Composition and process for selectively etching a layer comprising an aluminium compound in the presence of layers of low-k materials, copper and/or cobalt

Patent metadata

Field	Value
Publication number	US-12331239-B2
Application number	US-202318519571-A
Country	US
Kind code	B2
Filing date	Nov 27, 2023
Priority date	Dec 8, 2017
Publication date	Jun 17, 2025
Grant date	Jun 17, 2025

Abstract

A composition for selectively etching a layer including an aluminum compound in the presence of a layer of a low-k material and/or a layer including copper and/or cobalt, and a corresponding process, are described. Further described is a process for the manufacture of a semiconductor device, including the step of selectively etching at least one layer including an aluminum compound in the presence of a layer of a low-k material and/or a layer including copper and/or cobalt by contacting the at least one layer including an aluminum compound with the described composition.

First claim

What is claimed is:

1. A method comprising:
contacting a composition with a substrate,
wherein the composition comprises:
(A) at least one solubilizer, selected from the group consisting of
a compound of formula I:

wherein R 1 is at least one selected from the group consisting of hydrogen and —C(O)—R 2 wherein R 2 is selected from the group consisting of hydrogen and alkyl having 1, 2, 3 or 4 carbon atoms;
a compound of formula II:

wherein R 3 is alkyl having 1, 2, 3 or 4 carbon atoms;
trimethylamine-N-oxide,
triethylamine-N-oxide,
triethanolamine-N-oxide,
pyridine-N-oxide,
N-ethylpyrrolidine-N-oxide, and
mixtures thereof;

(B) an etchant comprising fluoride anions;
(C) at least one corrosion inhibitor, selected from the group consisting of benzotriazole which is unsubstituted or substituted once or twice independently by C 1-4 -alkyl, amino-C 1-4 -alkyl, phenyl, thiophenyl, halogen, hydroxy, nitro and/or thiol;
ethylene urea, ethylene thiourea, 1,2,4-triazole, 5-aminotetrazole, 5-amino-1,3,4-thiadiazol-2-thiol, 3-amino-1H-1,2,4 triazole, 3,5-diamino-1,2,4-triazole, tolyltriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, naphthotriazole, 1H-tetrazole-5-acetic acid, 1-phenyl-2-tetrazoline-5-thione, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, imidazole, benzimidazole, triazine, methyltetrazole, 1,3-dimethyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, 2H-imidazole-2-thione, 4-methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl phosphate, indazole, adenine, cytosine, guanine, thymine, 2,2′-azanediyldiacetic acid, propanethiol, citric acid, ascorbic acid, thiourea, 1,1,3,3-tetramethylurea, urea, uric acid, glycine, dodecylphosphonic acid, oxalic acid, malonic acid, succinic acid, nitrilotriacetic acid, and mixtures thereof;
(D) at least one chelating agent selected from the group consisting of histidine, 1,2-cyclohexylenedinitrilotetraacetic acid, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, acetylacetonate, 2,2′-azanediyldiacetic acid, ethylenediaminetetraacetic acid, etidronic acid, methanesulfonic acid, acetylacetone, 1,1,1-trifluoro-2,4-pentanedione, 1,4-benzoquinone, 8-hydroxyquinoline, salicylidene aniline; tetrachloro-1,4-benzoquinone, 2-(2-hydroxyphenyl)-benzoxazol, 2-(2-hydroxyphenyl)-benzothiazole, hydroxyquinoline sulfonic acid, sulfosalicylic acid, salicylic acid, pyridine, 2-ethylpyridine, 2-methoxypyridine, 3-methoxypyridine, 2-picoline, dimethylpyridine, piperidine, piperazine, triethylamine, triethanolamine, ethylamine, methylamine, isobutylamine, tert-butylamine, tributylamine, dipropylamine, dimethylamine, diglycol amine, monoethanolamine, methyldiethanolamine, pyrrole, isoxazole, bipyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, indole, 1-methylimidazole, diisopropylamine, diisobutylamine, aniline, pentamethyldiethylenetriamine, acetoacetamide, ammonium carbamate, ammonium pyrrolidinedithiocarbamate, dimethyl malonate, methyl acetoacetate, N-methyl acetoacetamide, tetramethylammonium thiobenzoate, 2,2,6,6-tetramethyl-3,5-heptanedione, tetramethylthiuram disulfide, lactic acid, ammonium lactate, formic acid, propionic acid, gamma-butyrolactone, and mixtures thereof; and
(G) water,
wherein the method is suitable
for selectively etching a layer comprising an aluminum compound in the presence of a layer of a low-k material and/or a layer comprising copper and/or cobalt;
for selectively removing from a substrate a layer comprising an aluminum compound in the presence of a layer of a low-k material and/or a layer comprising copper and/or cobalt, and/or
for selectively removing from a surface of a semiconductor substrate a layer comprising an aluminum compound in the presence of a layer of a low-k material and/or a layer comprising copper and/or cobalt.

2. The method according to claim 1 , wherein the method comprises a two-step-process of removing
(i) a metal hard mask, and
(ii) an etch-stop layer of an aluminum compound deposited on a layer comprising copper and/or a layer comprising cobalt.

3. The method according to claim 1 , wherein
the at least one solubilizer (A) is selected from the group consisting of
a compound of formula I; and
a compound of formula II;
the etchant (B) is at least one selected from the group consisting of ammonium fluoride, ammonium bifluoride, triethanolammonium fluoride, diglycolammonium fluoride, methyldiethanolammonium fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof, and/or
the at least one corrosion inhibitor (C) is selected from the group consisting of
benzotriazole which is unsubstituted or substituted once or twice independently by C 1-4 -alkyl, amino-C 1-4 -alkyl, phenyl, thiophenyl, halogen, hydroxy, nitro and/or thiol;
succinic acid; and

mixtures thereof.

4. The method according to claim 1 ,
wherein
the at least one chelating agent (D) is selected from the group consisting of histidine, 1,2-cyclohexylenedinitrilotetraacetic acid, and mixtures thereof, and/or
the composition comprises as further component:

(E) a surfactant.

5. The method according to claim 1 ,
wherein
a pH of the composition is in the range of from 3.5 to 8, and/or
the composition comprises as further component:

(F) a buffering system which is suitable to buffer a pH of the composition in the range of from 3.5 to 8.

6. The method according to claim 1 , comprising
(A) at least one solubilizer selected from the group consisting of
a compound of formula I, and
a compound of formula II;

(B) at least one etchant, selected from the group consisting of ammonium fluoride, ammonium bifluoride, triethanolammonium fluoride, diglycolammonium fluoride, methyldiethanolammonium fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroboric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid, fluorosilicic acid, ammonium fluorosilicate, tetrabutylammonium tetrafluoroborate, and mixtures thereof;
(C) at least one corrosion inhibitor, selected from the group consisting of
benzotriazole which is unsubstituted or substituted once or twice independently by C 1-4 -alkyl, amino-C 1-4 -alkyl, phenyl, thiophenyl, halogen, hydroxy, nitro and/or thiol,
succinic acid, and

mixtures thereof,
(D) at least one chelating agent selected from the group consisting of histidine, 1,2-cyclohexylenedinitrilotetraacetic acid, and mixtures thereof, and
(G) water,
wherein a pH of the composition is in the range of from 3.5 to 8.

7. The method according to claim 1 , the composition comprising:
(A) at least one solubilizer, selected from the group consisting of 4-methylmorpholine-4-oxide, trimethylamine-N-oxide, triethylamine-N-oxide, triethanolamine-N-oxide, pyridine-N-oxide, N-ethylmorpholine-N-oxide, N-ethylpyrrolidine-N-oxide, and mixtures thereof;
(B) an etchant comprising fluoride anions;
(

Assignees

• Basf Se

Inventors

• Hoogboom Joannes Theodorus Valentinus
• Ke Jhih Jheng
• Wang Che Wei
• Klipp Andreas
• Cheng Yi Ping

Classifications

• H10P50/283

  by chemical means · CPC title

• C23F1/44 Primary

  Compositions for etching metallic material from a metallic material substrate of different composition · CPC title

• C23F1/20

  for etching aluminium or alloys thereof · CPC title

• C07D265/30

  not condensed with other rings · CPC title

• C09K13/00 Primary

  Etching, surface-brightening or pickling compositions (for glass C03C15/00, {C03C25/66; for mortars, concrete, artificial or natural stone or ceramics C04B41/5338}; for metallic material C23F, C23G1/00, C25F1/00; {for semi-conductors H10P52/40}) · CPC title