Microelectronic cleaning agent(s) and method(s) of fabricating semiconductor device(s) using the same
According to an example embodiment of the present invention, the microelectronic cleaning agent may include a fluoride component, an acid component, a chelating agent, a surfactant and water. Example embodiments of the present invention provide a microelectronic cleaning agent which can selectively remove, for example, a high-k dielectric layer. The microelectronic cleaning agent includes from about 0.001 weight % to about 10 weight % of a fluoride component, from about 0.001 weight % to about 30 weight % of an acid component, from about 0.001 weight % to about 20 weight % of a chelating agent, from about 0.001 weight % to about 10 weight % of a surfactant, and water (H 2 O). The water may comprise the remainder of the cleaning agent. According to another embodiment of the present invention, a method of fabricating a semiconductor device using the microelectronic cleaning agent is also provided.
1 . A microelectronic cleaning agent comprising a fluoride component, an acid component, a chelating agent, a surfactant and water.
2 . The microelectronic cleaning agent of claim 1 comprising from about 0.001 weight % to about 10 weight % of the fluoride component, from about 0.001 weight % to about 30 weight % of the acid component, from about 0.001 weight % to about 20 weight % of the chelating agent, from about 0.001 weight % to about 10 weight % of the surfactant, and water (H 2 O), based on a total weight of the microelectronic cleaning agent.
3 . The microelectronic cleaning agent according to claim 1 , wherein the fluoride component includes HF, NH 4 F, or a mixture thereof.
4 . The microelectronic cleaning agent according to claim 1 , wherein the acid component includes at least one member selected from the group consisting of HNO 3 , HCl, HClO 4 , H 3 PO 4 , H 2 SO 4 , H 5 IO 6 , and CH 3 COOH.
5 . The microelectronic cleaning agent of claim 1 , wherein the chelating agent includes at least one amine.
6 . The microelectronic cleaning agent according to claim 1 , wherein the chelating agent includes at least one amine selected from the group consisting of monoethanolamine (C 2 H 7 NO), diethanolamine (C 4 H 11 NO 2 ), triethanolamine (C 6 H 15 NO 3 ), diethylenetriamine (C 4 H 13 N 3 ), methylamine (CH 3 NH 2 ), ethylamine (C 2 H 5 NH 2 ), propyl (C 3 H 7 —NH 2 ), butyl (C 4 H 9 —NH 2 ), and pentyl (C 5 H 11 —NH 2 ).
7 . The microelectronic cleaning agent of claim 1 , wherein the chelating agent includes a ligand.
8 . The microelectronic cleaning agent according to claim 7 , wherein the ligand is an aminecarboxylic acid.
9 . The microelectronic cleaning agent according to claim 8 , wherein the aminecarboxylic acid is diethylenetriaminepentaacetic acid (C 6 H 16 N 3 O 2 ).
10 . The microelectronic cleaning agent of claim 1 , wherein the chelating agent includes at least one amino acid.
11 . The microelectronic cleaning agent according to claim 10 , wherein the at least one amino acid is selected from the group consisting of glycine (C 8 H 9 NO 3 ), alanine (C 3 H 7 NO 2 ), valine ((CH 3 ) 2 CHCH(NH 2 )COOH), leucine (C 6 H 13 NO 2 ), isoleucine (C 6 H 13 NO 2 ), serine (HOCH 2 CH(NH 2 )COOH), threonine (C 4 H 9 NO 3 ), tyrosine (C 9 H 11 NO 3 ), tryptophane (C 11 H 12 N 2 O 2 ), aspartic acid (C 4 H 7 O 4 N), glutamine (C 6 O 3 H 10 N 2 ), aspartic acid (C 4 H 7 O 4 N), lysine (H 2 N(CH 2 ) 4 (NH 2 )COOH), arginine (C 6 H 14 N 4 O 2 ), histidine (C 6 H 9 N 3 O 2 ), cysteine (C 3 H 7 NO 2 S), methionine (C 5 H 11 NO 2 S), cystine (C 6 H 12 N 2 O 4 S 2 ), proline (lumino acid) (C 5 H 9 NO 2 ), sulfamine (C 6 H 8 N 2 O 2 S), and hydroxyproline (C 5 H 9 NO 3 ).
12 . The microelectronic cleaning agent of claim 1 , wherein the surfactant includes at least one polymer.
13 . The microelectronic cleaning agent according to claim 12 , wherein the at least one polymer has at least an ethylene oxide (—C—C—O—) group and an —OH group.
14 . The microelectronic cleaning agent according to claim 12 , wherein the at least one polymer is selected from the group consisting of ethylene glycol (C 2 H 6 O 2 ), propylene glycol (C 3 H 8 O 2 ), diethylene glycol (C 4 H 10 O 3 ), triethylene glycol (C 6 H 14 O 4 ), dipropylene glycol (C 6 H 14 O 3 ), ethylene glycol methyl butyl ether (C 7 H 16 O 2 ), polyoxyethylene dodecyl ether (C 12 H 25 O(C 2 H 4 O) n H), polyoxyethylene oleyl ether (C 18 H 37 O(C 2 H 4 O) n H), polyoxyethylene cetyl ether (C 16 H 33 O(C 2 H 4 O) n H), polyoxyethylene stearyl ether (C 18 H 35 O(C 2 H 4 O) n H), polyoxyethylene octyl ether (C 8 H 17 O(C 2 H 4 O) n H), polyoxyethylene tridecyl ether (C 13 H 37 O(C 2 H 4 O) n H), polyoxyethylene dodecyl ester (C 12 H 25 COO(C 2 H 4 O) n H), polyoxyethylene oleyl ester (C 18 H 37 COO(C 2 H 4 O) n H), polyoxyethylene cetyl ester (C 16 H 33 COO(C 2 H 4 O) n H), polyoxyethylene stearyl ester (C 18 H 35 COO(C 2 H 4 O) n H), and polyoxyethylene octyl ester (C 8 H 17 COO(C 2 H 4 O) n H),
wherein n is an integer so that n≧1.
15 . The microelectronic cleaning agent of claim 1 comprising from about 0.1 weight % to about 1 weight % of the fluoride component, from about 0.001 weight % to about 30 weight % of the acid component, from about 0.1 weight % to about 1 weight % of the chelating agent, from about 0.1 weight % to about 1 weight % of the surfactant, and water (H 2 O), based on a total weight of the cleaning agent.
16 . A method of fabricating a semiconductor device comprising:
forming a dielectric layer on a semiconductor substrate;
forming a mask pattern on the semiconductor substrate forming exposed regions of the dielectric layer; and
etching the exposed regions of the dielectric layer using a microelectronic cleaning agent.
17 . The method of claim 16 , wherein the microelectronic cleaning agent comprises from about 0.001 weight % to about 10 weight % of a fluoride component, from about 0.001 weight % to about 30 weight % of an acid component, from 0.001 weight % to about 20 weight % of a chelating agent, from about 0.001 weight % to about 10 weight % of a surfactant, and water (H 2 O), based on a total weight of the microelectronic cleaning agent.
18 . The method according to claim 16 , wherein the dielectric layer includes at least one high-k dielectric material selected from the group consisting of AlO, GdO, YbO, DyO, NbO, YO, HfO, HfSiO, HfAlO, HfSiON, ZrSiO, ZrAlO, ZrO, LaO, TaO, TiO, SrTiO, and BaSrTiO.
19 . The method according to claim 16 , wherein the mask pattern includes a gate electrode.
20 . The method according to claim 16 , wherein the mask pattern further includes a hard mask pattern laminated on the gate electrode.
21 . The method according to claim 16 , wherein the etching of the exposed regions of the dielectric layer is performed at a temperature from about 10° C. to about 80° C.
22 . The method of claim 16 , wherein the microelectronic cleaning agent comprises from about 0.1 weight % to about 1 weight % of a fluoride component, from about 0.001 weight % to about 30 weight % of an acid component, from about 0.1 weight % to about 1 weight % of a chelating agent, from about 0.1 weight % to about 1 weight % of a surfactant, and water (H 2 O), based on a total weight of the cleaning agent.
23 . The method of claim 17 , wherein the water comprises a remainder of the microelectronic cleaning agent.
24 . The method of claim 22 , wherein the water comprises a remainder of the microelectronic cleaning agent.