Method for deposition of gallium-containing film with gallium precursors

Patent metadata

Field	Value
Publication number	US-12467134-B2
Application number	US-202218570260-A
Country	US
Kind code	B2
Filing date	Jun 17, 2022
Priority date	Jun 18, 2021
Publication date	Nov 11, 2025
Grant date	Nov 11, 2025

Abstract

A method of deposition of a gallium-containing oxide film on a substrate comprises a) simultaneously or sequentially, exposing the substrate to a vapor of a gallium precursor, additional metal precursor(s) and an oxidizer; b) depositing at least part of the gallium precursor and at least part of the additional metal precursor(s) onto the substrate to form the gallium-containing oxide film on the substrate through a vapor deposition process, wherein the gallium precursor has the formula:

(NR 8 R 9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]  (I)

(Cy-N) 2 Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]  (II)

wherein, R 1 to R 9 are independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; R 1 to R 9 may be the same or different; x=2, 3, 4, preferably x=2; Cy-N refers to saturated N-containing rings or unsaturated N-containing rings.

First claim

What is claimed is:

1 . A method of deposition of a gallium-containing oxide film on a substrate, the method comprising the steps of:
a) exposing the substrate to a vapor of a gallium-containing film-forming composition that contains a gallium precursor and an oxidizer; and b) depositing at least part of the gallium precursor onto the substrate to form the gallium-containing oxide film on the substrate through a vapor deposition process,
wherein the gallium precursor has the formula:
(NR 8 R 9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]  (I)

(Cy-N) 2 Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]  (II)

and the corresponding structures:

wherein, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; provided that when R 1 , R 2 , R 3 , R 4 , R 8 , R 9 each is Me, R 5 , R 6 are not H and R 7 is not Me or Et; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 may be the same or different; x=2, 3, 4; the N-containing rings comprising at least one nitrogen atom and 4-6 carbon atoms in a chain.

2 . The method of claim 1 , wherein the gallium precursor include (NMe 2 ) 2 Ga(EtNCH 2 CH 2 NEt 2 ), (NEtMe) 2 Ga(EtNCH 2 CH 2 NMe 2 ), (NEtMe) 2 Ga(EtNCH 2 CH 2 NEt 2 ), (NEt 2 ) 2 Ga(EtNCH 2 CH 2 NMe 2 ), and (NEt 2 ) 2 Ga(EtNCH 2 CH 2 NEt 2 ).

3 . The method of claim 1 , wherein x=2.

4 . The method of claim 1 , further comprising the step of
a1) at steps a), simultaneously or sequentially, exposing the surface to a vapor of a first metal (M 1 ) precursor, so that at least part of the first metal (M 1 ) precursor and the at least part of the gallium precursor are deposited onto the substrate to form the gallium-containing oxide film on the substrate through the vapor deposition process, wherein the gallium-containing oxide film is a M 1 GaO film.

5 . The method of claim 4 , further comprising the step of
a2) at steps a1), simultaneously or sequentially, exposing the surface to a vapor of a second metal (M 2 ) precursor, so that at least part of the second metal (M 2 ) precursor, the at least part of the gallium precursor and the at least part of the first metal (M 1 ) precursor are deposited onto the substrate to form the gallium-containing oxide film on the substrate through the vapor deposition process, wherein the gallium-containing oxide film is a M 1 M 2 GaO film, wherein the first metal (M 1 ) precursor is an indium precursor and the second metal (M 2 ) precursor is a zinc precursor, and vice versa.

6 . The method of claim 5 , wherein the indium precursor is selected from trialkyl indium, sec-Pentyl-cyclopentadienyl Indium or iso-Pentyl-cyclopentadienyl Indium.

7 . The method of claim 5 , wherein the zinc precursor is a diethyl zinc derivative selected from diethyl zinc-tetramethylethylenediamine adduct (TMEDA), diethyl zinc-tetraethylethylenediamine adduct (TEEDA), diethyl zinc-N,N′-diethyl-N,N′-diethyl-ethylenediamine adduct, diethyl zinc-N,N-dimethyl-N′,N′-diethylethylenediamine adduct, or diethyl zinc-N,N,N′-trimethyl-N′ethylethylenediamine adduct.

8 . The method of claim 1 , wherein the melting point of the gallium precursor is below approximately 60° C.

9 . A method of deposition of a gallium-containing quaternary oxide (M 1 M 2 GaO) film on a substrate, the method comprising the steps of:
a) exposing the substrate to a vapor of a gallium-containing film-forming composition that contains a gallium precursor, a first metal (M 1 ) precursor, a second metal (M 2 ) precursor, and an oxidizer; and b) depositing at least part of the gallium precursor, at least part of the first metal (M 1 ) precursor and at least part of the second metal (M 2 ) precursor onto the substrate to form the gallium-containing quaternary oxide film (M 1 M 2 GaO) on the substrate through a vapor deposition process,
wherein the gallium precursor has the formula:
(NR 8 R 9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]  (I)

(Cy-N) 2 Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]  (II)

and the corresponding structures:

wherein, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; provided that when R 1 , R 2 , R 3 , R 4 , R 8 , R 9 each is Me, R 5 , R 6 are not H and R 7 is not Me or Et; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 may be the same or different; x=2, 3, 4; the N-containing rings comprising at least one nitrogen atom and 4-6 carbon atoms in a chain.

10 . The method of claim 9 , wherein the gallium precursor includes (NMe 2 ) 2 Ga(EtNCH 2 CH 2 NEt 2 ), (NEtMe) 2 Ga(EtNCH 2 CH 2 NMe 2 ), (NEtMe) 2 Ga(EtNCH 2 CH 2 NEt 2 ), (NEt 2 ) 2 Ga(EtNCH 2 CH 2 NMe 2 ), and (NEt 2 ) 2 Ga(EtNCH 2 CH 2 NEt 2 ).

11 . The method of claim 9 , wherein x=2.

12 . The method of claim 9 , wherein the first metal (M 1 ) precursor is an indium precursor and the second metal (M 2 ) precursor is a zinc precursor, and vice versa.

13 . The method of claim 12 , wherein the indium precursor is selected from trialkyl indium, sec-Pentyl-cyclopentadienyl Indium or iso-Pentyl-cyclopentadienyl Indium.

14 . The method of claim 12 , wherein the zinc precursor is a diethyl zinc derivative selected from diethyl zinc-tetramethylethylenediamine adduct (TMEDA), diethyl zinc-tetraethylethylenediamine adduct (TEEDA), diethyl zinc-N,N′-diethyl-N,N′-diethyl-ethylenediamine adduct, diethyl zinc-N,N-dimethyl-N′,N′-diethylethylenediamine adduct, or diethyl zinc-N,N,N′-trimethyl-N′ethylethylenediamine adduct.

15 . The method of claim 9 , wherein the melting point of the Ga precursor is below 60° C.

16 . A method of deposition of an Indium Gallium Zinc oxide (IGZO) film on a substrate, the method comprising the steps of:
a) exposing the substrate to a vapor of a gallium-containing film-forming composition that contains a gallium precursor, an indium precursor, a zinc precursor, and O 3 ; and b) depositing at least part of the gallium precursor, at least part of the indium precursor and at least part of the zinc precursor onto the substrate to form the IGZO film on the substrate through a vapor deposition process,
wherein the gallium precursor has the formula:
(NR 8 R 9 )(NR 1 R 2 )Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]  (I)

(Cy-N) 2 Ga[(R 3 R 4 N)C x (R 5 R 6 )(NR 7 )]  (II)

and the corresponding structures:

wherein, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are independently selected from H, Me, Et, nPr, iPr, nBu, iBu, sBu, or tBu; provided that when R 1 , R 2 , R 3 , R 4 , R 8 , R 9 each is Me, R 5 , R 6 are not H and R 7 is not Me or Et; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 may be the same or different; x=2, 3, 4; the N-containing rings comprising at least one nitrogen atom and 4-6 carbon atoms in a chain.

17 . The method of claim 16 , wherein x=2.

18 . The method of claim 16 , wherein the indium precursor is iso-Pentyl-cyclopentadienyl Indium.

19 . The method of claim 16 , wherein the zinc precursor is diethyl zinc-tetraethylethylenediamine adduct (TEEDA).

20 . The method of claim 16 , wherein the melting point of the Ga precursor is below 60° C.

Assignees

• Air Liquide
• Air Liquide Electronics Us Lp
• Air Liquide American

Inventors

• Peng Bo
• Gatineau Julien
• Wang Ziyun
• Liu Yumin

Classifications

• C23C16/45553 Primary

  characterized by the use of precursors specially adapted for ALD · CPC title

• C23C16/45531

  specially adapted for making ternary or higher compositions · CPC title

• C07F3/06

  Zinc compounds · CPC title

• C07F5/003

  without C-Metal linkages · CPC title

• C23C16/40 Primary

  Oxides · CPC title