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US-12624450-B2 - Methods for forming and utilizing antimony containing films, and related structures

US12624450B2US 12624450 B2US12624450 B2US 12624450B2US-12624450-B2

Abstract

Systems and methods for forming an antimony containing film on a substrate. Related structures and films are also disclosed. The antimony films are be formed by a plasma enhanced atomic layer deposition process. The antimony films can be utilized as underlayers in EUV lithography processes.

Inventors

  • Paul Chatelain
  • Arpita Saha
  • David Kurt De Roest
  • Yoann Tomczak
  • Charles DEZELAH
  • Daniele Piumi

Assignees

  • ASM IP HOLDING B.V.

Dates

Publication Date
20260512
Application Date
20231228

Claims (15)

  1. 1 . A method for forming and utilizing an antimony containing film, the method comprising: seating a substrate in a reaction chamber; depositing an antimony containing film on the substrate by performing one or more unit deposition cycles of a plasma enhanced atomic layer deposition (PEALD) process, wherein a unit deposition cycle comprises: contacting the substrate with a vapor phase reactant comprising an antimony precursor; and contacting the substrate with one or more reactive species generated from a plasma produced from a gas comprising at least one of, argon (Ar), hydrogen (H 2 ), helium (He), and mixtures thereof; forming an extreme ultraviolet (EUV) responsive layer over the antimony containing film; irradiating the EUV responsive layer and the underlying antimony containing film with EUV radiation, thereby generating a plurality of secondary electrons from the antimony containing film, wherein a portion of the secondary electrons are absorbed in the EUV responsive layer; and developing the EUV responsive layer, wherein the deposited antimony containing film has a composition including metallic antimony (Sb).
  2. 2 . The method of claim 1 , wherein the antimony precursor comprises an alkylamine antimony precursor.
  3. 3 . The method of claim 2 , wherein the alkylamine antimony precursor comprises tris(dimethylamine) antimony (Sb(NMe 2 ) 3 ).
  4. 4 . The method of claim 1 , further comprising, applying an RF power of less than 50 Watts to generate the plasma.
  5. 5 . The method of claim 1 , further comprising, tuning the composition of the antimony containing film by adjusting at least one of a composition, flow rate, and flow rate ratio, of the gas employed in the production of the plasma.
  6. 6 . The method of claim 1 , wherein the plasma is produced from a gas consisting essentially of argon (Ar), and hydrogen (H 2 ).
  7. 7 . The method of claim 1 , wherein the deposited antimony containing film comprises, a surface composition (atomic-%) of metallic antimony (Sb) between 5 atomic-% and 45 atomic-%.
  8. 8 . The method of claim 1 , wherein the deposited antimony containing film comprises, a surface composition (atomic-%) of carbon (C) between 5 atomic-% and 30 atomic-%, and a surface composition of oxygen (O) between 20 atomic-% and 55 atomic-%.
  9. 9 . The method of claim 1 , wherein the plasma is produced from a gas consisting essentially of helium (He).
  10. 10 . The method of claim 9 , wherein the deposited antimony containing film comprises, a bulk composition (atomic-%) of metallic antimony (Sb) greater than 90 atomic-%, and a surface composition comprising an antimony oxide (SbO x ).
  11. 11 . A method for forming and utilizing an antimony containing film, the method comprising: seating a substrate in a reaction chamber; depositing an antimony containing film on the substrate by performing one or more unit deposition cycles of a plasma enhanced atomic layer deposition (PEALD) process, wherein a unit deposition cycle comprises: contacting the substrate with a vapor phase reactant comprising an antimony precursor; and contacting the substrate with one or more reactive species generated from a plasma produced from a gas comprising at least one of, argon (Ar), hydrogen (H 2 ), helium (He), and mixtures thereof; and heating the substrate to a deposition temperature of less than 50° C., wherein the deposited antimony containing film has a composition including metallic antimony (Sb).
  12. 12 . A method for forming and utilizing a metallic antimony containing film, the method comprising: depositing a metallic antimony containing film on a substrate by alternately and sequentially contacting the substrate with an alkylamine antimony precursor, and one or more plasma generated reactive species produced from a gas comprising, argon (Ar), hydrogen (H 2 ), helium (He), and mixtures thereof; forming an extreme ultraviolet (EUV) responsive layer over the metallic antimony containing film; irradiating select areas of the EUV responsive layer and the underlying metallic antimony containing film with EUV radiation thereby generating a plurality of secondary electrons from the metallic antimony containing film; and developing the EUV responsive layer.
  13. 13 . The method of claim 12 , wherein the alkylamine antimony precursor comprises tris(dimethylamine) antimony (Sb(NMe 2 ) 3 ).
  14. 14 . The method of claim 12 , wherein the one or more plasma generated reactive species is produced from a gas consisting essentially of argon (Ar), and hydrogen (H 2 ), and the metallic antimony containing film comprises a surface composition (atomic-%) of metallic antimony (Sb) between 5 atom-% and 45 atomic-%.
  15. 15 . The method of claim 12 , wherein the one or more plasma generated reactive species is produced from a gas consisting essentially of helium (He), and the metallic antimony containing film comprises a bulk composition (atomic-%) of metallic antimony (Sb) greater than 90 atomic-%, and a surface composition comprising, an antimony oxide (SbO x ).

Description

CROSS-REFERENCE TO RELATED APPLICATION(S) This application claims the benefit of U.S. Provisional Application 63/478,016 filed on Dec. 30, 2022, the entire contents of which are incorporated herein by reference. FIELD OF INVENTION The present disclosure relates generally to the field of semiconductor processing methods and systems, and to the field of device and integrated circuit manufacture. More particularly, the present disclosure relates to methods for forming and utilizing antimony containing films, as well as structures including such antimony containing films. BACKGROUND OF THE DISCLOSURE Antimony (Sb) containing films have been utilized in a number semiconductor technology applications, including, but not limited to, non-volatile phase change memory, optical detectors, high-speed digital circuits, and quantum well structures. However, the wider adoption of antimony (Sb) containing films in semiconductor device structures and integrated circuits has been limited due to a number of factors, including, but not limited to, an inability to deposit films with a controlled composition, an insufficient deposition rate, and poor deposition quality at low temperatures. Accordingly, improved methods for depositing antimony containing films are desirable, as well as methods for utilizing said improved antimony containing films. Any discussion, including discussion of problems and solutions, set forth in this section has been included in this disclosure solely for the purpose of providing a context for the present disclosure. Such discussion should not be taken as an admission that any or all of the invention was previously known or otherwise constitutes prior ar. SUMMARY OF THE DISCLOSURE This summary is provided to introduce a selection of concepts in a simplified form. These concepts are described in further detail in the detailed description of example embodiments of the disclosure below. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. In particular, the present disclosure describes methods for forming and utilizing an antimony containing film, the methods comprising, seating a substrate in a reaction chamber, and depositing an antimony containing film on the substrate by performing one or more unit deposition cycles of a plasma enhanced atomic layer deposition (PEALD) process, wherein a unit deposition cycle comprises, contacting the substrate with a vapor phase reactant comprising an antimony precursor, and contacting the substrate with one or more reactive species generated from a plasma produced from a gas comprising at least one of, argon (Ar), hydrogen (H2), helium (He), and mixtures thereof, wherein the deposited antimony containing film has a composition including metallic antimony (Sb). In some embodiment, the antimony precursor comprises an alkylamine antimony precursor. In some embodiment, the alkylamine antimony precursor comprises tris(dimethylamine)antimony (Sb(NMe2)3). In some embodiment, the methods of the current disclosure further include, heating the substrate to a deposition temperature of less than 100° C. In some embodiment, the methods of the current disclosure further include, applying an RF power of less than 50 Watts to generate the plasma. In some embodiment, the methods of the current disclosure further include, tuning the composition of the antimony containing film by adjusting at least one of the composition, the flow rate, and flow rate ratio, of the gas employed in the generation of the plasma. In some embodiment, the plasma is produced from a gas consisting essentially of argon (Ar), and hydrogen (H2). In some embodiment, the deposited antimony containing film comprises, a surface composition (atomic-%) of metallic antimony (Sb) between 5 atomic-% and 45 atomic-%. In some embodiment, the deposited antimony containing film comprises, a surface composition (atomic-%) of carbon (C) between 5 atomic-% and 30 atomic-%, and a surface composition of oxygen (O) between 20 atomic-% and 55 atomic-%. In some embodiment, the plasma pulse is produced from a gas consisting essentially of helium (He). In some embodiment, the deposited antimony containing film comprises, a bulk composition (atomic-%) of metallic antimony (Sb) greater than 90 atomic-%, and a surface composition comprising an antimony oxide (SbOx). In some embodiment, the methods of the present disclosure can further include, forming an extreme ultraviolet (EUV) responsive layer over the antimony containing film, irradiating the EUV responsive layer and the underlying antimony containing film with EUV radiation, thereby generating a plurality of secondary electrons from the antimony containing film, wherein a portion of said secondary electrons are absorbed in the EUV responsive layer. The methods of the present disclosure can further include, developing the EUV responsive layer. The prese