Composition for selectively removing oxide compounds and etching residues of Co and / or Cu

Abstract

Described are compositions for selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more of Co, Cu, W, Ru, and Mo, methods for using the compositions for selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more of Co, Cu, W, Ru, and Mo in a process for manufacturing a semiconductor device, and a method for manufacturing a semiconductor device comprising selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more of Co, Cu, W, Ru, and Mo.

Description

[Technical Field]

[0001] Described are a composition for selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more metals selected from the group consisting of Co, Cu, W, Ru, and Mo; a method for using the composition for selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more metals selected from the group consisting of Co, Cu, W, Ru, and Mo in a process for manufacturing a semiconductor device; and a method for manufacturing a semiconductor device, comprising selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more metals selected from the group consisting of Co, Cu, W, Ru, and Mo. [Background technology]

[0002] In semiconductor manufacturing, the International Technology Roadmap for Semiconductors defines the 7nm process as the MOSFET technology node following the 10nm node. It is based on FinFET (Fin Field Effect Transistor) technology, a type of multi-gate MOSFET technology. 7nm and sub-7nm IC process technologies are expected to not only significantly reduce power consumption, but also achieve significant improvements in switching performance and higher density.

[0003] In sub-7 nm IC process technology, new materials such as cobalt (Co) and tungsten (W) have been introduced to improve the performance of integrated circuits. However, these materials are susceptible to oxidation, which is difficult to control in wet cleaning processes. Therefore, when aqueous cleaning compositions are applied to remove oxide compounds and etching residues resulting from etching of one or both of Co and Cu, especially dry etching, in wet cleaning processes, undesirable recess formation and pit corrosion are usually observed in interconnects containing cobalt. Furthermore, wiring materials such as tungsten are damaged during exposure to cleaning solutions, which severely impacts the yield and quality of the IC manufacturing process.

[0004] US 2020 / 0339523 A1 discloses a composition for selectively etching a layer containing an aluminum compound in the presence of a layer of a low-k material and / or a layer containing copper and / or cobalt, the composition comprising one or more etchants containing fluoride anions; preferably ammonium fluoride.

[0005] US 2015 / 0159124 A1 discloses a cleaning composition for cleaning semiconductor substrates that have been subjected to plasma etching, said composition comprising: 1) at least one redox agent 2) at least one first chelating agent which is a polyaminopolycarboxylic acid; 3) at least one second chelating agent, different from the first chelating agent and containing at least two nitrogen-containing groups; 4) at least one metal corrosion inhibitor which is a substituted or unsubstituted benzotriazole; 5) at least one organic solvent selected from the group consisting of water-soluble alcohols, water-soluble ketones, water-soluble esters, and water-soluble ethers; 6) water; and 7) At least one pH adjuster, optionally a metal ion-free base wherein the pH of the composition is preferably from 6 to about 11.

[0006] US 2015 / 0159124 A1 does not indicate that the proposed cleaning composition is suitable for selectively removing oxide compounds and etching residues of one or both of Co and Cu, especially in the presence of one or more metals selected from the group consisting of Co, Cu, W, Ru, and Mo.

[0007] US 2017 / 0200601 A1 discloses an aqueous cleaning composition comprising at least one nonionic surfactant corrosion inhibitor, at least one etchant source, at least one passivating agent, water, optionally at least one organic solvent, optionally at least one buffering species, optionally at least one additional corrosion inhibitor, and optionally at least one oxidizing agent, wherein the aqueous cleaning composition is suitable for cleaning post-plasma etching residue from microelectronic devices having the residue thereon. Preferably, the at least one etchant comprises a fluoride species selected from the group consisting of hydrofluoric acid, fluoroboric acid, tetramethylammonium hexafluorophosphate, ammonium fluoride, ammonium difluoride, tetrabutylammonium tetrafluoroborate, tetranetylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetranetylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, and combinations thereof.

[0008] WO 2015 / 060954 A1 1) at least one chelating agent which is a polyaminopolycarboxylic acid; 2) at least one organic solvent selected from the group consisting of water-soluble alcohols, water-soluble ketones, water-soluble esters, and water-soluble ethers; 3) at least one monocarboxylic acid containing a primary or secondary amino group and at least one additional basic group containing nitrogen; 4) at least one metal corrosion inhibitor which is a substituted or unsubstituted benzotriazole; and 5)Water The present invention discloses a cleaning composition comprising:

[0009] EP 3 664 125 A1 discloses a liquid composition containing 0.01 to 30% by weight of tetrafluoroboric acid, or boric acid and hydrogen fluoride in a (boric acid) / (hydrogen fluoride) ratio of (0.0001 to 5.0% by weight) / (0.005 to 5.0% by weight), and having a pH value of 0.0 to 4.0.

[0010] US 2015 / 290765 A1 has a pH of 8 or higher and contains the following components (A) to (F): (A) Tetramethylammonium hydroxide (B) a diamine selected from the group consisting of ethylenediamine and 1,2-diaminopropane (C) an organic acid selected from the group consisting of oxalic acid, citric acid, tartaric acid, malic acid, and picolinic acid (D) histidine or its derivatives (E) at least one selected from the group consisting of benzotriazole, imidazole, triazole, tetrazole, and derivatives thereof; (F)Water The present invention discloses a rinse solution containing: [Prior art documents] [Patent documents]

[0011] [Patent Document 1] US 2020 / 0339523 A1 [Patent Document 2] US 2015 / 0159124 A1 [Patent Document 3] US 2017 / 0200601 A1 [Patent Document 4] WO 2015 / 060954 A1 [Patent Document 5] EP 3 664 125 A1 [Patent Document 6] US 2015 / 290765 A1 Summary of the Invention [Problem to be solved by the invention]

[0012] There is a continuing need for cleaning compositions that can selectively remove oxide compounds and etching residues of one or both of Co and Cu, said cleaning compositions having good compatibility with interconnect materials selected from the group consisting of the metals Co, Cu, W, Ru, and Mo. [Means for solving the problem]

[0013] These and other objects are achieved by the composition disclosed herein for selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more metals selected from the group consisting of Co, Cu, W, Ru, and Mo, comprising: (A) one or more compounds selected from the group consisting of benzotriazoles; (B) one or more compounds that do not have a triazole structure, and are selected from the group consisting of compounds having one or more primary amine groups and secondary amine groups, provided that if the compound has only one primary amine group, then the compound has at least three carbon atoms; (C) one or more compounds selected from the group consisting of carboxylic acids and chelating agents; (D) one or more water-miscible organic solvents (E)Water Including, wherein the total concentration of the compounds containing fluorine-containing anions is 0.0008% by mass or less based on the total mass of the composition; The composition has a pH value of less than 6. DETAILED DESCRIPTION OF THE INVENTION

[0014] More specifically, the composition comprises (A) one or more compounds selected from the group consisting of benzotriazoles (B) one or more compounds that do not have a triazole structure and are selected from the group consisting of compounds having one or more primary amine groups and secondary amine groups, provided that if the compound has only one primary amine group, it has at least three carbon atoms, and if the compound has one or more carboxyl groups and one or more amino groups, it also contains sulfur. (C) one or more compounds selected from the group consisting of carboxylic acids and chelating agents (D) one or more water-miscible organic solvents (E)Water Includes.

[0015] Component (A) of the composition acts as a corrosion inhibitor and comprises one or more compounds selected from the group consisting of benzotriazoles, including 1H-benzotriazole (unsubstituted benzotriazole) and substituted benzotriazoles.

[0016] Component (B) of the composition acts as a corrosion inhibitor and comprises one or more compounds that do not have a triazole structure, and the one or more compounds of component (B) are selected from the group consisting of compounds having one or more primary amine groups and secondary amine groups, provided that the compound has at least three carbon atoms if it has only one primary amine group, and also contains sulfur if it has one or more carboxyl groups and one or more amino groups.

[0017] It has surprisingly been found that a combination of one or more first corrosion inhibitors selected from the group consisting of benzotriazoles (component (A) defined above) and one or more second corrosion inhibitors selected from the group consisting of compounds having one or more primary amine groups and one or more secondary amine groups (having at least three carbon atoms if the compound has only one primary amino group, and sulfur if the compound has one or more carboxyl groups and one or more amino groups (component (B) defined above)) can simultaneously protect a wide variety of interconnect materials selected from the group consisting of metals consisting of Co, Cu, W, Ru, and Mo from damage during the process of removing oxide compounds and etching residues of one or both of Co and Cu.

[0018] Component (C) of the composition comprises one or more compounds that function as an etchant to remove oxide compounds of one or both Co and Cu and etching residues. The component (C) compounds are selected from the group consisting of carboxylic acids and chelating agents. The component (C) compounds do not have a triazole structure and are not polyaminocarboxylic acids. One or more of the component (C) compounds may be selected from compounds having a primary amino group that do not fall within the definition of component (B). Polyaminocarboxylic acids such as those disclosed in US 2015 / 0159124 A1 are not used as component (C). Preferably, component (C) comprises a carboxylic acid that does not have an amino group, more preferably a carboxylic acid that does not have a nitrogen-containing group.

[0019] Component (D) of the composition comprises one or more organic solvents that are miscible with water at least in a 1:1 weight ratio at 20° C. and atmospheric pressure.

[0020] In certain embodiments, the composition consists of components (A), (B), (C), (D) and (E) as defined above.

[0021] The composition defined above is a homogeneous (i.e., single-phase) liquid under standard conditions (298 K and 101.325 kPa), where components (A), (B), and (C) are dissolved in the liquid. The composition described herein does not contain a solid abrasive and is therefore not a chemical-mechanical polishing composition. Unlike the compositions disclosed herein, chemical-mechanical polishing compositions are not single-phase liquids.

[0022] Surprisingly, it has been found that a composition comprising or consisting of components (A), (B), (C), (D) and (E) as defined above fulfils the objectives defined above.

[0023] Preferably, in the compositions described herein, the concentration of hydroxylamine is 0.1% by weight or less, preferably 0.05% by weight or less, and most preferably 0.01% by weight or less, in each case based on the total weight of the composition. Most preferably, the concentration of hydroxylamine is so low that it cannot be analytically detected in the composition.

[0024] More preferably, the compositions described herein do not contain compounds that can act as redox agents, i.e., compounds that can induce oxidation and reduction in semiconductor cleaning processes.

[0025] Preferably, in the composition as defined above, butylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,6-hexamethylenediamine-N,N,N' The total concentration of polyaminopolycarboxylic acids selected from the group consisting of 1,4,7,10-tetraazacyclododecanetetraacetic acid, N,N-bis-(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid, diaminopropanetetraacetic acid, 1,4,7,10-tetraazacyclododecanetetraacetic acid, diaminopropanoltetraacetic acid, and (hydroxyethyl)ethylenediaminetriacetic acid is, in each case, 0.008% by weight or less, more preferably 0.005% by weight or less, and most preferably 0.001% by weight or less, based on the total weight of the composition. Most preferably, the concentration of said polyaminopolycarboxylic acids is so low that it cannot be analytically detected in the composition. Even more preferably, in the composition defined above, the total concentration of polyaminopolycarboxylic acids (excluding cysteine) is, in each case, 0.008% by weight or less, more preferably 0.005% by weight or less, and most preferably 0.001% by weight or less, based on the total weight of the composition. Most preferably, the total concentration of polyaminopolycarboxylic acids is so low that it cannot be analytically detected in the composition.

[0026] Preferably, in the composition defined above, the total concentration of compounds containing fluorine-containing anions is 0.0008% by weight or less, preferably 0.0005% by weight or less, more preferably 0.0001% by weight or less, based on the total weight of the composition in each case.More preferably, the composition described herein does not contain fluorine-containing anions.Most preferably, the concentration of fluorine-containing components is so low that elemental fluorine cannot be analytically detected in the composition.

[0027] In the compositions described herein, preferably, the total amount of component (A) ranges from 0.5% to 5%, based on the combined mass of components (A), (B), (C), (D), and (E).

[0028] In the compositions described herein, preferably, the total amount of component (B) ranges from 500 ppm to 2000 ppm, based on the combined mass of components (A), (B), (C), (D), and (E).

[0029] In the compositions described herein, preferably, the total amount of component (C) ranges from 0.01% to 0.1%, based on the combined mass of components (A), (B), (C), (D), and (E).

[0030] In the compositions described herein, preferably, the total amount of component (D) ranges from 5% to 20%, based on the combined mass of components (A), (B), (C), (D), and (E).

[0031] Most preferably, in the composition as defined above, in each case based on the sum of the masses of components (A), (B), (C), (D) and (E), The total amount of component (A) is in the range of 0.5% to 5%; The total amount of component (B) is in the range of 500 ppm to 2000 ppm, The total amount of component (C) is in the range of 0.01% to 0.1%; The total amount of component (D) is in the range of 5% to 20%.

[0032] In the above-defined composition consisting of components (A), (B), (C), (D) and (E), the concentrations of components (A), (B), (C) and (D) may be in the ranges defined above, with water (E) making up the remainder.

[0033] Preferably, one or more compounds of component (A) that act as corrosion inhibitors are (i) unsubstituted benzotriazoles, and (ii) C1~4 Alkyl, Amino-C 1~4 Benzotriazole substituted with one or two substituents independently selected from the group consisting of alkyl, phenyl, halogen, hydroxy, nitro, and thiol. is selected from the group consisting of:

[0034] Preferably, all of the compounds of component (A) are selected from the group above.

[0035] More preferably, the one or more compounds of component (A) that function as corrosion inhibitors are selected from the group consisting of 1H-benzotriazole (i.e., unsubstituted benzotriazole), 6-methyl-benzotriazole, 5-methyl-benzotriazole, 5,6-dimethyl-1H-benzotriazole, 1-hydroxybenzotriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 2-(5-amino-pentyl)-benzotriazole, 5-nitro-1-phenyl-1H-benzotriazole, and 5-halobenzotriazoles (such as 5-chlorobenzotriazole).

[0036] Preferably, all of the compounds of component (A) are selected from the preferred group above.

[0037] Preferably, one or more compounds of component (B) that function as corrosion inhibitors are - 2-amino acids with 3 or more carbon atoms, such as histidine, sulfur-containing amino acids, such as cysteine, - di- and tripeptides of 2-amino acids, such as glutathione; disulfides of sulfur-containing 2-amino acids, such as cystine, and biguanides of formula (I) [ka] (In the formula, R 1 is H, C 1~6 -alkyl, phenyl, halophenyl (e.g., chlorophenyl) and C 1~3-alkylphenyl, R 2 is H, C 1~6 -Alkyl, phenyl, halophenyl (e.g., chlorophenyl), C 1~3 - selected from the group consisting of alkylphenyl and biguanidine groups (I'), [ka] [In the formula, R 1 is H, C 1~6 -alkyl, phenyl, halophenyl (e.g., chlorophenyl) and C 1~3 -alkylphenyl, and R 3 is C1-C8 alkylene]).

[0038] In a particular embodiment, the biguanide as defined above is preferably a biguanide of formula (II) [ka] (Wherein, each R 1 are independently H, C 1~6 -alkyl, phenyl, halophenyl (preferably chlorophenyl) and C 1~3 -alkylphenyl). Preferably, both R of the biguanide of formula (II) are selected from the group consisting of: 1 is the same.

[0039] A preferred example of a biguanide of formula (II) is chlorhexidine (ie, 1,1'-hexamethylenebis[5-(4-chlorophenyl)biguanide]).

[0040] Preferably, all of the compounds of component (B) are selected from the group above.

[0041] Particularly preferably, the one or more compounds of component (B) that function as corrosion inhibitors are selected from the group consisting of biguanides of formula (II) (e.g., chlorhexidine (i.e., 1,1'-hexamethylenebis[5-(4-chlorophenyl)biguanide]), histidine, glutathione, cysteine, and cystine). Chlorhexidine (i.e., 1,1'-hexamethylenebis[5-(4-chlorophenyl)biguanide]) is most preferred.

[0042] Preferably, all of the compounds of component (B) are selected from the preferred group above.

[0043] Preferably, the one or more compounds of component (C) that function as an etchant are selected from the group consisting of citric acid, oxalic acid, glycolic acid, lactic acid, ethylenediaminetetra(methylenephosphonic acid) (EDTMP), succinic acid, malonic acid, nitrilotriacetic acid, methylsulfonic acid, lactic acid, propionic acid, formic acid, acetic acid, sulfosalicylic acid, salicylic acid, ascorbic acid, and glycine.

[0044] Preferably, all of the compounds of component (C) are selected from the group above.

[0045] Preferably, component (C) comprises a carboxylic acid that does not have an amino group, and more preferably a carboxylic acid that does not have a nitrogen-containing group. Thus, diaminetetra(methylenephosphonic acid) (EDTMP), glycine, and nitrilotriacetic acid are less preferred in certain cases.

[0046] The one or more organic water-miscible solvents of component (D) are preferably selected from the group consisting of ethanol, isopropanol, n-propanol, 1,4-butanediol, diethylene glycol butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 4-methylmorpholine-4-oxide, trimethylamine-N-oxide, triethylamine-N-oxide, triethanolamine-N-oxide, pyridine-N-oxide, N-formylmorpholine, N-ethylmorpholine-N-oxide, N-ethylpyrrolidine-N-oxide, dimethyl sulfoxide, dipropyl sulfoxide, diethyl sulfoxide, methyl ethyl sulfoxide, diphenyl sulfoxide, methyl phenyl sulfoxide, 1,1′-dihydroxyphenyl sulfoxide.

[0047] Preferably, all solvents in component (D) are selected from the group above.

[0048] In a preferred composition, - one, several or all compounds of component (A) are selected from the preferred group disclosed above, and - one, several or all compounds of component (B) are selected from the preferred group disclosed above, and - one, several or all compounds of component (C) are selected from the preferred group disclosed above, and One, more or all of the solvents of component (D) are selected from the preferred group disclosed above.

[0049] Preferably, the compositions described herein have a pH value measured by a pH meter at 25°C and 101.325 kPa of less than 6, preferably in the range of 2 to 5.5, more preferably in the range of 2 to 5, even more preferably 2.5 to 4.5, most preferably 2.5 to 4, and especially preferably 2.8 to 3.7.

[0050] According to the Pourbaix diagram, tungsten is more effectively inhibited from corrosion at the acidic pH in the preferred ranges described above compared to the higher pH range of the composition according to US 2015 / 0159124 A1.

[0051] Particularly preferred are those in which the total weight of components (A), (B), (C), (D) and (E) is: (A) one or both of 1H-benzatriaZole and 5-methyl-1H-benzotriazole (Where the total amount of 1H-benzatriaZole and 5-methyl-1H-benzotriazole is in the range of 0.5% to 5%); (B) one or both of histidine and chlorhexidine (wherein the total amount of histidine and chlorhexidine is in the range of 500 ppm to 2000 ppm); (C) one or both of lactic acid and glycolic acid (wherein the total amount of lactic acid and glycolic acid is in the range of 0.01% to 0.1%); (D) one or both of N-formyl-morpholine and dimethyl sulfoxide, wherein the total amount of N-formyl-morpholine and dimethyl sulfoxide is in the range of 5% to 20%; (E)Water A composition comprising or consisting of:

[0052] Preferably, the composition has a pH in the range of 2 to 5, more preferably 2.5 to 4.5, most preferably 2.5 to 4, and especially preferably 2.8 to 3.7, as measured with a pH meter at 25° C. and 101.325 kPa.

[0053] According to a further aspect, the present disclosure relates to a method of using a composition as defined above for selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more metals selected from the group consisting of Co, Cu, W, Ru and Mo in a process for the manufacture of a semiconductor device. Preferably, the semiconductor device is manufactured by the sub-7 nm IC process technology described above. Preferably, the semiconductor device is an integrated circuit (IC) or consists of an integrated circuit (IC).

[0054] With regard to specific preferred compositions for the above-described methods of use, reference is made to the disclosure provided above in the context of describing compositions for selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more metals selected from the group consisting of Co, Cu, W, Ru, and Mo.

[0055] In the above-mentioned method of use, the oxide compound may contain an oxide of one or both of Co and Cu.

[0056] In the above-described method of use, the etching residue may include fluorides of one or both of Co and Cu. Such etching residues are typically formed in dry etching processes.

[0057] In the above-described use, the semiconductor device may include one or more interconnects that include one or both of Co and Cu.

[0058] In the above use, the semiconductor device may include one or more interconnects that include one or more of W, Ru, and Mo.

[0059] In the above-described method of use, the semiconductor device may comprise one or more dielectric materials selected from the group consisting of polycrystalline Si, SiO2 and Si3N4.

[0060] More specifically, in the above-mentioned method of use, the semiconductor device comprises: - one or more first wirings comprising one or both of Co and Cu; - one or more second wirings comprising one or more of W, Ru, and Mo; and - one or more dielectric materials selected from the group consisting of polycrystalline Si, SiO2 and Si3N4 may include:

[0061] According to a further aspect, the present disclosure relates to a method for manufacturing a semiconductor device, comprising selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more metals selected from the group consisting of Co, Cu, W, Ru and Mo, by applying the composition defined above. Preferably, the semiconductor device is or comprises an integrated circuit (IC).

[0062] For specific preferred compositions for the above methods, reference is made to the disclosure provided above in the context of the description of the compositions.

[0063] Preferably, the semiconductor device is fabricated by the sub-7 nm IC process technology described above.

[0064] Typically, in the method, the composition is applied to clean the surface of a semiconductor device or its precursor after a dry etching step. Thus, the method for manufacturing a semiconductor device described herein comprises the following steps: - dry etching a surface of a semiconductor device or a precursor thereof; - selectively removing oxidized compounds and etching residues of one or both of Co and Cu by applying a composition as defined above to a surface that has been subjected to dry etching in the presence of one or more metals selected from the group consisting of Co, Cu, W, Ru and Mo. may include:

[0065] In the above method, applying the composition as defined above to the surface area of ​​the semiconductor device to be cleaned may be carried out by any suitable means and in any suitable manner. For example, the composition may be applied by immersion (immersing the surface area of ​​the semiconductor device to be cleaned in the composition), rinsing, or spraying. Usually, the cleaning step is followed by drying.

[0066] In the above method, the oxide compound may include an oxide of one or both of Cu and Co.

[0067] In the above method, the etching residue may include fluorides of one or both of Cu and Co. Such etching residues are typically formed in dry etching processes.

[0068] In the above method, the semiconductor device may include one or more interconnects that include one or both of Cu and Co.

[0069] In the above method, the semiconductor device may include one or more interconnects comprising one or more of W, Ru, and Mo.

[0070] In the above method, the semiconductor device may include one or more dielectric materials selected from the group consisting of polycrystalline Si, SiO2, and Si3N4.

[0071] More specifically, in the above method, the semiconductor device comprises: - one or more first wirings comprising one or both of Co and Cu; - one or more second wirings comprising one or more of W, Ru, and Mo; and - one or more dielectric materials selected from the group consisting of polycrystalline Si, SiO2 and Si3N4 may include:

[0072] A particularly preferred method according to the present disclosure comprises the steps of: (A) one or both of 1H-benzatriaZole and 5-methyl-1H-benzotriazole (Where the total amount of 1H-benzatriaZole and 5-methyl-1H-benzotriazole is in the range of 0.5% to 5%); (B) one or both of histidine and chlorhexidine (wherein the total amount of histidine and chlorhexidine is in the range of 500 ppm to 2000 ppm); (C) one or both of lactic acid and glycolic acid (wherein the total amount of lactic acid and glycolic acid is in the range of 0.01% to 0.1%); (D) one or both of N-formyl-morpholine and dimethyl sulfoxide, wherein the total amount of N-formyl-morpholine and dimethyl sulfoxide is in the range of 5% to 20%; (E)Water The method includes selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more metals selected from the group consisting of Co, Cu, W, Ru, and Mo by applying a composition comprising or consisting of:

[0073] Preferably, the composition has a pH in the range of 2 to 5, more preferably 2.5 to 4.5, most preferably 2.5 to 4, and especially preferably 2.8 to 3.7, as measured with a pH meter at 25° C. and 101.325 kPa.

[0074] According to a further aspect, the present disclosure relates to the use of a biguanidine according to formula (I) as defined above, preferably a biguanidine according to formula (II) as defined above, as a corrosion inhibitor for inhibiting the corrosion of tungsten. Preferably, the biguanidine is chlorhexidine (i.e., 1,1'-hexamethylenebis[5-(4-chlorophenyl)biguanide]). Surprisingly, it has been found that such biguanidines as chlorhexidine, which have been used mainly for pharmaceutical purposes until now, are effective corrosion inhibitors for tungsten. Preferably, the biguanidine according to formula (I) as defined above is used in the composition as defined above and / or the method for manufacturing the semiconductor device as defined above. [Example]

[0075] The following examples are intended to further illustrate the invention without limiting its scope.

[0076] In each case, the films were deposited on a Si substrate. (i) a film made of a metal selected from the group consisting of Co, Cu, W, Mo, Ti and Ru, or (ii) Cobalt (Co) coated with its oxide (CoOx), its oxide (CuO X a film made of copper (Cu) coated with (iii) Nonmetallic films consisting of TEOS or TiN or to a sample having (iv) On a bare Si substrate The compositions defined above and comparative compositions (see the table below for details) were applied.

[0077] The composition was brought to a temperature of 40° C. and applied to the sample by spin washing.

[0078] In cases (i) and (ii), the etching rate was determined by measuring the thickness change as a function of etching time using XRF (X-ray fluorescence) analysis. In case (ii), the thickness decrease is steep while the oxide is being etched, then abruptly levels off once the oxide is removed and the metal surface is exposed.

[0079] In cases (iii) and (iv), the etching rate was determined by measuring the change in thickness as a function of etching time by ellipsometry.

[0080] Etch rates are given in Angstroms / minute (A / min).

[0081] In Tables 1-4, concentrations of all components are given in mass % except for those components where the concentration is explicitly stated as ppm.

[0082] 1. Screening of suitable corrosion inhibitors for Co The purpose of this series of tests was to identify an effective corrosion inhibitor for Co. The compositions shown in Table 1 (not in accordance with the present invention) were applied to a Co film deposited on a Si substrate. The etching rate was determined as described above (case (i)). In these compositions, the etchant (C) was oxalic acid, and the solvent (D) was either N-formylmorpholine (NFM) or dimethyl sulfoxide (DMSO). Each of Compositions #1-2 through #1-10 contains a heterocyclic compound with one or more N atoms in the heterocyclic ring, which is tested for its efficiency in inhibiting Co corrosion. Comparative Composition #1-1 does not contain a heterocyclic compound with one or more N atoms in the heterocyclic ring. Comparative Composition #1-1 is a cleaning composition commonly used for removing CoOx.

[0083] The lower the etching rate of Co, the more efficient the corrosion inhibitor. Table 1 shows that compounds selected from the group consisting of benzotriazoles are superior corrosion inhibitors for Co compared to other heterocyclic compounds containing one or more N atoms in the heterocyclic ring (imidazoles and thiazoles). Therefore, benzotriazole, 5-methyl-1h-benzotriazole, and 5-chlorobenzotriazole are suitable candidates for component (A) of the above composition.

[0084] [Table 1]

[0085] 2. Screening of suitable etchants for CoOx This series of tests aimed to identify an efficient etchant for CoOx that has higher selectivity for etching CoOx than for etching metallic Co. The compositions shown in Table 2 (not in accordance with the present invention) were applied to a film of Co deposited on a Si substrate, where the Co film was covered by CoOx. The etch rate was determined as described above (case (ii)). In these compositions, one or both of benzotriazole and 5-methyl-1H-benzotriazole acted as corrosion inhibitors (A), and the solvent (D) was N-formyl-morpholine (NFM). Compositions #2-2 through #2-11 each contained a compound to be tested for its efficiency in selectively etching CoOx, which may be formed by dry etching of Co. Comparative composition #2-1 did not contain a compound capable of acting as an etchant.

[0086] [Table 2]

[0087] Table 2 shows that glycolic acid and lactic acid have higher selectivity for etching CoOx than for etching metallic Co (compositions #2.6, 2.7, and 2.8). Therefore, glycolic acid and lactic acid are suitable candidates for component (C) in the above compositions. In contrast, fluorine-containing etchants used in the prior art (see US 2020 / 0339523A1) have lower selectivity for etching CoOx than for etching metallic Co.

[0088] 3.Screening of corrosion inhibitors suitable for W The purpose of this series of tests was to identify effective corrosion inhibitors for tungsten (W). The compositions shown in Table 3a were applied to different films deposited on Si substrates or on the bare surface of Si substrates (see Table 3b for details), and the etching rates were determined as described above (cases (i), (ii), (iii), and (iv)). In these compositions, the etchant (C) was glycolic acid, and the solvent (D) was N-formylmorpholine (NFM). Compositions #3-2 to #3-11 each contained one or more compounds to be tested for their corrosion inhibition effect on W. Comparative composition #3-1 contained no corrosion inhibitors other than benzotriazole.

[0089] Table 3b shows that chlorhexidine, histidine, glutathione, cystine, and cysteine ​​(compositions #3.2 to #3.7, and #3.9 to #3.11) are superior corrosion inhibitors for W compared to hexadecyltrimethylammonium hydroxide (composition #3.8, not according to the invention).

[0090] Therefore, chlorhexidine, histidine, glutathione, cystine and cysteine ​​are suitable candidates for component (B) of the composition defined above.

[0091] For comparison, the composition FE1 disclosed in US 2015 / 0159124 A1 was also tested (see Table 4). Surprisingly, the tungsten etching rate is significantly higher, probably due to the basic pH > 6. Furthermore, the etching selectivity of CuOx relative to metallic Cu is significantly lower than that of the composition according to the invention.

[0092] [Table 3]

[0093] TIFF2025542507000007.tif24987

[0094] [Table 4]

Claims

1. 1. A composition for selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more metals selected from the group consisting of Co, Cu, W, Ru, and Mo, comprising: (A) one or more compounds selected from the group consisting of benzotriazoles; (B) one or more compounds that do not have a triazole structure, and are selected from the group consisting of compounds having one or more primary amine groups and secondary amine groups, with the proviso that if the compound has only one primary amine group, then the compound has at least three carbon atoms; (C) one or more compounds selected from the group consisting of carboxylic acids and chelating agents; (D) one or more water-miscible organic solvents (E) Water Including, the total concentration of compounds containing fluorine-containing anions is 0.0008% by weight or less, based on the total weight of the composition; The composition has a pH value of less than 6.

2. 10. The composition of claim 1, wherein the total concentration of compounds comprising fluorine-containing anions is 0.0005% by weight or less, more preferably 0.0001% by weight or less, based on the total weight of the composition.

3. 3. The composition according to claim 1 or 2, having a pH value in the range of from 2 to 5.5, more preferably in the range of from 2.5 to 4.

4. in each case based on the sum of the masses of components (A), (B), (C), (D) and (E), the total amount of component (A) is in the range of 0.5% to 5%, and / or the total amount of component (B) is in the range of 500 ppm to 2000 ppm; and / or the total amount of component (C) is in the range of 0.01% to 0.1%, and / or The composition of any one of claims 1 to 3, wherein the total amount of component (D) ranges from 5% to 20%.

5. One or more compounds of component (A) are unsubstituted benzotriazole and C １～４ Alkyl, amino-C １～４ benzotriazoles substituted with one or two substituents independently selected from the group consisting of alkyl, phenyl, halogen, hydroxy, nitro, and thiol; 5. The composition of any one of claims 1 to 4, wherein the one or more compounds of component (A) are selected from the group consisting of 1H-benzotriazole, 6-methyl-benzotriazole, 5-methyl-benzotriazole, 5,6-dimethyl-1H-benzotriazole, 1-hydroxybenzotriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 2-(5-amino-pentyl)-benzotriazole, 5-nitro-1-phenyl-1H-benzotriazole, and 5-halobenzotriazoles.

6. One or more compounds of component (B) - 2-amino acids with 3 or more carbon atoms, - di- and tripeptides of 2-amino acids, disulfides of sulfur-containing 2-amino acids, and biguanides of formula (I) 【Chemistry 1】 (In the formula, R １ is H, C １～６ - alkyl, phenyl, chlorophenyl and C １～３ - alkylphenyl, R ２ is H, C １～６ - alkyl, phenyl, halophenyl, C １～３ - selected from the group consisting of alkylphenyl and biguanidine radicals (I'), 【Chemistry 2】 [In the formula, R １ is H, C １～６ - alkyl, phenyl, halophenyl and C １～３ - alkylphenyl, and R ３ is C １ ~C ８ alkylene] is selected from the group consisting of The biguanide is preferably a biguanide of formula (II) 【Transformation 3】 (Wherein, each R １ are independently H, C １～６ - alkyl, phenyl, halophenyl and C １～３ -alkylphenyl) 6. The composition of claim 1, wherein the one or more compounds of component (B) are selected from the group consisting of chlorhexidine, histidine, glutathione, cysteine, and cystine.

7. 7. The composition of any one of claims 1 to 6, wherein the one or more compounds of component (C) are selected from the group consisting of citric acid, oxalic acid, glycolic acid, lactic acid, ethylenediaminetetra(methylenephosphonic acid) (EDTMP), succinic acid, malonic acid, nitrilotriacetic acid, methylsulfonic acid, lactic acid, propionic acid, formic acid, acetic acid, sulfosalicylic acid, salicylic acid, ascorbic acid, and glycine.

8. 8. The composition of any one of claims 1 to 7, wherein the one or more organic solvents (D) are selected from the group consisting of ethanol, isopropanol, n-propanol, 1,4-butanediol, diethylene glycol butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 4-methylmorpholine-4-oxide, trimethylamine-N-oxide, triethylamine-N-oxide, triethanolamine-N-oxide, pyridine-N-oxide, N-formylmorpholine, N-ethylmorpholine-N-oxide, N-ethylpyrrolidine-N-oxide, dimethyl sulfoxide, dipropyl sulfoxide, diethyl sulfoxide, methyl ethyl sulfoxide, diphenyl sulfoxide, methyl phenyl sulfoxide, and 1,1'-dihydroxyphenyl sulfoxide.

9. in each case based on the sum of the masses of components (A), (B), (C), (D) and (E), (A) one or both of 1H-benzatriaZole and 5-methyl-1H-benzotriazole, Wherein the total amount of 1H-benzatriaZole and 5-methyl-1H-benzotriazole is in the range of 0.5% to 5%; (B) one or both of histidine and chlorhexidine, wherein the total amount of histidine and chlorhexidine is in the range of 500 ppm to 2000 ppm; (C) one or both of lactic acid and glycolic acid, wherein the total amount of lactic acid and glycolic acid is in the range of 0.01% to 0.1%; (D) one or both of N-formyl-morpholine and dimethyl sulfoxide, wherein the total amount of N-formyl-morpholine and dimethyl sulfoxide is in the range of 5% to 20%; (E) Water 9. The composition of claim 1, comprising:

10. 10. Use of the composition according to any one of claims 1 to 9 for selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more metals selected from the group consisting of Co, Cu, W, Ru and Mo in a process for the manufacture of semiconductor devices, preferably wherein the semiconductor devices are manufactured by sub-7 nm IC process technology.

11. 10. A method for manufacturing a semiconductor device, comprising the step of selectively removing oxide compounds and etching residues of one or both of Co and Cu in the presence of one or more metals selected from the group consisting of Co, Cu, W, Ru, and Mo, by applying the composition of any one of claims 1 to 9.

12. The method of claim 11 , wherein the semiconductor device is fabricated by sub-7 nm IC process technology.

13. the oxide compound comprises an oxide of one or both of Cu and Co, and / or 13. The method of claim 11 or 12, wherein the etching residue comprises fluorides of one or both of Cu and Co.

14. the semiconductor device is one or more interconnects comprising one or both of Co and Cu; and / or one or more wires comprising one or more of W, Ru, and Mo; and / or Polycrystalline Si, SiO ２ and Si ３ N ４ one or more materials selected from the group consisting of 14. The method of any one of claims 11 to 13, comprising:

15. Use of a biguanidine according to formula (I) as defined in claim 6, preferably a biguanidine according to formula (II) as defined in claim 6, as a corrosion inhibitor for inhibiting the corrosion of tungsten, in particular in a composition as defined in any one of claims 1 to 9 and / or in a method as defined in any one of claims 11 to 14.

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