Method of manufacturing semiconductor device

1. A method of manufacturing a semiconductor device comprising:

attaching, by a liquid treatment, a first liquid to a surface of a semiconductor substrate having a fine pattern formed therein;

substituting the first liquid attached to the surface of the semiconductor substrate with a solution, the solution comprising a sublimate dissolved in a second liquid;

vaporizing the second liquid and precipitating the sublimate to the surface of the semiconductor substrate to form a solid precipitate comprising the sublimate; and

removing the precipitate by sublimation,

the sublimate comprising at least one material selected from a group consisting of:

materials represented by chemical formulae A1, A2, A3, and A4 indicated in FIG. 5A , FIG. 5B , FIG. 5C , and FIG. 5D where X 1 , X 2 , and X 3 in the chemical formulae A1, A2, A3, and A4 each independently represent either of a hydroxy group (—OH), a carboxyl group (—COOH), an amino group (—NH 2 ), an amide group (—CONH 2 ), a nitro group (—NO 2 ), and a methylester group (—COO—CH 3 ),

materials represented by chemical formulae B1, B2, B3, B4, and B5 indicated in FIG. 6A , FIG. 6B , FIG. 6C , FIG. 6D , and FIG. 6E where X 1 , X 2 , X 3 , and X 4 in the chemical formulae B1, B2, B3, B4 and B5 each independently represent either of a hydroxy group (—OH), a carboxyl group (—COOH), an amino group (—NH 2 ), an amide group (—CONH 2 ), a nitro group (—NO 2 ), a methylester group (—COO—CH 3 ), a methoxy group (—OCH 3 ), an ethoxy group (—OCH 2 CH 3 ), and a propoxy group (—OCH 2 CH 2 CH 3 ),

materials represented by chemical formulae C1 and C2 indicated in FIG. 7A and FIG. 7B where X 1 and X 2 in the chemical formulae C1 and C2 each independently represent either of a hydroxy group (—OH), a carboxyl group (—COOH), an amino group (—NH 2 ), an amide group (—CONH 2 ), a nitro group (—NO 2 ), a methylester group (—COO—CH 3 ), a methoxy group (—OCH 3 ), an ethoxy group (—OCH 2 CH 3 ), and a propoxy group (—OCH 2 CH 2 CH 3 ), and

materials represented by chemical formulae D1 and D2 indicated in FIG. 8A and FIG. 8B where X 1 , X 2 , X 3 , and X 4 in the chemical formulae D1 and D2 each independently represent either of a hydroxy group (—OH), a carboxyl group (—COOH), an amino group (—NH 2 ), an amide group (—CONH 2 ), a nitro group (—NO 2 ), a methylester group (—COO—CH 3 ), a methoxy group (—OCH 3 ), an ethoxy group (—OCH 2 CH 3 ), and a propoxy group (—OCH 2 CH 2 CH 3 ) and where R in the chemical formulae D1 and D2 represent either of a carbonyl group (—CO—), a peptide bond (—CONH—), an ester bond (—COO—), an ether bond (—O—), (—NHNHO—) bond, (—COCOO—) bond, and a (—CHCH—) bond.

2. The method according to claim 1 , wherein the sublimate comprises a material having at least two carboxyl groups bonded to cyclohexane.

3. The method according to claim 1 , wherein the sublimate comprises two carboxyl groups bonded to benzene, bonding sites of the two carboxyl groups being adjacent to one another.

4. The method according to claim 1 , wherein X 1 , X 2 , X 3 , and X 4 in the chemical formulae A1, A2, A3, A4, B1, B2, B3, B4, B5, C1, C2, D1 and D2 each independently represent a hydroxy group or a carboxyl group.

5. The method according to claim 1 , wherein the chemical formula A1 represents cyclohexane-1,2-dicarboxylic acid, the chemical formula A2 represents cyclohexane-1,3-dicarboxylic acid, the chemical formula A3 represents cyclohexane-1,4-dicarboxylic acid, and the chemical formula A4 represents cyclohexane-1,2,4-tricarboxylic acid.

6. The method according to claim 1 , wherein the chemical formula B1 represents phtalic acid and the chemical formula B2 represents aminoacetphenone.

7. The method according to claim 1 , wherein the chemical formula B3 represents a material including either of barinin, 4-hydroxyphtalic acid, trimellitic acid, trimellitic anhydride, and dimethoxyacetphenone.

8. The method according to claim 1 , wherein the chemical formula B4 represents 5-hydroxyisophtalic acid.

9. The method according to claim 1 , wherein the chemical formula B5 represents a material including either gallic acid or gallic acid methyl.

10. The method according to claim 1 , wherein the chemical formula C1 or C2 represents 1,7-dihydronaphthalene.

11. The method according to claim 1 , wherein the chemical formula D1 represents 4,4′-dihydroxybenzophenone and the chemical formula D2 represents 2,2′,4,4′-tetrahydroxybenzophenone.

12. The method according to claim 1 , wherein the first liquid comprises at least one material selected from a group consisting of water, aliphatic hydrocarbon, aromatic hydrocarbon, esters, ketones, alcohols and ethers, polyalcohols, and pyrrolidone solvent.

13. The method according to claim 1 , wherein the second liquid comprises at least one material selected from a group consisting of aliphatic hydrocarbon, aromatic hydrocarbon, esters, ketones, alcohols and ethers, polyalcohols, and pyrrolidone solvent.

14. The method according to claim 1 , wherein the second liquid comprises at least one material selected from a group consisting of water, methanol, ethanol, IPA (isopropyl alcohol), butanol, propanol, ethylene glycol, propylene glycol, NMP (N-methyl-2-pyrrolidone), DMF (N,N-dimethyformamide), DMA (N,N-dimethylacetamide) and DMSO (dimethylsulfoxide), hexane, toluene, propyleneglycol monomethylether acetate (PGMEA), propyleneglycol monomethylether (PGME), propyleneglycol monopropylether (PGPE), propyleneglycol monoethylether (PGEE), gamma butyrolactone (GBL), acetylacetone, 3-pentanone, 2-pentanone, ethyl lactate, cyclohexanone, dibutylether, hydrofluoroether (HFE), ethyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, m-xylenehexafluoride, cyclohexane, formic acid, acetic acid, pyridine, diethylamine, dimethylamine, ethylenediamine, triethylamine, dimethylacetamide, diethylacetamide, and formamide.

15. A method of manufacturing a semiconductor device comprising:

attaching, by a liquid treatment, a first liquid to a surface of a semiconductor substrate having a fine pattern formed therein;

substituting the first liquid attached to the surface of the semiconductor substrate with a third liquid, the third liquid having an affinity for the first liquid;

substituting the third liquid with a solution, the solution comprising a sublimate dissolved in a second liquid, the second liquid having an affinity for the third liquid;

vaporizing the second liquid and precipitating the sublimate to the surface of the semiconductor substrate to form a solid precipitate comprising the sublimate; and

removing the precipitate by sublimation,

the sublimate comprising at least one material selected from a group consisting of:

materials represented by chemical formulae A1, A2, A3, and A4 indicated in FIG. 5A , FIG. 5B , FIG. 5C , and FIG. 5D where X 1 , X 2 , and X 3 in the chemical formulae A1, A2, A3, and A4 each independently represent either of a hydroxy group (—OH), a carboxyl group (—COOH), an amino group (—NH 2 ), an amide group (—CONH 2 ), a nitro group (—NO 2 ) and a methylester group (—COO—CH 3 ),

materials represented by chemical formulae B1, B2, B3, B4, and B5 indicated in FIG. 6A , FIG. 6B , FIG. 6C , FIG. 6D , and FIG. 6E where X 1 , X 2 , X 3 , and X 4 in the chemical formulae B1, B2, B3, B4 and B5 each independently represent either of a hydroxy group (—OH), a carboxyl group (—COOH), an amino group (—NH 2 ), an amide group (—CONH 2 ), a nitro group (—NO 2 ), a methylester group (—COO—CH 3 ), a methoxy group, an ethoxy group, and a propoxy group,

materials represented by chemical formulae C1 and C2 indicated in FIG. 7A and FIG. 7B where X 1 and X 2 in the chemical formulae C1 and C2 each independently represent either of a hydroxy group (—OH), a carboxyl group (—COOH), an amino group (—NH 2 ), an amide group (—CONH 2 ), a nitro group (—NO 2 ), a methylester group (—COO—CH 3 ), a methoxy group (—OCH 3 ), an ethoxy group (—OCH 2 CH 3 ), and a propoxy group (—OCH 2 CH 2 CH 3 ), and

materials represented by chemical formulae D1 and D2 indicated in FIG. 8A and FIG. 8B where X 1 , X 2 , X 3 , and X 4 in the chemical formulae D1 and D2 each independently represent either of a hydroxy group (—OH), a carboxyl group (—COOH), an amino group (—NH 2 ), an amide group (—CONH 2 ), a nitro group (—NO 2 ), a methylester group (—COO—CH 3 ), a methoxy group (—OCH 3 ), an ethoxy group (—OCH 2 CH 3 ) and a propoxy group (—OCH 2 CH 2 CH 3 ) and where R in the chemical formulae D1 and D2 represent either of a carbonyl group (—CO—), a peptide bond (—CONH—), an ester bond (—COO—), an ether bond (—O—), (—NHNHO—) bond, (—COCOO—) bond, and a (—CHCH—) bond.

16. The method according to claim 15 , wherein the sublimate comprises a material having at least two carboxyl groups bonded to cyclohexane.

17. The method according to claim 15 , wherein the sublimate comprises two carboxyl groups bonded to benzene, bonding sites of the two carboxyl groups being adjacent to one another.

18. The method according to claim 15 , wherein X 1 , X 2 , X 3 , and X 4 in the chemical formulae A1, A2, A3, A4, B1, B2, B3, B4, B5, C1, C2, D1 and D2 each independently represent a hydroxy group or a carboxyl group.

19. The method according to claim 15 , wherein the second liquid comprises at least one material selected from a group consisting of aliphatic hydrocarbon, aromatic hydrocarbon, esters, ketones, alcohols and ethers, polyalcohols, and pyrrolidone solvent.

20. The method according to claim 15 , wherein the second liquid comprises at least one material selected from a group consisting of water, methanol, ethanol, IPA (isopropyl alcohol), butanol, propanol, ethylene glycol, propylene glycol, NMP (N-methyl-2-pyrrolidone), DMF (N,N-dimethyformamide), DMA (N,N-dimethylacetamide) and DMSO (dimethylsulfoxide), hexane, toluene, propyleneglycol monomethylether acetate (PGMEA), propyleneglycol monomethylether (PGME), propyleneglycol monopropylether (PGPE), propyleneglycol monoethylether (PGEE), gamma butyrolactone (GBL), acetylacetone, 3-pentanone, 2-pentanone, ethyl lactate, cyclohexanone, dibutylether, hydrofluoroether (HFE), ethyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, m-xylenehexafluoride, cyclohexane, formic acid, acetic acid, pyridine, diethylamine, dimethylamine, ethylenediamine, triethylamine, dimethylacetamide, diethylacetamide, and formamide.