Method for forming thin film

Patent metadata

Field	Value
Publication number	US-12473645-B2
Application number	US-202217749153-A
Country	US
Kind code	B2
Filing date	May 20, 2022
Priority date	Sep 25, 2019
Publication date	Nov 18, 2025
Grant date	Nov 18, 2025

Abstract

The present invention relates to a method for forming a thin film, and more particularly, to a method for forming a thin film comprising steps of:
i) adsorbing a growth inhibitor for forming a thin film on a surface of a substrate; and ii) adsorbing a metal film precursor, metal oxide film precursor, metal nitride film precursor or silicon nitride film precursor on a surface of a substrate on which the growth inhibitor is adsorbed, wherein the growth inhibitor for forming a thin film is represented by Chemical Formula 1 below, and the metal is at least one selected from a group consisting of tungsten, cobalt, chrome, aluminum, hafnium, vanadium, niobium, germanium, lanthanide, actinoids, gallium, tantalum, zirconium, ruthenium, copper, titanium, is nickel, iridium and molybdenum.

A n B m X o   [Chemical Formula 1]
wherein A is carbon or silicon, B is hydrogen or a C1-C3 alkyl, X is a halogen, n is an integer of 1 to 15, o is an integer of 1 or more, and m is 0 to 2n+1.

According to the present invention, it is possible to suppress side reactions to appropriately lower a thin film growth rate and remove process byproducts in the thin film, thereby preventing corrosion or deterioration and greatly improving step coverage and thickness uniformity of a thin film, even when the thin film is formed on a substrate having a complex structure.

First claim

What is claimed is:

1 . A method for forming a thin film comprising steps of:
i) adsorbing a growth inhibitor for forming a thin film on a surface of a substrate; and ii) adsorbing a metal film precursor, metal oxide film precursor, metal nitride film precursor or silicon nitride film precursor on a surface of a substrate on which the growth inhibitor is adsorbed, and the metal is zirconium, wherein the growth inhibitor is one or more selected from the group consisting of 1,1-dichloroethane, 1,2-dichloroethane, dichloromethane, 2-chloropropane, 1-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 2,2-dichloropropane, 1-chloropentane, 2-chloropentane, 3-chloropentane, chlorocyclopentane, n-butylchloride, tert-butyl chloride, sec-butyl chloride, isobutyl chloride, 1,2-dichlorobenzene, 1,4-dichlorobenzene, trichloropropane, 2-chloro-2-methylbutane, and 2-methyl-1-pentene, and wherein in the step of i) adsorbing the growth inhibitor for forming a thin film on the surface of the substrate, a feeding amount of the growth inhibitor is 1-25 mg/cycle.

2 . The method for forming a thin film of claim 1 , wherein in the step of i) adsorbing the growth inhibitor for forming a thin film on the surface of the substrate, the feeding time for the growth inhibitor is 2 to 5 seconds.

3 . The method for forming a thin film of claim 1 , wherein the step of i) adsorbing the growth inhibitor for forming a thin film on the surface of the substrate comprises a step of injecting the growth inhibitor for forming a thin film into an atomic layer deposition (ALD) chamber and adsorbing the growth inhibitor onto a surface of a loaded substrate.

4 . The method for forming a thin film of claim 1 , wherein the step of i) adsorbing the growth inhibitor for forming a thin film on the surface of the substrate comprises a step of purging the remaining inhibitor unadsorbed on the surface of the substrate for forming the thin film with a purge gas.

5 . The method for forming a thin film of claim 1 , wherein the step of ii) adsorbing a film precursor comprises a step of purging the remaining unadsorbed film precursor with a purge gas.

6 . The method for forming a thin film of claim 1 , further comprising steps of supplying a reaction gas after adsorption of a film precursor on the surface of the substrate, and purging reaction byproducts of the film precursor and the reaction gas with a purge gas.

7 . The method for forming a thin film of claim 6 , wherein the reaction gas comprises a reducing agent, a nitriding agent, or an oxidizing agent.

8 . The method for forming a thin film of claim 1 , wherein the growth inhibitor for forming a thin film and the film precursor are transferred into the ALD chamber by a vapor flow control (VFC) method, a delivery liquid injection (DLI) method, or a liquid delivery system (LDS) method.

9 . The method for forming a thin film of claim 1 , wherein a ratio of the feeding amount (mg/cycle) between the growth inhibitor for forming a thin film and the film precursor in the ALD chamber is from 1:1.5 to 1:20.

10 . The method for forming a thin film of claim 1 , wherein a reduction rate of a thin film growth rate per cycle (Å/cycle) calculated by the following Equation 1 is −5% or less:
Reduction rate of thin film growth rate per cycle (%)=[(thin film growth rate per cycle when growth inhibitor for forming thin film is used−thin film growth rate per cycle when growth inhibitor for forming thin film is not used)/thin film growth rate per cycle when growth inhibitor for forming thin film is not used]×100  [Equation 1].

11 . The method for forming a thin film of claim 1 , wherein the residual halogen intensity (c/s) of the thin film formed after 200 cycles, which is measured based on SIMS, is 10,000 or less.

12 . The method for forming a thin film of claim 1 , wherein the metal precursor comprises tris(dimethylamino)cyclopentadienyl zirconium.

13 . The method for forming a thin film of claim 1 , wherein the thin film is a diffusion barrier film.

14 . The method for forming a thin film of claim 1 , wherein in the step of i) adsorbing the growth inhibitor for forming a thin film on the surface of the substrate, a feeding amount of the growth inhibitor is 1-25 mg/cycle, and
wherein a reduction rate of a thin film growth rate per cycle (Å/cycle) calculated by the following Equation 1 is −45% or less:
Reduction rate of thin film growth rate per cycle (%)=[(thin film growth rate per cycle when growth inhibitor for forming thin film is used−thin film growth rate per cycle when growth inhibitor for forming thin film is not used)/thin film growth rate per cycle when growth inhibitor for forming thin film is not used]×100  [Equation 1].

Assignees

• Soulbrain Co Ltd

Inventors

• Yeon Changbong
• Jung Jaesun
• Byun Hyeran
• Song Taeho
• Kim Sojung
• Lee Seokjong

Classifications

• H10P14/418

  the conductive layers comprising transition metals · CPC title

• H10W20/032

  of conductive barrier, adhesion or liner layers · CPC title

• H10P14/412

  Deposition of metallic or metal-silicide materials · CPC title

• H10P14/61

  using masks · CPC title

• H10P14/432

  using selective deposition · CPC title