 Example 4 S-1 2.5 AA-1 200 — 0 — — 0 AH-1 200 0.0000000350 Example 5 S-1 2.5 — 0 AN-1 200 13 — 0 AH-1 200 0.0000000350 Example 6 S-1 2.5 — 0 — 0 — AC-1 200 AH-1 200 0.0000000350 Example 7 S-1 2.5 AA-1 300 — 0 — — 0 — 0 0.0000000700 Example 8 S-1 2.5 — 0 AN-1 300 13 — 0 — 0 0.0000000700 Example 9 S-1 2.5 — 0 — 0 — AC-1 300 — 0 0.0000000700 Example 10 S-1 2.5 AA-1 300 — 0 — — 0 AH-1 300 0.0000000350 Example 11 S-1 2.5 — 0 AN-1 300 13 — 0 AH-1 300 0.0000000350 Example 12 S-1 2.5 — 0 — 0 — AC-1 300 AH-1 300 0.0000000350 Example 13 S-1 2.5 AA-1 300 — 0 — — 0 — 0 0.0000001050 Example 14 S-1 2.5 — 0 AN-1 300 13 — 0 — 0 0.0000001050 Example 15 S-1 2.5 — 0 — 0 — AC-1 300 — 0 0.0000001050 Example 16 S-1 2.5 AA-1 300 — 0 — — 0 AH-1 300 0.0000000525 Example 17 S-1 2.5 — 0 AN-1 300 13 — 0 AH-1 300 0.0000000525 Example 18 S-1 2.5 — 0 — 0 — AC-1 300 AH-1 300 0.0000000525

(20) TABLE-US-00002 TABLE 1-2 A: Additive Quaternary Anionic Cationic Chelating Ammonium Surfactant Nonionic Surfactant Surfactant Agent Compound mass mass mass mass Metal Atom Kind mass % Kind ppm Kind ppm HLB Kind ppm Kind ppm Ratio T.sub.1 Example 19 S-1 2.5 AA-1 200 — 0 — — 0 — 0 0.0000000700 Example 20 S-1 2.5 — 0 AN-2 200 5 — 0 — 0 0.0000000700 Example 21 S-1 2.5 — 0 — 0 — AC-1 200 — 0 0.0000000700 Example 22 S-1 2.5 AA-1 200 — 0 — — 0 AH-1 200 0.0000000350 Example 23 S-1 2.5 — 0 AN-2 200 5 — 0 AH-1 200 0.0000000350 Example 24 S-1 2.5 — 0 — 0 — AC-1 200 AH-1 200 0.0000000350 Example 25 S-2 2.5 — 0 AN-1 200 13 — 0 — 0 0.0000000700 Example 26 S-2 2.5 — 0 AN-1 200 13 — 0 AH-1 200 0.0000000350 Example 27 S-1 2.5 — 0 AN-1 200 13 — 0 — 0 0.0000000700 Example 28 S-1 2.5 — 0 AN-1 200 13 — 0 AH-1 200 0.0000000350 Example 29 S-1 2.5 — 0 AN-3 200 13.8 — 0 — 0 0.0000000700 Example 30 S-1 2.5 — 0 AN-3 200 13.8 — 0 AH-1 200 0.0000000350 Example 31 S-1 2.5 — 0 AN-3 200 13.8 — 0 AH-2 200 0.0000000350 Example 32 S-2 2.5 — 0 AN-1 200 13 — 0 — 0 0.0000000750 Example 33 S-1 2.5 — 0 AN-3 200 13.8 — 0 AH-3 200 0.0000000350 Comparative S-1 2.5 AA-1 200 — 0 — — 0 — 0 0.0000061200 Example 1 Comparative S-1 2.5 AA-1 200 — 0 — — 0 — 0 0.0000061200 Example 2 Comparative S-1 2.5 — 0 AN-1 200 13 — 0 — 0 0.0000061800 Example 3

(21) TABLE-US-00003 TABLE 1-3 A: Additive Quaternary Anionic Cationic Chelating Ammonium Surfactant Nonionic Surfactant Surfactant Agent Compound mass mass mass mass Metal Atom Kind mass % Kind ppm Kind ppm HLB Kind ppm Kind ppm Ratio T.sub.1 Comparative S-1 2.5 — 0 AN-1 200 13 — 0 — 0 0.0000061800 Example 4 Comparative S-1 2.5 — 0 AN-1 200 13 — 0 — 0 0.0000062400 Example 5 Comparative S-1 2.5 — 0 AN-1 200 13 — 0 — 0 0.0000063000 Example 6 Comparative S-1 2.5 — 0 — 0 — AC-1 200 — 0 0.0000063600 Example 7 Comparative S-1 2.5 — 0 — 0 — AC-1 200 — 0 0.0000064200 Example 8 Comparative S-1 2.5 AA-1 200 — 0 — — 0 AH-1 200 0.0000030600 Example 9 Comparative S-1 2.5 AA-1 200 — 0 — — 0 AH-1 200 0.0000030600 Example 10 Comparative S-1 2.5 — 0 AN-1 200 13 — 0 AH-1 200 0.0000030900 Example 11 Comparative S-1 2.5 — 0 AN-1 200 13 — 0 AH-1 200 0.0000031200 Example 12 Comparative S-1 2.5 — 0 AN-1 200 13 — 0 AH-1 200 0.0000031500 Example 13 Comparative S-1 2.5 — 0 — 0 — AC-1 200 AH-1 200 0.0000031800 Example 14 Comparative S-1 2.5 — 0 — 0 — AC-1 200 AH-1 200 0.0000032100 Example 15 Example 34 S-1 2.5 AA-1 20000 — 0 — — 0 — 0 0.0000000007 Example 35 S-1 2.5 — 0 AN-1 20000 13 — 0 — 0 0.0000000007 Example 36 S-1 2.5 — 0 — 0 — AC-1 20000 — 0 0.0000000007 Example 37 S-1 2.5 AA-1 20000 — 0 — — 0 AH-1 20000 0.0000000004 Example 38 S-1 2.5 — 0 AN-1 20000 13 — 0 AH-1 20000 0.0000000004 Example 39 S-1 2.5 — 0 — 0 — AC-1 20000 AH-1 20000 0.0000000004

(22) [Measurement of Metal Atoms]

(23) One kind or two or more kinds of metal atoms selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn in the developer were measured as follows.

(24) (1) Preparation of Standard Material and Calibration Curve of Each Metal Atom

(25) Ultrapure water was weighed and charged into a clean glass container, and metal atoms as a measurement target having a median size of 60 nm were added thereto such that the concentration was 10000 atoms/ml. Next, the solution was treated using an ultrasonic cleaning machine for 30 minutes to obtain a dispersion. The obtained dispersion was used as a standard material for transport efficiency measurement. Using an inductively coupled plasma (ICP) standard solution, the calibration curve of each of the metal atoms was created.

(26) In addition, a standard material solution for transport efficiency measurement in a SP-ICP-MS method was prepared as follows. Ultrapure water was weighed and charged into a clean glass container, and gold particles having a median size of 50 nm were added thereto such that the concentration was 10000 atoms/ml. Next, the solution was treated using an ultrasonic cleaning machine for 30 minutes to obtain a dispersion.

(27) (2) Measurement

(28) In an inductively coupled plasma-mass spectrometry (ICP-MS) device, the measurement target liquid was aspirated at about 0.2 mL/min using a PFA coaxial nebulizer formed of PFA, a cyclonic spray chamber formed of quartz, and a torch injector having an inner diameter of 1 mm formed of quartz. The addition amount of oxygen was set as 0.1 L/min, the plasma power was set as 1600 W, and the inside of the cell was purged using ammonia gas. The temporal resolution was set as 50 μs for analysis.

(29) Manufacturer: PerkinElmer

(30) Model: NexION 350S

(31) In addition, for the measurement of particulate metal, SP-ICP-MS was measured using software Syngistix for ICP-MS of the above-described ICP-MS device.

(32) The temporal resolution was set as 50 μs for analysis. Based on the transport efficiency determined by the measurement result of the standard material for transport efficiency measurement and the analysis thereof, and the calibration curve of each metal atom determined by the measurement result of the ICP standard solution and the analysis thereof, the concentration (Mp) of the particulate metal including target atoms in the measurement target liquid was measured using the above-described analysis software.

(33) All the analysis and measurement described above were performed in a clean room satisfying a level of ISO Class 2 or lower. The measurement results are shown in Tables 2-1 to 2-6.

(34) [Metal Atom Ratio Ti and Particulate Metal Ratio T.sub.2] A ratio T.sub.1 of the total mass of the metal atoms obtained as described above to the sum of the total mass of the additive and the total mass of the metal atoms was calculated.

(35) T.sub.1=[Total Mass of Metal Atoms]/[Total Mass of Additive+Total Mass of Metal Atoms] In addition, a ratio T.sub.2 of the total mass of the particulate metal obtained as described above to the sum of the total mass of the additive and the total mass of the particulate metal was calculated.

(36) T.sub.2=[Total Mass of Particulate Metal]/[Total Mass of Additive+Total Mass of Particulate Metal] The calculation results are shown in Tables 1-1 to 1-3 and Tables 2-1 to 2-6.

(37) [Measurement of Impurities]

(38) A ratio of the mass of each of a peroxide, an ester compound, an amine compound, and a chelate complex in the developer to the developer was analyzed using a high-performance liquid chromatography (HPLC: detector RI); LC-2000, manufactured by Jasco Corporation).

(39) A ratio of the total mass of an inorganic salt in the developer to the developer was analyzed using an ion chromatography method (DX-500, manufactured by Nippon Dionex K.K.).

(40) All the analysis and measurement described above were performed in a clean room satisfying a level of ISO Class 2 or lower. The results are shown in Tables 2-1 to 2-3.

A-3. Examples 1 to 39, Comparative Examples 1 to 15

(41) [Evaluation of Defects]

(42) Using a wafer surface inspection device (SP-5, manufactured by KLA-Tencor Corporation), the number of foreign matters having a diameter of 32 nm or more present on a silicon substrate surface having a diameter of 300 mm and the address of each of the foreign matters were calculated. After the calculation of the number of foreign matters present on the silicon substrate surface, the wafer was set on a rotational type wafer spin processor (manufactured by EKC Technology Inc.). The above-described treatment liquid for manufacturing a semiconductor was discharged to the surface of the set wafer at a flow rate of 1.5 L/min for 1 hour. Next, the wafer was spin-dried. Using the wafer surface inspection device, the number of foreign matters on the wafer and the address of each of the foreign matter were calculated. After spin-drying the treatment liquid for manufacturing a semiconductor, elemental analysis was performed on newly increased foreign matters by energy dispersive X-ray spectrometry (EDX) using a defect analyzer (SEMVISION G6, manufactured by Applied Materials Inc.). Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn were set as target metal elements, and foreign matters including the target metal elements were counted as particles. The obtained number of particles was evaluated based on the following evaluation standards. The results are shown in Tables 2-4 to 2-6.

(43) A: the number of particles having a diameter of 32 nm or more including the target metal elements is 0 or more and less than 100

(44) B: the number of particles having a diameter of 32 nm or more including the target metal atoms is 100 or more and less than 300

(45) C: the number of particles having a diameter of 32 nm or more including the target metal atoms is 300 or more and less than 500

(46) D: the number of particles having a diameter of 32 nm or more including the target metal atoms is 500 or more and less than 700

(47) E: the number of particles having a diameter of 32 nm or more including the target metal atoms is 700 or more

A-4. Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition: Examples 1 to 39, Comparative Examples 1 to 15

(48) [Synthesis Example 1: Synthesis of Resin (1)] 8.6 g of cyclohexanone was put into a three-neck flask in a nitrogen stream and was heated to 80° C. Next, 9.8 g of 2-adamantyl isopropyl methacrylate, 4.4 g of dihydroxyadamantyl methacrylate, 8.9 g of norbornane lactone methacrylate, and 8 mol % (with respect to the monomers) of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 79 g of cyclohexanone to prepare a monomer solution. The obtained monomer solution was added dropwise to the flask heated to 80° C. for 6 hours. After completion of the dropwise addition, a reaction was performed at 80° C. for 2 hours. The obtained reaction solution was cooled to room temperature and was added dropwise to a mixed solution of 800 ml of hexane and 200 ml of ethyl acetate for 20 minutes. The precipitated powder was separated by filtration and was dried. As a result, 19 g of a resin (1) was obtained. In a case where the obtained resin (1) was measured by gel permeation chromatography (GPC; solvent: tetrahydrofuran (THF)) in terms of standard polystyrene, the weight-average molecular weight (Mw) was 9800, and the molecular weight dispersity (Mw/Mn) was 1.9. A composition ratio (molar ratio) of the obtained resin (1) was calculated by .sup.1H-nuclear magnetic resonance (NMR) measurement. The composition ratio was 39/20/41 in order from the left repeating unit.

(49) ##STR00089##

Synthesis Example 2: Synthesis of Hydrophobic Resin (C-1)

(50) 0.06 mol of (3,5-bis(1,1,1,3,3,3-hexafluoro-2-hydroxypropane-2-yl)cyclohexyl) 2-trifluoromethylmethacrylate and 0.04 mol of (5-norbornene-2-methyl)-1,1,1,3,3,3-hexafluoropropane-2-ol were prepared. While stirring the mixture in a nitrogen atmosphere at 80° C., 1.5 mol % of a polymerization initiator V-59 (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and the solution was stirred for 3 hours. Next, while adding 1.5 mol % of the polymerization initiator V-59 every 3 hours, the solution was stirred 12 hours to cause the components to react with each other. The reaction solution was dissolved in 20 mL of tetrahydrofuran (THF) and was cooled to room temperature. 800 mL of hexane was added, and the crystallized and precipitated white powder was separated by filtration. As a result, a hydrophobic resin (C-1) was obtained.

(51) A polymer composition ratio obtained by .sup.1H-NMR was 60/40 (in order from the left structural formula). In addition, in a case where the hydrophobic resin (C-1) was measured by GPC in terms of standard polystyrene, the weight-average molecular weight was 8800, and the dispersity was 1.5.

(52) ##STR00090##

(53) [Configuration of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition]

(54) The following compounds were prepared as components of the actinic ray-sensitive or radiation-sensitive resin composition.

(55) TABLE-US-00004 Resin (1)  2 g Photoacid generator (z2) 80 mg Basic compound (N,N-dihydroxyethylaniline)  7 mg Hydrophobic resin (C-1)  2 mg Solvent (cyclohexanone/propyleneglycol monomethyl ether acetate) 60/40 (mass ratio) Surfactant (MEGAFACE F176 (manufactured by  3 mg DIC Corporation) (fluorine surfactant)

(56) <A-5. Preparation of Resist Solution>

(57) The above-described components were dissolved in the above-described solvent to prepare solution in which the concentration of solid contents was 7 mass %. This mixed solution was filtered through a polyethylene filter having a pore size of 0.1 m to prepare a positive type resist solution.

(58) <A-6. Coloring Curable Resin Composition>

(59) [Green Pigment Dispersion (Pigment Dispersion 1)]

(60) A mixed solution was mixed using beads mills for 15 hours to prepare a Green pigment dispersion, the mixed solution including: 12.6 parts of a mixture of C.I. Pigment Green 36 and C.I. Pigment yellow 139 at a mass ratio of 100/55 as a pigment; 5.2 parts of BYK2001 (Disperbyk; manufactured by BYK Chemie, concentration of solid contents: 45.1 mass %) as a dispersant; and 2.7 parts of a benzyl methacrylate/methacrylic acid copolymer (acid value=134 mgKOH/g, Mw=30000) as a dispersion resin; and 78.3 parts of propylene glycol monomethyl ether acetate as a solvent.

(61) [Red Pigment Dispersion (Pigment Dispersion 2)]

(62) A mixed solution was mixed using beads mills for 15 hours to prepare a Red pigment dispersion, the mixed solution including: 12.1 parts of C.I. Pigment Red 254 as a pigment; 10.4 parts of BYK2001 (Disperbyk; manufactured by BYK Chemie, concentration of solid contents: 45.1 mass %) as a dispersant; and 3.8 parts of a benzyl methacrylate/methacrylic acid copolymer (acid value=134 mgKOH/g, Mw=30000) as a dispersion resin; and 73.7 parts of propylene glycol monomethyl ether acetate as a solvent.

(63) [Blue Pigment Dispersion (Pigment Dispersion 3)]

(64) A mixed solution was mixed using beads mills for 15 hours to prepare a Blue pigment dispersion, the mixed solution including: 14 parts of a mixture of C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23 at a mass ratio of 100/25 as a pigment; 4.7 parts of BYK2001 (Disperbyk; manufactured by BYK Chemie, concentration of solid contents: 45.1 mass %) as a dispersant; and 3.5 parts of a benzyl methacrylate/methacrylic acid copolymer (acid value=134 mgKOH/g, Mw=30000) as a dispersion resin; and 77.8 parts of propylene glycol monomethyl ether acetate as a solvent.

A-7. Preparation of Color Resist Solution: Examples 1 to 39, Comparative Examples 1 to 15

(65) Any one of the pigment dispersions 1 to 3 was mixed and stirred to obtain the following composition A. As a result, a coloring curable resin composition was prepared.

(66) [Composition A]

(67) TABLE-US-00005 Pigment dispersion (any one of the 82.35 parts pigment dispersions 1 to 3) Alkali-Soluble Resin 2.05 parts Polymerization initiator: 1.2 parts DPHA (polymerizable compound) 1.4 parts M-305 (polymerizable compound) 1.4 parts p-methoxyphenol 0.001 parts PEGMEA 7.4 parts F781 4.2 parts

(68) The respective components included in the composition A are as follows.

(69) Polymerization initiator: IRGACURE OXE01 [trade name], manufactured by BASF SE

(70) DPHA: KAYARAD DPHA [trade name], manufactured by Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate,

(71) M-305: a mixture of triacrylate and pentaerythritol tetraacrylate [trade name], manufactured by Toagosei Co., Ltd.

(72) PEGMEA: propylene glycol monomethyl ether acetate

(73) F781: MEGAFACE F-781 [trade name], manufactured by DIC Corporation

(74) Alkali-soluble resin: a copolymer including benzyl methacrylate, methacrylic acid, and 2-hydroxyethyl methacrylate (60/22/18 [molar ratio], weight-average molecular weight: 15000, number-average molecular weight: 8000)

(75) The weight-average molecular weight was measured as a value in terms of polystyrene using a gel permeation chromatography (GPC) method.

(76) The GPC Method is based on a method in which RLC-8020 GPC (manufactured by Tosoh Corporation) was used, Tsk gel Super HZM-H, TSK gel Super HZ4000, and TSK gel Super HZ2000 (manufactured by Tosoh Corporation; 4.6 mm ID×15 cm) was used as a column, and tetrahydrofuran (THF) was used as an eluent.

(77) <A-8. Examples 1 to 39, Comparative Examples 1 to 15: Resist Pattern>

(78) An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries Ltd.) was applied to a silicon wafer and was baked at 205° C. for 60 seconds to form an antireflection film having a thickness of 78 nm. The prepared positive type resist composition was applied to the antireflection film and was baked at 130° C. for 60 seconds to form a resist film having a thickness of 250 nm. The obtained wafer was exposed in a pattern shape using an ArF excimer laser scanner (PAS5500/1100, manufactured by ASML, NA: 0.75, σo/σi=0.85/0.55). Next, the wafer was heated at 120° C. for 90 seconds, was developed using the developer shown in Tables 1-1 to 1-3 for 30 seconds, was rinsed with ultrapure water, and was spin-dried. As a result, a silicon wafer on which a resist pattern was formed was obtained.

(79) [Evaluation of Resist Pattern]

(80) The obtained pattern shape was observed and evaluated using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). In addition, the line width of a pattern cross-section was measured at three points of the pattern including (a) a pattern top portion, (b) a pattern middle portion, and (c) a pattern-substrate interface. In a case where a difference in line width between (a) to (c) was less than 5%, the profile was defined as “rectangular”. A case where the line width of (a) was less than that of (b) by 5% or more and the line width of (b) was less than that of (c) by 5% or more, the profile was defined as “forward tapered”. In a case where the line width of (a) was more than that of (b) by 5% or more and the line width of (b) was more than that of (c) by 5% or more, the profile was defined as “reverse tapered”. In a case where a difference in line width between (a) and (b) was less than 5% and the line width of (b) was more than that of (c) by 5% or more, the profile was defined as “fitting”. In a case where a difference in line width between (b) and (c) was less than 5% and the line width of (a) was more than that of (b) by 5% or more, the profile was defined as “T-Top”. The evaluation results are shown in Tables 2-4 to 2-6.

(81) [Evaluation of Pattern Defects]

(82) Regarding the pattern formed as described above, the number of defects having a diameter of 20 nm or more present on the substrate surface was measured using a wafer surface inspection device (PUMA 9850; manufactured by KLA-Tencor Corporation). The obtained number of defects was evaluated based on the following standards, and the results thereof are shown in the tables. In the following standards, the evaluation C represents that an ability of suppressing defects that is required for the treatment liquid for manufacturing a semiconductor is achieved.

(83) A: the number of defects was 0 to 500

(84) B: the number of defects was more than 500 and 1000 or less

(85) C: the number of defects was more than 1000 and 3000 or less

(86) D: the number of defects was more than 3000 and 5000 or less

(87) E: the number of defects was more than 5000

A-9. Examples 1 to 39, Comparative Examples 1 to 15: Color Filter

(88) The coloring curable resin compositions of each of the colors prepared as described above was applied to a 8-inch silicon wafer to which hexamethyldisilazane was sprayed in advance. As a result, a photocurable coating film was formed. The coating film was heated (pre-baked) using a hot plate at 100° C. for 180 seconds such that the thickness of the coating film after drying was 1.0 μm. Next, using a stepper exposure device FPA-3000 i5+ (manufactured by Canon Corporation), the coating film was irradiated with i-rays having a wavelength of 365 nm through a Bayer pattern mask having a size of 1.0 μm×1.0 μm at 50 to 1000 mJ/cm.sup.2 (the exposure dose changed by 50 mJ/cm.sup.2). Next, the silicon wafer on which the irradiated coating film was disposed was placed on a horizontal rotary table of a spin-shower developing machine (DW-30, manufactured by Chemitronics Co., Ltd.). Puddle development was performed using the developer shown in Tables 1-1 to 1-3 at 23° C. for 180 seconds. As a result, a colored pattern was formed on the silicon wafer.

(89) The silicon wafer on which the colored pattern was formed was fixed to the horizontal rotary table using a vacuum chuck method. While rotating the silicon wafer at a rotation speed of 50 rpm using a rotating device, the silicon wafer was rinsed with ultrapure water supplied from a region above the rotation center through a spray nozzle and then was spray-dried. Next, the obtained silicon wafer was heated using a hot plate at 200° C. for 5 minutes. As a result, a silicon wafer on which the color filter was disposed was obtained.

(90) [Evaluation of Linearity of Color Resist]

(91) The prepared color filter was cut with a glass cutter, and the obtained cross-section was observed with a scanning electron microscope (S-4800, manufactured by Hitachi Ltd.) at a magnification of 15000 times and was evaluated based on the following evaluation standards. The evaluation results are shown in Tables 2-4 and 2-6 together with the content of the metal atoms with respect to the additive.

(92) A: as compared to a case where the line width of the pattern was 1.2 μm, the line width was 1.08 μm to 1.32 μm and the linearity was excellent

(93) B: as compared to a case where the line width of the pattern was 1.2 μm, the line width was in a range of 1.02 μm or more and less than 1.08 μm or in a range of more than 1.32 μm and 1.38 μm or less

(94) C: as compared to a case where the line width of the pattern was 1.2 μm, the line width was in a range of 0.96 μm or more and less than 1.02 μm or in a range of more than 1.38 μm and 1.44 μm or less, and there were no problems in practice

(95) D: as compared to a case where the line width of the pattern was 1.2 μm, the line width was in a range of 0.9 μm or more and less than 0.96 μm or in a range of more than 1.44 μm and 1.5 μm or less, and there were no problems in practice although the linearity was poor

(96) E: as compared to a case where the line width of the pattern was 1.2 μm, the line width was less than 0.9 μm or more than 1.5 μm, and the linearity was significantly poor

(97) TABLE-US-00006 TABLE 2-1 B: Metal Atom (mass ppt) Na K Ca Fe Cu Mg Mn Li Al Cr Ni Zn Example 1 2 1 1 2 1 1 1 1 1 1 1 1 Example 2 2 2 1 1 1 1 1 1 1 1 1 1 Example 3 1 2 2 1 1 1 1 1 1 1 1 1 Example 4 2 1 1 2 1 1 1 1 1 1 1 1 Example 5 2 2 1 1 1 1 1 1 1 1 1 1 Example 6 1 2 2 1 1 1 1 1 1 1 1 1 Example 7 3 1.5 1.5 3 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Example 8 3 3 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Example 9 1.5 3 3 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Example 10 3 1.5 1.5 3 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Example 11 3 3 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Example 12 1.5 3 3 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Example 13 4.5 2.25 2.25 4.5 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 Example 14 4.5 4.5 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 Example 15 2.25 4.5 4.5 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 Example 16 4.5 2.25 2.25 4.5 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 Example 17 4.5 4.5 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 Example 18 2.25 4.5 4.5 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 2.25 C (mass ppt) Ester Amine Inorganic Chelate Metal Atom Peroxide Compound Compound Salt Complex Ratio T.sub.1 Example 1 0 0 0 1 0 0.0000000700 Example 2 1 1 1 0 0 0.0000000700 Example 3 0 0 0 1 0 0.0000000700 Example 4 0 0 0 1 1 0.0000000350 Example 5 1 1 1 0 1 0.0000000350 Example 6 0 0 0 1 1 0.0000000350 Example 7 0 0 0 1.1 0 0.0000000700 Example 8 1.2 1.2 1.3 0 0 0.0000000700 Example 9 0 0 0 1.2 0 0.0000000700 Example 10 0 0 0 1.5 1.4 0.0000000350 Example 11 1.1 1.3 1.4 0 1.5 0.0000000350 Example 12 0 0 0 1.1 1.4 0.0000000350 Example 13 0 0 0 2 0 0.0000001050 Example 14 1.8 1.7 2.1 0 0 0.0000001050 Example 15 0 0 0 1.8 0 0.0000001050 Example 16 0 0 0 1.5 1.6 0.0000000525 Example 17 1.9 1.4 1.8 0 1.6 0.0000000525 Example 18 0 0 0 1.8 1.5 0.0000000525

(98) TABLE-US-00007 TABLE 2-2 B: Metal Atom (mass ppt) Na K Ca Fe Cu Mg Mn Li Al Cr Ni Zn Example 19 2 1 1 2 1 1 1 1 1 1 1 1 Example 20 2 2 1 1 1 1 1 1 1 1 1 1 Example 21 1 2 2 1 1 1 1 1 1 1 1 1 Example 22 2 1 1 2 1 1 1 1 1 1 1 1 Example 23 2 2 1 1 1 1 1 1 1 1 1 1 Example 24 1 2 2 1 1 1 1 1 1 1 1 1 Example 25 2 2 1 1 1 1 1 1 1 1 1 1 Example 26 2 2 1 1 1 1 1 1 1 1 1 1 Example 27 2 2 1 1 1 1 1 1 1 1 1 1 Example 28 2 2 1 1 1 1 1 1 1 1 1 1 Example 29 2 2 1 1 1 1 1 1 1 1 1 1 Example 30 2 2 1 1 1 1 1 1 1 1 1 1 Example 31 2 2 1 1 1 1 1 1 1 1 1 1 Example 32 1 1 1 1 1 1 1 1 1 1 1 1 Example 33 2 2 1 1 1 1 1 1 1 1 1 1 Comparative 105 100 101 103 100 99 100 104 100 107 100 105 Example 1 Comparative 105 100 101 103 100 99 100 104 100 107 100 105 Example 2 Comparative 106 101 102 104 101 100 101 105 101 108 101 106 Example 3 C (mass ppt) Ester Amine Inorganic Chelate Metal Atom Peroxide Compound Compound Salt Complex Ratio T.sub.1 Example 19 0 0 0 1 0 0.0000000700 Example 20 1 1 1 0 0 0.0000000700 Example 21 0 0 0 1 0 0.0000000700 Example 22 0 0 0 1 1 0.0000000350 Example 23 1 1 1 0 1 0.0000000350 Example 24 0 0 0 1 1 0.0000000350 Example 25 1 1 1 0 0 0.0000000700 Example 26 1 1 1 0 1 0.0000000350 Example 27 1 1 1 0 0 0.0000000700 Example 28 1 1 1 0 1 0.0000000350 Example 29 1 1 1 0 0 0.0000000700 Example 30 1 1 1 0 1 0.0000000350 Example 31 1 1 1 0 1 0.0000000350 Example 32 1 1 1 0 0 0.0000000750 Example 33 1 1 1 0 1 0.0000000350 Comparative 0 0 0 1 0 0.0000061200 Example 1 Comparative 0 0 0 1500 0 0.0000061200 Example 2 Comparative 1 1 1 0 0 0.0000061800 Example 3

(99) TABLE-US-00008 TABLE 2-3 B: Metal Atom (mass ppt) Na K Ca Fe Cu Mg Mn Li Al Cr Ni Zn Comparative 106 101 102 104 101 100 101 105 101 108 101 106 Example 4 Comparative 107 102 103 105 102 101 102 106 102 109 102 107 Example 5 Comparative 108 103 104 106 103 102 103 107 103 110 103 108 Example 6 Comparative 109 104 105 107 104 103 104 108 104 111 104 109 Example 7 Comparative 110 105 106 108 105 104 105 109 105 112 105 110 Example 8 Comparative 105 100 101 103 100 99 100 104 100 107 100 105 Example 9 Comparative 105 100 101 103 100 99 100 104 100 107 100 105 Example 10 Comparative 106 101 102 104 101 100 101 105 101 108 101 106 Example 11 Comparative 107 102 103 105 102 101 102 106 102 109 102 107 Example 12 Comparative 108 103 104 106 103 102 103 107 103 110 103 108 Example 13 Comparative 109 104 105 107 104 103 104 108 104 111 104 109 Example 14 Comparative 110 105 106 108 105 104 105 109 105 112 105 110 Example 15 Example 34 2 1 1 2 1 1 1 1 1 1 1 1 Example 35 2 2 1 1 1 1 1 1 1 1 1 1 Example 36 1 2 2 1 1 1 1 1 1 1 1 1 Example 37 2 1 1 2 1 1 1 1 1 1 1 1 Example 38 2 2 1 1 1 1 1 1 1 1 1 1 Example 39 1 2 2 1 1 1 1 1 1 1 1 1 C (mass ppt) Ester Amine Inorganic Chelate Metal Atom Peroxide Compound Compound Salt Complex Ratio T.sub.1 Comparative 1500 1 1 0 0 0.0000061800 Example 4 Comparative 1 1500 1 0 0 0.0000062400 Example 5 Comparative 0 1 1500 0 0 0.0000063000 Example 6 Comparative 0 0 0 1 0 0.0000063600 Example 7 Comparative 0 0 0 1500 0 0.0000064200 Example 8 Comparative 0 0 0 1 1 0.0000030600 Example 9 Comparative 0 0 0 100 1 0.0000030600 Example 10 Comparative 100 1 1 0 1 0.0000030900 Example 11 Comparative 1 100 1 0 1 0.0000031200 Example 12 Comparative 1 1 100 0 1 0.0000031500 Example 13 Comparative 0 0 0 1 1 0.0000031800 Example 14 Comparative 0 0 0 100 1 0.0000032100 Example 15 Example 34 0 0 0 1 0 0.0000000007 Example 35 1 1 1 0 0 0.0000000007 Example 36 0 0 0 1 0 0.0000000007 Example 37 0 0 0 1 1 0.0000000004 Example 38 1 1 1 0 1 0.0000000004 Example 39 0 0 0 1 1 0.0000000004

(100) TABLE-US-00009 TABLE 2-4 D: Particulate Metal (mass ppt) Na K Ca Fe Cu Mg Mn Li Al Cr Ni Zn Example 1 0.200 0.100 0.100 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 2 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 3 0.100 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 4 0.200 0.100 0.100 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 5 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 6 0.100 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 7 0.300 0.150 0.150 0.300 0.150 0.150 0.150 0.150 0.150 0.150 0.150 0.150 Example 8 0.300 0.300 0.150 0.150 0.150 0.150 0.150 0.150 0.150 0.150 0.150 0.150 Example 9 0.150 0.300 0.300 0.150 0.150 0.150 0.150 0.150 0.150 0.150 0.150 0.150 Example 10 0.300 0.150 0.150 0.300 0.150 0.150 0.150 0.150 0.150 0.150 0.150 0.150 Example 11 0.300 0.300 0.150 0.150 0.150 0.150 0.150 0.150 0.150 0.150 0.150 0.150 Example 12 0.150 0.300 0.300 0.150 0.150 0.150 0.150 0.150 0.150 0.150 0.150 0.150 Example 13 0.450 0.225 0.225 0.450 0.225 0.225 0.225 0.225 0.225 0.225 0.225 0.225 Example 14 0.450 0.450 0.225 0.225 0.225 0.225 0.225 0.225 0.225 0.225 0.225 0.225 Example 15 0.225 0.450 0.450 0.225 0.225 0.225 0.225 0.225 0.225 0.225 0.225 0.225 Example 16 0.450 0.225 0.225 0.450 0.225 0.225 0.225 0.225 0.225 0.225 0.225 0.225 Example 17 0.450 0.450 0.225 0.225 0.225 0.225 0.225 0.225 0.225 0.225 0.225 0.225 Example 18 0.225 0.450 0.450 0.225 0.225 0.225 0.225 0.225 0.225 0.225 0.225 0.225 Color Resist Filter Particulate Pattern Pattern Defect Linearity Metal Ratio T.sub.2 Defect Shape Performance of Pattern Example 1 0.00000000700 A Rectangular A A Example 2 0.00000000700 A Rectangular A A Example 3 0.00000000700 A Rectangular A A Example 4 0.00000000350 A Rectangular A A Example 5 0.00000000350 A Rectangular A A Example 6 0.00000000350 A Rectangular A A Example 7 0.00000000700 A Rectangular A A Example 8 0.00000000700 A Rectangular A A Example 9 0.00000000700 A Rectangular A A Example 10 0.00000000350 A Rectangular A A Example 11 0.00000000350 A Rectangular A A Example 12 0.00000000350 A Rectangular A A Example 13 0.00000001050 A Rectangular A A Example 14 0.00000001050 A Rectangular A A Example 15 0.00000001050 A Rectangular A A Example 16 0.00000000525 A Rectangular A A Example 17 0.00000000525 A Rectangular A A Example 18 0.00000000525 A Rectangular A A

(101) TABLE-US-00010 TABLE 2-5 D: Particulate Metal (mass ppt) Na K Ca Fe Cu Mg Mn Li Al Cr Ni Example 19 0.200 0.100 0.100 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 20 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 21 0.100 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 22 0.200 0.100 0.100 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 23 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 24 0.100 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 25 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 26 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 27 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 28 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 29 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 30 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 31 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 32 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 33 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Comparative 10.500 10.000 10.100 10.300 10.000 9.900 10.000 10.400 10.000 10.700 10.000 Example 1 Comparative 10.500 10.000 10.100 10.300 10.000 9.900 10.000 10.400 10.000 10.700 10.000 Example 2 Comparative 10.600 10.100 10.200 10.400 10.100 10.000 10.100 10.500 10.100 10.800 10.100 Example 3 Color D: Particulate Resist Filter Metal (mass ppt) Particulate Pattern Pattern Defect Linearity Zn Metal Ratio T.sub.2 Defect Shape Performance of Pattern Example 19 0.100 0.00000000700 B Rectangular A B Example 20 0.100 0.00000000700 B Rectangular A C Example 21 0.100 0.00000000700 B Rectangular A B Example 22 0.100 0.00000000350 B Rectangular A B Example 23 0.100 0.00000000350 B Rectangular A C Example 24 0.100 0.00000000350 B Rectangular A B Example 25 0.100 0.00000000700 B Rectangular A B Example 26 0.100 0.00000000350 B Rectangular A B Example 27 0.100 0.00000000700 A Rectangular A B Example 28 0.100 0.00000000350 A Rectangular A B Example 29 0.100 0.00000000700 B Rectangular A B Example 30 0.100 0.00000000350 B Rectangular A B Example 31 0.100 0.00000000350 B Rectangular A B Example 32 0.100 0.00000000750 A Rectangular A A Example 33 0.100 0.00000000350 B Rectangular A B Comparative 10.500 0.00000061200 D Forward E D Example 1 Tapered Comparative 10.500 0.00000061200 E Forward E D Example 2 Tapered Comparative 10.600 0.00000061800 D Forward E D Example 3 Tapered

(102) TABLE-US-00011 TABLE 2-6 D: Particulate Metal (mass ppt) Na K Ca Fe Cu Mg Mn Li Al Cr Ni Comparative 10.600 10.100 10.200 10.400 10.100 10.000 10.100 10.500 10.100 10.800 10.100 Example 4 Comparative 10.700 10.200 10.300 10.500 10.200 10.100 10.200 10.600 10.200 10.900 10.200 Example 5 Comparative 10.800 10.300 10.400 10.600 10.300 10.200 10.300 10.700 10.300 11.000 10.300 Example 6 Comparative 10.900 10.400 10.500 10.700 10.400 10.300 10.400 10.800 10.400 11.100 10.400 Example 7 Comparative 11.000 10.500 10.600 10.800 10.500 10.400 10.500 10.900 10.500 11.200 10.500 Example 8 Comparative 10.500 10.000 10.100 10.300 10.000 9.900 10.000 10.400 10.000 10.700 10.000 Example 9 Comparative 10.500 10.000 10.100 10.300 10.000 9.900 10.000 10.400 10.000 10.700 10.000 Example 10 Comparative 10.600 10.100 10.200 10.400 10.100 10.000 10.100 10.500 10.100 10.800 10.100 Example 11 Comparative 10.700 10.200 10.300 10.500 10.200 10.100 10.200 10.600 10.200 10.900 10.200 Example 12 Comparative 10.800 10.300 10.400 10.600 10.300 10.200 10.300 10.700 10.300 11.000 10.300 Example 13 Comparative 10.900 10.400 10.500 10.700 10.400 10.300 10.400 10.800 10.400 11.100 10.400 Example 14 Comparative 11.000 10.500 10.600 10.800 10.500 10.400 10.500 10.900 10.500 11.200 10.500 Example 15 Example 34 0.200 0.100 0.100 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 35 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 36 0.100 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 37 0.200 0.100 0.100 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 38 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Example 39 0.100 0.200 0.200 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Color D: Particulate Resist Filter Metal (mass ppt) Particulate Pattern Pattern Defect Linearity Zn Metal Ratio T.sub.2 Defect Shape Performance of Pattern Comparative 10.600 0.00000061800 E Forward E D Example 4 Tapered Comparative 10.700 0.00000062400 E Forward E D Example 5 Tapered Comparative 10.800 0.00000063000 E Forward E D Example 6 Tapered Comparative 10.900 0.00000063600 D Forward E D Example 7 Tapered Comparative 11.000 0.00000064200 E Forward E D Example 8 Tapered Comparative 10.500 0.00000030600 D Forward E D Example 9 Tapered Comparative 10.500 0.00000030600 E Forward E D Example 10 Tapered Comparative 10.600 0.00000030900 E Forward E D Example 11 Tapered Comparative 10.700 0.00000031200 E Forward E D Example 12 Tapered Comparative 10.800 0.00000031500 E Forward E D Example 13 Tapered Comparative 10.900 0.00000031800 D Forward E D Example 14 Tapered Comparative 11.000 0.00000032100 E Forward E D Example 15 Tapered Example 34 0.100 0.00000000007 C Forward A D Tapered Example 35 0.100 0.00000000007 C Forward A D Tapered Example 36 0.100 0.00000000007 C Forward A D Tapered Example 37 0.100 0.00000000004 C Forward A D Tapered Example 38 0.100 0.00000000004 C Forward A D Tapered Example 39 0.100 0.00000000004 C Forward A D Tapered

B-1. Treatment Liquid for Manufacturing Semiconductor: Examples 101 to 152, Comparative Examples 101 and 102

(103) [Quaternary Ammonium Compound]

(104) The following quaternary ammonium compound was used under the same conditions as in Examples 1 to 39 and Comparative Examples 1 to 15.

(105) S-1: tetramethylammonium hydroxide (TMAH)

(106) [Additive]

(107) The following compounds were used as an additive.

(108) AA-2: NEWKALGEN FS-3 (manufactured by Takemoto Oil & Fat Co., Ltd.) (anionic surfactant: amine salt)

(109) AA-3: NEWKALGEN FS-7 (manufactured by Takemoto Oil & Fat Co., Ltd.) (anionic surfactant: amine salt)

(110) AA-4: EMAL 20C (manufactured by Takemoto Oil & Fat Co., Ltd.) (anionic surfactant: ether)

(111) AN-4: Surfynol S420 (manufactured by Air Products & Chemicals Ltd.) (nonionic surfactant: acetylene)

(112) AN-5: Surfynol S440 (manufactured by Air Products & Chemicals Ltd.) (nonionic surfactant: acetylene)

(113) AN-1: Surfynol S465 (manufactured by Air Products & Chemicals Ltd.) (nonionic surfactant: acetylene)

(114) AN-6: Surfynol S485 (manufactured by Air Products & Chemicals Ltd.) (nonionic surfactant: acetylene)

(115) AN-7: OLFINE E1004 (manufactured by Nissin Chemical Co., Ltd.) (nonionic surfactant: acetylene)

(116) AN-8: OLFINE E1010 (manufactured by Nissin Chemical Co., Ltd.) (nonionic surfactant: acetylene)

(117) AN-9: OLFINE E1020 (manufactured by Nissin Chemical Co., Ltd.) (nonionic surfactant: acetylene)

(118) AN-10: BLAUNON EL-1502.2 (manufactured by Aoki Oil Industrial Co., Ltd.) (nonionic surfactant: ether)

(119) AN-11: BLAUNON EL-1505 (manufactured by Aoki Oil Industrial Co., Ltd.) (nonionic surfactant: ether)

(120) AN-12: BLAUNON EL-1507.5 (manufactured by Aoki Oil Industrial Co., Ltd.) (nonionic surfactant: ether)

(121) AN-13: BLAUNON EL-1509.5 (manufactured by Aoki Oil Industrial Co., Ltd.) (nonionic surfactant: ether)

(122) AN-14: BLAUNON L-207 (manufactured by Aoki Oil Industrial Co., Ltd.) (nonionic surfactant: amine)

(123) AN-15: BLAUNON L-220 (manufactured by Aoki Oil Industrial Co., Ltd.) (nonionic surfactant: amine)

(124) AN-16: RHEODOL TW-L120 (manufactured Kao Corporation) (nonionic surfactant: fatty acid ester)

(125) AN-17: RHEODOL SP-L10 (manufactured Kao Corporation) (nonionic surfactant: fatty acid ester)

(126) AN-18: RHEODOL 430V (manufactured Kao Corporation) (nonionic surfactant: fatty acid ester)

(127) AC-2: PIONIN B-251 (manufactured by Takemoto Oil & Fat Co., Ltd.) (cationic surfactant: pyridinium salt)

(128) AC-3: PIONIN B-111 (manufactured by Takemoto Oil & Fat Co., Ltd.) (cationic surfactant: pyridinium salt)

(129) AC-4: AMPHITOL 24B (manufactured Kao Corporation) (cationic surfactant: betaine) AH-2: diethylenetriaminepentaacetic acid (chelating agent)

(130) [Water]

(131) Water was the same as that of Examples 1 to 39 and Comparative Examples 1 to 15.

B-2. Preparation of Developer: Examples 101 to 152, Comparative Examples 101 and 102

(132) Tables 3-1 to 3-4 show ratios of the addition amounts of the quaternary ammonium compounds and the additives with respect to the treatment liquid for manufacturing a semiconductor. 1000 g of each of mixed solutions was prepared according to the ratio shown in Tables 3-1 to 3-4 with respect to water as a balance. The obtained mixed solution was treated under the same conditions as in Examples 1 to 39 and Comparative Examples 1 to 15 to obtain a treatment liquid for manufacturing a semiconductor. This treatment liquid for manufacturing a semiconductor was used as a developer.

(133) The preparation, charging, storage, and the like of the above-described treatment liquid for manufacturing a semiconductor (developer) were performed and the container to be used was treated under the same conditions as in Examples 1 to 39 and Comparative Examples 1 to 15.

(134) [Measurement of Metal Atoms]

(135) One kind or two or more kinds of metal atoms selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn in the developer were measured under the same conditions as in Examples 1 to 39 and Comparative Examples 1 to 15.

(136) [Metal Atom Ratio Ti and Particulate Metal Ratio T2] The metal atom ratio T.sub.1 and the particulate metal ratio T.sub.2 were calculated under the same conditions as in Examples 1 to 39 and Comparative Examples 1 to 15. The calculation results are shown in Tables 3-1 to 3-4 and Tables 4-1 to 4-8.

(137) TABLE-US-00012 TABLE 3-1 A: Additive Quaternary Anionic Cationic Chelating Ammonium Surfactant Nonionic Surfactant Surfactant Agent Compound mass mass mass mass Metal Atom Kind mass % Kind ppm Kind ppm HLB Kind ppm Kind ppm Ratio T.sub.1 Example 101 S-1 2 — — AN-4 100 4 — — — — 0.00000033000 Example 102 S-1 2 — — AN-5 100 8 — — — — 0.00000027000 Example 103 S-1 2 — — AN-5 1,000 8 — — — — 0.00000003000 Example 104 S-1 2 — — AN-5 10,000 8 — — — — 0.00000000310 Example 105 S-1 2 — — AN-5 15,000 8 — — — — 0.00000000227 Example 106 S-1 2 — — AN-1 100 13 — — — — 0.00000031000 Example 107 S-1 2 — — AN-6 100 17 — — — — 0.00000027000 Example 108 S-1 2 — — AN-7 100 7 to 9 — — — — 0.00000030000 Example 109 S-1 2 — — AN-8 100 13 to 14 — — — — 0.00000034000 Example 110 S-1 2 — — AN-9 100 15 to 16 — — — — 0.00000033000 Example 111 S-1 2 — — AN-10 100 6 — — — — 0.00000032000 Example 112 S-1 2 — — AN-11 100 11 — — — — 0.00000033000 Example 113 S-1 2 — — AN-12 100 12 — — — — 0.00000036000

(138) TABLE-US-00013 TABLE 3-2 A: Additive Quaternary Anionic Cationic Chelating Ammonium Surfactant Nonionic Surfactant Surfactant Agent Compound mass mass mass mass Metal Atom Kind mass % Kind ppm Kind ppm HLB Kind ppm Kind ppm Ratio T.sub.1 Example 114 S-1 2 — — AN-13 100 15 — — — — 0.00000028000 Example 115 S-1 2 — — AN-14 100 12 — — — — 0.00000029000 Example 116 S-1 2 — — AN-15 100 16 — — — — 0.00000028000 Example 117 S-1 2 — — AN-16 100 17 — — — — 0.00000029000 Example 118 S-1 2 — — AN-17 100 9 — — — — 0.00000034000 Example 119 S-1 2 — — AN-18 100 11 — — — — 0.00000033000 Example 120 S-1 2 AA-2 100 — — — — — — — 0.00000031000 Example 121 S-1 2 AA-3 100 — — — — — — — 0.00000032000 Example 122 S-1 2 AA-4 100 — — — — — — — 0.00000029000 Example 123 S-1 2 — — — — — AC-2 100 — — 0.00000034000 Example 124 S-1 2 — — — — — AC-3 100 — — 0.00000029000 Example 125 S-1 2 — — — — — AC-4 100 — — 0.00000030000 Example 126 S-1 2 — — — — — — — AH-2 1,000 0.00000003100

(139) TABLE-US-00014 TABLE 3-3 A-2: Additive Quaternary A-1: Additive Anionic Ammonium Nonionic Surfactant Surfactant Nonionic Surfactant Compound mass mass mass Kind mass % Kind ppm HLB Kind ppm Kind ppm HLB Example 127 S-1 2 AN-4 100 4 — — AN-5 100 8 Example 128 S-1 2 AN-4 100 4 — — AN-1 100 13 Example 129 S-1 2 AN-5 100 8 — — AN-1 100 13 Example 130 S-1 2 AN-5 1,000 8 — — AN-1 1,000 13 Example 131 S-1 2 AN-5 200 8 — — AN-1 200 13 Example 132 S-1 2 AN-5 50 8 — — AN-1 50 13 Example 133 S-1 2 AN-5 100 8 — — AN-6 100 17 Example 134 S-1 2 AN-1 100 13 — — AN-6 100 17 Example 135 S-1 2 AN-5 100 8 AA-2 100 — — — Example 136 S-1 2 AN-5 100 8 AA-3 100 — — — Example 137 S-1 2 AN-5 100 8 AA-4 100 — — — Example 138 S-1 2 AN-5 100 8 — — — — — Example 139 S-1 2 AN-5 100 8 — — — — — Example 140 S-1 2 AN-5 100 8 — — — — — A-2: Additive Cationic Chelating Additive Surfactant Agent Sum mass mass (A-2)/ mass Metal Atom Kind ppm Kind ppm (A-1) ppm Ratio T.sub.1 Example 127 — — — — 1 200 0.00000014500 Example 128 — — — — 1 200 0.00000014500 Example 129 — — — — 1 200 0.00000015000 Example 130 — — — — 1 2,000 0.00000016500 Example 131 — — — — 1 400 0.00000001500 Example 132 — — — — 1 100 0.00000008500 Example 133 — — — — 1 200 0.00000034000 Example 134 — — — — 1 200 0.00000015500 Example 135 — — — — 1 200 0.00000018000 Example 136 — — — — 1 200 0.00000017500 Example 137 — — — — 1 200 0.00000016000 Example 138 AC-2 100 — — 1 200 0.00000014500 Example 139 AC-3 100 — — 1 200 0.00000015500 Example 140 AC-4 100 — — 1 200 0.00000015000

(140) TABLE-US-00015 TABLE 3-4 A-2: Additive Quaternary A-1: Additive Anionic Ammonium Nonionic Surfactant Surfactant Nonionic Surfactant Compound mass mass mass Kind mass % Kind ppm HLB Kind ppm Kind ppm HLB Example 141 S-1 2 AN-5 100 8 — — — — — Example 142 S-1 2 AN-7 100 7 to 9 — — AN-8 100 13 to 14 Example 143 S-1 2 AN-7 85 7 to 9 — — AN-8 200 13 to 14 Example 144 S-1 2 AN-7 100 7 to 9 — — AN-8 350 13 to 14 Example 145 S-1 2 AN-7 100 7 to 9 — — AN-8 50 13 to 14 Example 146 S-1 2 AN-7 100 7 to 9 — — AN-9 100 15 to 16 Example 147 S-1 2 AN-5 100 8 — — AN-1 100 13 Example 148 S-1 2 AN-5 100 8 — — AN-1 100 13 Example 149 S-1 2 AN-5 100 8 — — AN-1 100 13 Example 150 S-1 12 AN-5 100 8 — — AN-1 100 13 Example 151 S-1 24 AN-5 100 8 — — AN-1 100 13 Example 152 S-1 29 AN-5 100 8 — — AN-1 100 13 Example 153 S-1 2 AN-5 100 8 — — AN-1 100 13 Comparative S-1 2 AN-5 100 8 — — AN-1 100 13 Example 101 Comparative S-1 2 AN-5 100,000 8 — — AN-1 100,000 13 Example 102 A-2: Additive Cationic Chelating Additive Surfactant Agent Sum mass mass (A-2)/ mass Metal Atom Kind ppm Kind ppm (A-1) ppm Ratio T.sub.1 Example 141 — — AH-2  1,000 10 1,100 0.00000014500 Example 142 — — — — 1 200 0.00000003364 Example 143 — — — — 2 285 0.00000014000 Example 144 — — — — 4 450 0.00000011228 Example 145 — — — — 1 150 0.00000007111 Example 146 — — — — 1 200 0.00000019333 Example 147 — — — — 1 200 0.00000018500 Example 148 — — — — 1 200 0.00000075500 Example 149 — — — — 1 200 0.00000192000 Example 150 — — — — 1 200 0.00000534997 Example 151 — — — — 1 200 0.00000018000 Example 152 — — — — 1 200 0.00000018000 Example 153 — — — — 1 200 0.00000015000 Comparative — — — — 1 200 0.00204580610 Example 101 Comparative — — AH-2 200,000 1 400,000 0.0000000000006 Example 102

B-3. Examples 101 to 152, Comparative Examples 101 and 102

(141) [Evaluation of Defects]The evaluation was performed under the same conditions as in Examples 1 to 39 and Comparative Examples 1 to 15. The results are shown in Tables 4-5 to 4-8.

B-4. Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition: Examples 101 to 152, Comparative Examples 101 and 102

(142) The components of the actinic ray-sensitive or radiation-sensitive resin composition were the same as in Examples 1 to 39 and Comparative Examples 1 to 15.

B-5. Preparation of Resist Solution: Examples 101 to 152, Comparative Examples 101 and 102

(143) The resist solution was prepared under the same conditions as in Examples 1 to 39 and Comparative Examples 1 to 16.

B-6. Examples 101 to 152, Comparative Example 101: Resist Pattern

(144) A silicon wafer on which a resist pattern was formed was obtained using the same method as that of the resist pattern in Examples 1 to 39 and Comparative Examples 1 to 16.

B-7. Evaluation of Pattern Defect Performance: Examples 101 to 152, Comparative Examples 101 and 102

(145) Regarding each of the patterns obtained in Examples 101 to 152 and Comparative Examples 101 and 102, the number of defects having a diameter of 20 nm or more present on the substrate surface was measured using a wafer surface inspection device (PUMA 9850; manufactured by KLA-Tencor Corporation). The obtained number of defects was evaluated based on the following standards, and the results thereof are shown in Tables 4-5 to 4-8. In the following standards, the evaluation C represents that an ability of suppressing defects that is required for the treatment liquid for manufacturing a semiconductor is achieved.

(146) A: the number of defects was 0 to 500

(147) B: the number of defects was more than 500 and 1000 or less

(148) C: the number of defects was more than 1000 and 3000 or less

(149) D: the number of defects was more than 3000 and 5000 or less

(150) E: the number of defects was more than 5000

B-8. Evaluation of Pattern Collapse: Examples 101 to 152, Comparative Example 101

(151) An area ratio of pattern collapse to the defects measured in the evaluation of the pattern defect performance was evaluated based on the following standards. The results are shown in Tables 4-5 to 4-8.

(152) A: 0.5% or lower

(153) B: 0.5% to 0.8%

(154) C: 0.8% to 1.0%

(155) D: 1.0% to 2.0%

(156) E: 2.0% or higher

C. Example 153

(157) The treatment liquid according to Example 148 was further filtered using a nylon filter 5A (ULTIPLEAT P-Nylon, manufactured by Pall Corporation, 20 inch, pore size: 20 nm) set on a high-density polyethylene filter. The defect performance was evaluated under the same conditions as in Examples 101 to 152 and Comparative Examples 101 and 102. Further, a resist solution was prepared under the same conditions as in Examples 101 to 152 and Comparative Examples 101 and 102, and the defect performance, the pattern defect performance, and the pattern collapse were evaluated under the same conditions as in Examples 101 to 152 and Comparative Examples 101 and 102. The evaluation results of the defect performance, the pattern defect performance, and the pattern collapse are shown in Table 4-8.

D. Example 154

(158) The defect performance, the pattern defect performance, and the pattern collapse were evaluated under the same conditions as in Example 153, except that a nylon-based microfilter membrane (manufactured by Entegris Japan Co., Ltd.) having a pore size of 10 nm was used instead of the filter used in Example 153 and that the filtration temperature was 15° C. The same result as in Example 153 was obtained.

E. Example 155

(159) A coloring curable resin composition was prepared under the same conditions as in Example 1, except that the following F-1 was used instead of F781 in the coloring curable resin composition. Using this coloring curable resin composition, a color resist solution was prepared. Using the prepared color resist solution and the same method as in Example 1, the pattern linearity was evaluated, and the same result was obtained.

(160) F-1: a mixture of resins represented by the following structural formulae (Mw=14000) was dissolved in a solution of 0.2% of PEGMEA

(161) ##STR00092##

(162) TABLE-US-00016 TABLE 4-1 B: Metal Atoms (mass ppt) Metal Atom Na K Ca Fe Cu Mg Mn Li Al Cr Ni Zr Total Ratio T.sub.1 Example 101 3 2 5 6 2 3 2 1 5 1 2 1 33 0.00000033000 Example 102 4 1 6 4 1 2 1 1 4 1 1 1 27 0.00000027000 Example 103 3 2 5 5 1 2 2 1 6 1 1 1 30 0.00000003000 Example 104 4 2 4 4 2 3 2 1 5 1 2 1 31 0.00000000310 Example 105 3 3 5 5 2 4 1 1 6 1 2 1 34 0.00000000227 Example 106 2 2 5 4 3 3 2 1 6 1 1 1 31 0.00000031000 Example 107 3 2 3 4 2 2 1 1 5 1 2 1 27 0.00000027000 Example 108 3 2 4 4 2 3 2 1 4 1 3 1 30 0.00000030000 Example 109 4 2 5 5 2 4 2 1 5 1 2 1 34 0.00000034000 Example 110 4 4 5 4 1 3 1 1 6 1 2 1 33 0.00000033000 Example 111 3 2 6 4 2 4 2 1 5 1 1 1 32 0.00000032000 Example 112 4 2 5 4 3 2 3 1 5 1 2 1 33 0.00000033000 Example 113 3 3 7 5 2 3 2 1 6 1 2 1 36 0.00000036000

(163) TABLE-US-00017 TABLE 4-2 B: Metal Atoms (mass ppt) Metal Atom Na K Ca Fe Cu Mg Mn Li Al Cr Ni Zr Total Ratio T.sub.1 Example 114 3 2 5 4 1 3 1 1 5 1 1 1 28 0.00000028000 Example 115 2 2 5 5 2 3 1 1 4 1 2 1 29 0.00000029000 Example 116 3 1 3 4 1 4 2 1 5 1 2 1 28 0.00000028000 Example 117 3 2 5 5 1 3 2 1 4 1 1 1 29 0.00000029000 Example 118 4 3 5 5 2 2 3 1 5 1 2 1 34 0.00000034000 Example 119 3 2 7 4 3 3 2 1 4 1 2 1 33 0.00000033000 Example 120 3 2 5 5 2 3 2 1 5 1 1 1 31 0.00000031000 Example 121 3 3 5 4 2 4 2 1 4 1 2 1 32 0.00000032000 Example 122 3 2 4 3 2 3 3 1 5 1 1 1 29 0.00000029000 Example 123 4 2 5 4 3 4 2 1 6 1 1 1 34 0.00000034000 Example 124 3 1 5 4 2 4 1 1 4 1 2 1 29 0.00000029000 Example 125 3 2 3 5 3 3 1 1 5 1 2 1 30 0.00000030000 Example 126 3 2 5 4 3 3 2 1 5 1 1 1 31 0.00000003100

(164) TABLE-US-00018 TABLE 4-3 B: Metal Atoms (mass ppt) Metal Atom Na K Ca Fe Cu Mg Mn Li Al Cr Ni Zr Total Ratio T.sub.1 Example 127 3 2 5 3 2 3 2 1 5 1 1 1 29 0.00000014500 Example 128 2 1 6 4 1 4 3 1 4 1 2 1 30 0.00000014500 Example 129 3 2 4 4 2 4 2 1 6 1 3 1 33 0.00000015000 Example 130 2 3 5 2 4 2 3 1 4 1 2 1 30 0.00000016500 Example 131 2 3 5 3 3 3 3 1 6 1 3 1 34 0.00000001500 Example 132 3 2 4 5 2 4 4 1 6 1 1 1 34 0.00000008500 Example 133 3 1 5 4 3 3 2 1 5 1 2 1 31 0.00000034000 Example 134 2 2 4 4 5 3 4 1 6 1 3 1 36 0.00000015500 Example 135 3 3 5 6 2 4 3 1 4 1 2 1 35 0.00000018000 Example 136 2 4 5 4 2 4 3 1 4 1 1 1 32 0.00000017500 Example 137 2 2 3 5 1 3 2 1 6 1 2 1 29 0.00000016000 Example 138 3 3 5 4 2 2 2 1 6 1 1 1 31 0.00000014500 Example 139 2 2 4 3 3 2 4 1 5 1 2 1 30 0.00000015500 Example 140 2 2 5 4 2 3 3 1 4 1 1 1 29 0.00000015000

(165) TABLE-US-00019 TABLE 4-4 B: Metal Atoms (mass ppt) Na K Ca Fe Cu Mg Mn Li Example 141 3 4 4 5 3 4 3 1 Example 142 2 2 5 4 2 3 2 1 Example 143 3 2 5 5 2 3 2 1 Example 144 3 1 4 4 3 4 3 1 Example 145 4 1 4 4 2 3 2 1 Example 146 3 2 5 5 3 4 3 1 Example 147 15 2 21 12 14 16 13 8 Example 148 50 2 63 48 21 36 26 19 Example 149 123 1 215 116 59 94 73 51 Example 150 4 2 5 5 3 4 3 1 Example 151 2 3 6 5 2 3 4 1 Example 152 3 2 3 4 1 4 2 1 Example 153 2 2 5 3 1 2 1 1 Comparative 50,000 65,000 65,000 60,000 20,000 30,000 20,000 10,000 Example 101 Comparative <1 <1 <1 <1 <1 <1 <1 <1 Example 102 B: Metal Atoms (mass ppt) Metal Atom Al Cr Ni Zr Total Ratio T.sub.1 Example 141 6 1 2 1 37 0.00000014500 Example 142 4 1 1 1 28 0.00000003364 Example 143 5 1 2 1 32 0.00000014000 Example 144 4 1 3 1 32 0.00000011228 Example 145 4 1 2 1 29 0.00000007111 Example 146 6 1 3 1 37 0.00000019333 Example 147 21 7 15 7 151 0.00000018500 Example 148 54 16 35 14 384 0.00000075500 Example 149 131 51 97 59 1,070 0.00000192000 Example 150 4 1 3 1 36 0.00000534997 Example 151 6 1 2 1 36 0.00000018000 Example 152 5 1 3 1 30 0.00000018000 Example 153 4 1 1 1 24 0.00000015000 Comparative 50,000 10,000 20,000 10,000 410,000 0.00204580610 Example 101 Comparative <1 <1 <1 <1 0.25 0.0000000000006 Example 102

(166) TABLE-US-00020 TABLE 4-5 D: Particulate Metal (mass ppt) Na K Ca Fe Cu Mg Mn Li Al Cr Ni Zr Example 101 0.300 0.200 0.600 0.700 0.100 0.200 0.100 0.100 0.600 0.100 0.100 0.100 Example 102 0.300 0.200 0.700 0.400 0.100 0.200 0.100 0.100 0.400 0.100 0.100 0.100 Example 103 0.200 0.300 0.500 0.500 0.100 0.200 0.100 0.100 0.600 0.100 0.100 0.100 Example 104 0.400 0.200 0.400 0.400 0.100 0.300 0.200 0.100 0.600 0.100 0.100 0.100 Example 105 0.200 0.200 0.600 0.400 0.100 0.400 0.100 0.100 0.500 0.100 0.100 0.100 Example 106 0.200 0.200 0.500 0.400 0.300 0.400 0.100 0.100 0.500 0.100 0.100 0.100 Example 107 0.200 0.100 0.300 0.400 0.200 0.200 0.100 0.100 0.500 0.100 0.100 0.100 Example 108 0.200 0.100 0.400 0.400 0.100 0.200 0.200 0.100 0.400 0.100 0.200 0.100 Example 109 0.500 0.100 0.500 0.500 0.100 0.400 0.200 0.100 0.500 0.100 0.100 0.100 Example 110 0.400 0.200 0.600 0.500 0.100 0.400 0.100 0.100 0.800 0.100 0.100 0.100 Example 111 0.200 0.100 0.600 0.500 0.200 0.500 0.100 0.100 0.600 0.100 0.100 0.100 Example 112 0.400 0.100 0.600 0.400 0.200 0.100 0.200 0.100 0.500 0.100 0.100 0.100 Example 113 0.200 0.200 0.800 0.500 0.200 0.200 0.100 0.100 0.500 0.100 0.100 0.100 Evaluation D: Particulate Defect Metal (mass ppt) Particulate Defect Pattern Pattern Defect Total Metal Ratio T.sub.2 Performance Collapse Performance Example 101 3.200 0.00000003200 C C C Example 102 2.800 0.00000002800 C C C Example 103 2.900 0.00000000290 C C C Example 104 3.000 0.00000000030 C C C Example 105 2.900 0.00000000019 C D C Example 106 3.000 0.00000003000 C C C Example 107 2.400 0.00000002400 C C C Example 108 2.500 0.00000002500 C C C Example 109 3.200 0.00000003200 C C C Example 110 3.500 0.00000003500 C C C Example 111 3.200 0.00000003200 C C C Example 112 2.900 0.00000002900 C C C Example 113 3.100 0.00000003100 C C C

(167) TABLE-US-00021 TABLE 4-6 D: Particulate Metal (mass ppt) Na K Ca Fe Cu Mg Mn Li Al Cr Ni Zr Example 114 0.300 0.200 0.500 0.400 0.100 0.200 0.100 0.100 0.400 0.100 0.100 0.100 Example 115 0.300 0.200 0.500 0.500 0.100 0.200 0.100 0.100 0.300 0.100 0.100 0.100 Example 116 0.300 0.100 0.300 0.400 0.100 0.300 0.100 0.100 0.300 0.100 0.100 0.100 Example 117 0.200 0.200 0.300 0.500 0.100 0.100 0.200 0.100 0.400 0.100 0.100 0.100 Example 118 0.400 0.200 0.300 0.500 0.200 0.100 0.300 0.100 0.400 0.100 0.100 0.100 Example 119 0.400 0.200 0.600 0.400 0.300 0.200 0.100 0.100 0.300 0.100 0.100 0.100 Example 120 0.300 0.200 0.700 0.500 0.200 0.300 0.100 0.100 0.300 0.100 0.100 0.100 Example 121 0.300 0.200 0.400 0.400 0.100 0.300 0.200 0.100 0.400 0.100 0.100 0.100 Example 122 0.300 0.100 0.300 0.400 0.200 0.200 0.300 0.100 0.400 0.100 0.100 0.100 Example 123 0.300 0.100 0.300 0.400 0.200 0.300 0.100 0.100 0.600 0.100 0.100 0.100 Example 124 0.400 0.100 0.300 0.400 0.100 0.400 0.100 0.100 0.300 0.100 0.100 0.100 Example 125 0.300 0.200 0.200 0.500 0.300 0.200 0.100 0.100 0.400 0.100 0.100 0.100 Example 126 0.300 0.200 0.400 0.400 0.300 0.300 0.100 0.100 0.400 0.100 0.100 0.100 Evaluation D: Particulate Defect Metal (mass ppt) Particulate Defect Pattern Pattern Defect Total Metal Ratio T.sub.2 Performance Collapse Performance Example 114 2.600 0.00000002600 C C C Example 115 2.600 0.00000002600 C C C Example 116 2.300 0.00000002300 C C C Example 117 2.400 0.00000002400 C C C Example 118 2.800 0.00000002800 C C C Example 119 2.900 0.00000002900 C C C Example 120 3.000 0.00000003000 C C C Example 121 2.700 0.00000002700 C C C Example 122 2.600 0.00000002600 C C C Example 123 2.700 0.00000002700 C C C Example 124 2.500 0.00000002500 C C C Example 125 2.600 0.00000002600 C C C Example 126 2.800 0.00000000280 C C C

(168) TABLE-US-00022 TABLE 4-7 D: Particulate Metal (mass ppt) Na K Ca Fe Cu Mg Mn Li Al Cr Ni Zr Example 127 0.200 0.200 0.600 0.200 0.200 0.200 0.200 0.100 0.500 0.100 0.100 0.100 Example 128 0.200 0.100 0.700 0.400 0.100 0.400 0.300 0.100 0.400 0.100 0.100 0.100 Example 129 0.300 0.100 0.400 0.400 0.200 0.300 0.200 0.100 0.600 0.100 0.200 0.100 Example 130 0.100 0.300 0.500 0.200 0.400 0.200 0.200 0.100 0.400 0.100 0.100 0.100 Example 131 0.200 0.200 0.500 0.300 0.200 0.300 0.300 0.100 0.500 0.100 0.100 0.100 Example 132 0.200 0.100 0.400 0.500 0.200 0.400 0.500 0.100 0.600 0.100 0.100 0.100 Example 133 0.200 0.100 0.500 0.400 0.200 0.300 0.200 0.100 0.500 0.100 0.100 0.100 Example 134 0.100 0.100 0.500 0.500 0.500 0.200 0.400 0.100 0.500 0.100 0.200 0.100 Example 135 0.200 0.200 0.500 0.600 0.200 0.300 0.300 0.100 0.400 0.100 0.100 0.100 Example 136 0.100 0.400 0.500 0.300 0.100 0.400 0.300 0.100 0.400 0.100 0.100 0.100 Example 137 0.200 0.200 0.300 0.400 0.100 0.300 0.100 0.100 0.600 0.100 0.100 0.100 Example 138 0.200 0.300 0.500 0.400 0.100 0.200 0.200 0.100 0.500 0.100 0.100 0.100 Example 139 0.200 0.200 0.400 0.400 0.400 0.100 0.400 0.100 0.500 0.100 0.100 0.100 Example 140 0.100 0.100 0.500 0.300 0.200 0.300 0.300 0.100 0.400 0.100 0.100 0.100 D: Particulate Evaluation Metal (mass ppt) Particulate Defect Pattern Defect Total Metal Ratio T.sub.2 Performance Lithography Performance Example 127 2.700 0.00000000900 C C C Example 128 3.000 0.00000001000 A A B Example 129 3.000 0.00000001000 A A B Example 130 2.700 0.00000000090 B B B Example 131 2.900 0.00000000483 A A B Example 132 3.300 0.00000002200 B B B Example 133 2.800 0.00000000933 A A B Example 134 3.300 0.00000001100 C C C Example 135 3.100 0.00000001550 C C C Example 136 2.900 0.00000001450 C C C Example 137 2.600 0.00000001300 C C C Example 138 2.800 0.00000001400 C C C Example 139 3.000 0.00000001500 C C C Example 140 2.600 0.00000001300 C C C

(169) TABLE-US-00023 TABLE 4-8 D: Particulate Metal (mass ppt) Na K Ca Fe Cu Mg Mn Li Al Cr Ni Example 141 0.300 0.400 0.400 0.400 0.200 0.400 0.300 0.100 0.700 0.100 0.100 Example 142 0.200 0.100 0.400 0.300 0.200 0.300 0.300 0.100 0.400 0.100 0.100 Example 143 0.200 0.100 0.500 0.400 0.100 0.300 0.200 0.100 0.500 0.100 0.100 Example 144 0.200 0.100 0.500 0.400 0.300 0.300 0.200 0.100 0.300 0.100 0.200 Example 145 0.400 0.100 0.400 0.300 0.200 0.300 0.200 0.100 0.400 0.100 0.100 Example 146 0.300 0.100 0.400 0.500 0.200 0.400 0.300 0.100 0.600 0.100 0.100 Example 147 1.700 0.100 2.300 1.300 2.100 1.500 1.200 0.700 2.800 0.800 2.300 Example 148 6.900 0.200 7.900 3.900 2.900 4.300 2.500 2.100 7.200 2.100 4.100 Example 149 13.800 0.100 11.900 9.200 7.800 10.800 6.900 5.700 15.800 4.900 10.200 Example 150 0.300 0.100 0.400 0.300 0.200 0.400 0.300 0.100 0.400 0.100 0.300 Example 151 0.200 0.200 0.600 0.400 0.200 0.300 0.300 0.100 0.600 0.100 0.200 Example 152 0.300 0.100 0.300 0.400 0.100 0.400 0.200 0.100 0.500 0.100 0.300 Example 153 0.200 0.100 0.500 0.300 0.100 0.200 0.100 0.100 0.400 0.100 0.100 Comparative 750.000 650.000 650.000 600.000 200.000 300.000 200.000 100.000 500.000 1,380 200.000 Example 101 Comparative 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001 Example 102 Evaluation D: Particulate Metal (mass ppt) Particulate Defect Pattern Defect Zr Total Metal Ratio T.sub.2 Performance Lithography Performance Example 141 0.100 3.500 0.00000000167 C C C Example 142 0.100 2.600 0.00000000867 A A B Example 143 0.100 2.700 0.00000000557 A A A Example 144 0.100 2.800 0.00000000350 A A A Example 145 0.100 2.700 0.00000001350 A A C Example 146 0.100 3.200 0.00000001067 A A B Example 147 0.800 17.600 0.00000005867 A B B Example 148 1.200 45.300 0.00000015100 B A B Example 149 6.300 103.400 0.00000034467 C A C Example 150 0.100 3.000 0.00000001000 B B C Example 151 0.100 3.300 0.00000001100 C C C Example 152 0.100 2.900 0.00000000967 C D C Example 153 0.100 2.300 0.00000000767 A A A Comparative 100.000 5,630.000 0.00001874105 E D E Example 101 Comparative 0.001 0.001 0.00000000000 C E E Example 102