Liquid composition for removing titanium nitride, semiconductor element cleaning method using the same, and semiconductor element manufacturing method

Abstract

A liquid composition which removes titanium nitride from a substrate without corroding tungsten or a low-k interlayer dielectric also present on the substrate, the liquid composition having a pH of 0 to 4 and comprising:at least one oxidizing agent (A) selected from the group consisting of potassium permanganate, ammonium peroxodisulfate, potassium peroxodisulfate and sodium peroxodisulfate;a fluorine compound (B); and a tungsten corrosion inhibitor (C), wherein the tungsten corrosion inhibitor (C) comprises at least one compound selected from a group of compounds (C1) consisting of alkylamines and salts thereof, fluoroalkylamines and salts thereof, alkylamine oxides, fluoroalkylamine oxides, alkylbetaines, fluoroalkylbetaines, quaternary alkylammonium and salts thereof, quaternary fluoroalkylammonium and salts thereof, quaternary alkylpyridinium salts, quaternary fluoroalkylpyridinium salts, quaternary alkylbipyridinium salts,quaternary fluoroalkylbipyridinium salts, quaternary alkylimidazolium salts, and quaternary fluoroalkylimidazolium salts, and at least one compound selected from a group of compounds (C2) consisting of polyoxyalkylenealkylamines, polyoxyalkylenefluoroalkylamines, polyoxyalkylenealkyl ethers, polyoxyalkylenefluoroalkyl ethers, polyoxyalkylenealkyl phosphates, polyoxyalkylenefluoroalkylphosphates, polyoxyalkylenealkyl ether sulfates, polyoxyalkylenefluoroalkyl ether sulfates, alkyldiphenyl ether sulfonates, and fluoroalkyldiphenyl ether sulfonates, and wherein, when the oxidizing agent (A) contains potassium permanganate, the concentration of potassium permanganate in the oxidizing agent (A) is 0.001 to 0.1 mass%, and wherein the concentration of the fluorine compound (B) is 0.01 to 1 mass%.

Claims

[1] A liquid composition which removes titanium nitride from a substrate without corroding tungsten or a low-k interlayer dielectric also present on the substrate, the liquid composition having a pH of 0 to 4 and comprising: at least one oxidizing agent (A) selected from the group consisting of potassium permanganate, ammonium peroxodisulfate, potassium peroxodisulfate and sodium peroxodisulfate; a fluorine compound (B); and a tungsten corrosion inhibitor (C), wherein the tungsten corrosion inhibitor (C) contains at least one compound selected from a group of compounds (C1) consisting of alkylamines and salts thereof, fluoroalkylamines and salts thereof, alkylamine oxides, fluoroalkylamine oxides, alkylbetaines, fluoroalkylbetaines, quaternary alkylammonium and salts thereof, quaternary fluoroalkylammonium and salts thereof, quaternary alkylpyridinium salts, quaternary fluoroalkylpyridinium salts, quaternary alkylbipyridinium salts, quaternary fluoroalkylbipyridinium salts, quaternary alkylimidazolium salts and quaternary fluoroalkylimidazolium salts, and at least one compound selected from a group of compounds (C2) consisting of polyoxyalkylenealkylamines, polyoxyalkylenefluoroalkylamines, polyoxyalkylenealkyl ethers, polyoxyalkylenefluoroalkyl ethers, polyoxyalkylenealkylphosphates, Polyoxyalkylene fluoroalkyl phosphates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene fluoroalkyl ether sulfates,Alkyldiphenylethersulfonates and fluoroalkyldiphenylethersulfonates, and, wherein, when the oxidizing agent (A) contains potassium permanganate, the concentration of potassium permanganate in the oxidizing agent (A) is 0.001 to 0.1 mass%, and wherein the concentration of the fluorine compound (B) is 0.01 to 1 mass%. [2] A liquid composition according to claim 1, which does not contain hydrogen peroxide. [3] The liquid composition according to claim 1, wherein the fluorine compound (B) is at least one compound selected from the group consisting of hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, tetramethylammonium fluoride, potassium fluoride, hexafluorosilicic acid and tetrafluoroboric acid. [4] A liquid composition according to claim 1, wherein the alkylamines or fluoroalkylamines in the group of compounds (C1) are represented by the following general formula (1): where: R 1represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; and R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group may be substituted by a fluorine atom. [5] The liquid composition according to claim 1, wherein the alkylamine salts or fluoroalkylamine salts in the group of compounds (C1) are at least one compound selected from the group consisting of hydrochlorides, nitrates, acetates, methanesulfonates, chlorates, perchlorates, hydrofluorides, hydrobromates, hydroiodides, hydrogensulfates, sulfates, hydrogencarbonates, carbonates, dihydrogenphosphates, hydrogenphosphates and phosphates. [6] A liquid composition according to claim 1, wherein the alkylamine oxides or fluoroalkylamine oxides in the group of compounds (C1) are represented by the following general formula (2): wherein: R 1 represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; and R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group may be substituted by a fluorine atom. [7] A liquid composition according to claim 1, wherein the alkylbetaines or fluoroalkylbetaines in the group of compounds (C1) are represented by the following general formula (3) or (4):wherein: R 1represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; and R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group may be substituted by a fluorine atom;wherein: R 1 represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; and R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group may be substituted by a fluorine atom. [8] The liquid composition according to claim 1, wherein the quaternary alkylammonium and salts thereof or quaternary fluoroalkylammonium and salts thereof in the group of compounds (C1) are represented by the following general formula (5), (6) or (7): wherein: R 1 represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; and R 2 , R 3 and R 4 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a benzyl group, and some or all of the hydrogen atoms bonded to the alkyl group may be substituted by a fluorine atom;wherein: R 1represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; R 2 , R 3 and R 4 a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a benzyl group, and some or all of the hydrogen atoms bonded to the alkyl group may be substituted by a fluorine atom; and X represents a halogen atom: F, Cl, Br or I;wherein: R 1 represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; and R 2 , R 3 and R 4represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a benzyl group, and some or all of the hydrogen atoms bonded to the alkyl group may be substituted by a fluorine atom. [9] The liquid composition according to claim 1, wherein the quaternary alkylpyridinium salts or quaternary fluoroalkylpyridinium salts in the group of compounds (C1) are represented by the following general formula (8): wherein: R 1 represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; R 2 , R 3 , R 4 , R 5 and R 6represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and part or all of the hydrogen atoms bonded to the alkyl group may be substituted by a fluorine atom; and X represents a halogen atom: F, Cl, Br or I. [10] The liquid composition according to claim 1, wherein the quaternary alkylbipyridinium salts or quaternary fluoroalkylbipyridinium salts in the group of compounds (C1) are represented by the following general formula (9): wherein: R 1 and R 2 represent an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; R 3 to R 10represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and part or all of the hydrogen atoms bonded to the alkyl group may be substituted by a fluorine atom; and X represents a halogen atom: F, Cl, Br or I. [11] The liquid composition according to claim 1, wherein the quaternary alkylimidazolium salts or quaternary fluoroalkylimidazolium salts in the group of compounds (C1) are represented by the following general formula (10) or (11): wherein: R 1 represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; R 2 represents an alkyl group having 1 to 4 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group may be substituted by a fluorine atom; R 3 to R5 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group may be substituted by a fluorine atom; and X represents a halogen atom: F, Cl, Br or I;wherein: R 1 and R 2 represent an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; R 3 to R 5 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and part or all of the hydrogen atoms bonded to the alkyl group may be substituted by a fluorine atom; and X represents a halogen atom: F, Cl, Br or I. [12] A liquid composition according to claim 1, wherein the polyoxyalkylenealkylamines or polyoxyalkylenefluoroalkylamines in the group of compounds (C2) are represented by the following general formula (12):wherein: R 1 represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; R 2 and R 3 represent an alkanediyl group having 2 to 6 carbon atoms; and m and n represent an integer from 2 to 20, and m and n may be the same or different. [13] A liquid composition according to claim 1, wherein the polyoxyalkylene alkyl ethers or polyoxyalkylene fluoroalkyl ethers in the group of compounds (C2) are represented by the following general formula (13):wherein: R 1represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; R 2 represents an alkanediyl group having 2 to 6 carbon atoms; and n represents an integer from 2 to 20. [14] The liquid composition according to claim 1, wherein the polyoxyalkylene alkyl phosphates or polyoxyalkylene fluoroalkyl phosphates in the group of compounds (C2) are represented by the following general formula (14) or (15):wherein: R 1 represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; R 2represents an alkanediyl group having 2 to 6 carbon atoms; and n represents an integer from 2 to 20;wherein: R 1 and R 2 represent an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; R 3 and R 4 represent an alkanediyl group having 2 to 6 carbon atoms; and m and n represent an integer from 2 to 20, and m and n may be the same or different. [15] A liquid composition according to claim 1, wherein the polyoxyalkylene alkyl ether sulfates or polyoxyalkylene fluoroalkyl ether sulfates in the group of compounds (C2) are represented by the following general formula (16):wherein: R 1represents an alkyl group having 8 to 18 carbon atoms, an alkenyl group having 8 to 18 carbon atoms, a phenyl group or a benzyl group, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; R 2 represents an alkanediyl group having 2 to 6 carbon atoms; n represents a number from 2 to 20; and M represents sodium (Na), potassium (K) or ammonium (NH4). [16] A liquid composition according to claim 1, wherein the alkyldiphenyl ether sulfonates or fluoroalkyldiphenyl ether sulfonates in the group of compounds (C2) are represented by the following general formula (17):wherein: R 1represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and some or all of the hydrogen atoms bonded to the alkyl group or alkenyl group may be substituted by a fluorine atom; and M represents sodium (Na), potassium (K) or ammonium (NH4). [17] The liquid composition according to claim 1, wherein the concentration of ammonium peroxodisulfate, potassium peroxodisulfate or sodium peroxodisulfate in the oxidizing agent (A) is 0.1 to 20 mass%. [18] The liquid composition according to claim 1, wherein the concentration of the tungsten corrosion inhibitor (C) is 0.002 to 2 mass%. [19] The liquid composition according to claim 1, wherein the concentration of compound C1 is 0.001 to 1 mass% and the concentration of compound C2 is 0.001 to 1 mass%. [20] A method for cleaning a semiconductor device using the liquid composition according to any one of claims 1 to 19. [21] A method of manufacturing a semiconductor device in which titanium nitride is removed from a substrate without corroding tungsten or a low-k interlayer dielectric also present on the substrate, the method comprising bringing the substrate comprising titanium nitride, tungsten and the low-k interlayer dielectric into contact with the liquid composition of any one of claims 1 to 19.

Images