Etchant compositions for metal-containing films and methods of manufacturing integrated circuit devices using the etchant compositions

Patent metadata

Field	Value
Publication number	US-11427759-B2
Application number	US-202016946495-A
Country	US
Kind code	B2
Filing date	Jun 24, 2020
Priority date	Oct 17, 2019
Publication date	Aug 30, 2022
Grant date	Aug 30, 2022

Abstract

Metal-containing film etchant compositions may include hydrogen peroxide (H2O2), a phosphoric acid compound, a heterocyclic organic amine compound including at least one heteroatom in a ring, and water. Manufacturing methods of an integrated circuit (IC) may include performing a dry etch process on a conductive structure including a metal nitride film and a metal film to form a conductive pattern intermediate product and performing a wet etch process on the conductive pattern intermediate product using an etching atmosphere providing a higher etch selectivity with respect to the metal nitride film than the metal film. The etching atmosphere may include an etchant composition including hydrogen peroxide, a phosphoric acid compound, a heterocyclic organic amine compound including at least one heteroatom in a ring, and water.

First claim

What is claimed is:

1. A metal-containing film etchant composition comprising:
aqueous hydrogen peroxide (H 2 O 2 .nH 2 O);
a phosphoric acid compound; and
a heterocyclic organic amine compound comprising at least one heteroatom in a ring,
wherein the aqueous hydrogen peroxide has a purity of 31%, and the phosphoric acid compound comprises phosphoric acid having a purity of 85%, and
wherein the sum of a content of the aqueous hydrogen peroxide and a content of the phosphoric acid compound is about 95% by weight to about 99% by weight based on a total weight of the metal-containing film etchant composition.

2. The metal-containing film etchant composition of claim 1 , wherein the phosphoric acid compound comprises phosphoric acid (H 3 PO 4 ), pyrophosphoric acid (H 4 P 2 O 7 ), polyphosphoric acid, or a combination thereof.

3. The metal-containing film etchant composition of claim 1 , wherein the heterocyclic organic amine compound comprises a six-membered heterocyclic organic tertiary amine compound comprising two heteroatoms in the ring.

4. The metal-containing film etchant composition of claim 1 , wherein the heterocyclic organic amine compound is a compound of Formula I:

wherein R 1 and R 2 are each independently —(CH 2 ) 2 — or —(CR′H) 2 —, and R′ is a hydrogen atom or C1-C2 alkyl group,
wherein R 3 and R 4 are each independently a hydrogen atom, C1-C4 alkyl group, C1-C4 hydroxyalkyl group, or C1-C4 aminoalkyl group, and optionally wherein at least one of R 3 and R 4 is absent, and
wherein X is a nitrogen atom (N), oxygen atom (O), or carbon atom (C) and forms a six-membered heterocyclic organic amine compound together with R 1 and R 2 .

5. The metal-containing film etchant composition of claim 1 , wherein the metal-containing film etchant composition comprises:
about 3% by weight to about 20% by weight of the aqueous hydrogen peroxide based on the total weight of the metal-containing film etchant composition;
about 75% by weight to about 95% by weight of the phosphoric acid compound based on the total weight of the metal-containing film etchant composition; and
about 0.01% by weight to about 10% by weight of the heterocyclic organic amine compound based on the total weight of the metal-containing film etchant composition.

6. The metal-containing film etchant composition of claim 1 , wherein the heterocyclic organic amine compound comprises piperidine, piperidine derivatives, pyrazine, pyrazine derivatives, or a combination thereof.

7. The metal-containing film etchant composition of claim 1 , wherein the heterocyclic organic amine compound comprises piperazine, 1-(2-hydroxyethyl)piperazine, 1-(2-aminoethyl)piperazine, piperidine, morpholine, 4-(2-hydroxyethyl)morpholine, or 2-methylpyrazine, and
the metal-containing film etchant composition comprises about 0.1% by weight to about 5% by weight of the heterocyclic organic amine compound based on the total weight of the metal-containing film etchant composition.

8. The metal-containing film etchant composition of claim 1 , wherein the metal-containing film etchant composition consists essentially of the aqueous hydrogen peroxide, the phosphoric acid compound, and the heterocyclic organic amine compound.

9. A metal-containing film etchant composition comprising: aqueous hydrogen peroxide (H 2 O 2 .nH 2 O);
a phosphoric acid compound; and
a heterocyclic organic amine compound comprising two heteroatoms in a ring,
wherein the aqueous hydrogen peroxide has a purity of 31%, and the phosphoric acid compound comprises phosphoric acid having a purity of 85%, and
wherein the sum of a content of the aqueous hydrogen peroxide and a content of the phosphoric acid compound is about 95% by weight to about 99% by weight based on a total weight of the metal-containing film etchant composition.

10. The metal-containing film etchant composition of claim 9 , wherein the heterocyclic organic amine compound comprises piperidine, piperidine derivatives, pyrazine derivatives, or a combination thereof.

11. The metal-containing film etchant composition of claim 9 , wherein the phosphoric acid compound comprises phosphoric acid (H 3 PO 4 ), pyrophosphoric acid (H 4 P 2 O 7 ), polyphosphoric acid, or a combination thereof.

12. The metal-containing film etchant composition of claim 9 , wherein the heterocyclic organic amine compound is a compound of Formula I:

wherein R 1 and R 2 are each independently —(CH 2 ) 2 — or —(CR′H) 2 —, and R′ is a hydrogen atom or C1-C2 alkyl group,
wherein R 3 and R 4 are each independently a hydrogen atom, C1-C4 alkyl group, C1-C4 hydroxyalkyl group, or C1-C4 aminoalkyl group, and optionally wherein at least one of R 3 and R 4 is absent, and
wherein X is a nitrogen atom (N) or oxygen atom (O) and forms a six-membered heterocyclic organic amine compound together with R 1 and R 2 .

13. The metal-containing film etchant composition of claim 9 ,
wherein the metal-containing film etchant composition comprises:
about 3% by weight to about 20% by weight of the aqueous hydrogen peroxide based on the total weight of the metal-containing film etchant, composition;
about 75% by weight to about 95% by weight of the phosphoric acid based on the total weight of the metal-containing film etchant composition; and
about 0.01% by weight to about 10% by weight of the heterocyclic organic amine compound based on the total weight of the metal-containing film etchant composition.

14. The metal-containing film etchant composition of claim 9 , wherein the metal-containing film etchant, composition is devoid of sulfuric acid.

15. The metal-containing film etchant composition of claim 9 , wherein the metal-containing film etchant composition consists essentially of the aqueous hydrogen peroxide, the phosphoric acid compound, and the heterocyclic organic amine compound.

16. A metal-containing film etchant composition comprising:
about 3% by weight to about 20% by weight of aqueous hydrogen peroxide having a purity of 31% based on a total weight of the metal-containing film etchant composition;
about 75% by weight to about 95% by weight of phosphoric acid compound comprising phosphoric acid having a purity of 85% based on the total weight of the metal-containing film etchant composition; and
about 0.01% by weight to about 10% by weight of a heterocyclic organic amine compound based on the total weight of the metal-containing film etchant composition,
wherein the heterocyclic organic amine compound comprises a six-membered heterocyclic organic tertiary amine compound comprising at least one nitrogen atom in a ring, and
wherein the sum of a content of the aqueous hydrogen peroxide and a content of the phosphoric acid compound is about 95% by weight to about 99% by weight based on the total weight of the metal-containing film etchant composition.

17. The metal-containing film etchant composition of claim 16 , wherein the heterocyclic organic amine compound comprises piperidine, piperidine derivatives, pyrazine, pyrazine derivatives, or a combination thereof.

18. The metal-containing film etchant composition of claim 16 , wherein the heterocyclic organic amine compound is a compound of Formula I:

wherein:
R 1 and R 2 are

Assignees

• Samsung Electronics Co Ltd
• Dongwoo Fine Chem Co Ltd

Inventors

• Song Kihun
• Oh Jungmin
• Lee Hyosan
• Yoon Hyojoong
• Kim Minjung
• Baek Jongwook

Classifications

• H10P50/667

  by liquid etching only · CPC title

• C09K13/06 Primary

  with organic material · CPC title

• H01L21/32134

  Electricity · mapped topic

• H01L27/10876

  Electricity · mapped topic

• H01L27/10888

  Electricity · mapped topic