IP Library › Granted Patent US 11,859,283
Granted Patent B2
US 11,859,283 · App. 16/941,088 · Granted Jan 2, 2024

Heteroalkylcyclopentadienyl indium-containing precursors and processes of using the same for deposition of indium-containing layers

Inventors: Antoine Bruneau (Liffre, FR); Takashi Ono (Yokosuka, JP); Christian Dussarrat (Tokyo, JP)
Assignee: L'Air Liquide Societe Anonyme Pour L'Etude Et L'Exploitation Des Procedes Georges Claude
C23C16/45514C07F5/00C23C16/18
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Quick Facts
Patent No.
US 11,859,283
App. No.
16/941,088
Granted
Jan 2, 2024
Kind
B2
Abstract

Methods for forming an Indium-containing film by a vapor deposition method using a heteroalkylcyclopentadienyl Indium (I) precursor having a general formula: In[R 1 R 2 R 3 R 4 CpL 1 ] or In[CpL 1 L 2 y ] wherein Cp represents a cyclopentadienyl ligand; R 1 to R 4 are each independently H, C 1 -C 4 linear, branched or cyclic alkyls; L 1 and L 2 are each independently a substituent bonded to the Cp ligand and consisting of an alkyl chain containing at least one heteroatom, such as Si, Ge, Sn, N, P, B, Al, Ga, In, O, S, Se, Te, F, Cl, Br, I; and y=1-4. Examplary heteroalkylcyclopentadienyl Indium (I) precursors include In(Cp(CH 2 ) 3 NMe 2 ) or In(CpPiPr 2 ).

Claims (20)

1. A method for forming an Indium-containing film, the method comprising the steps of:

exposing a substrate to a vapor of a film forming composition; wherein the film forming composition comprises a heteroalkylcyclopentadienyl Indium (I) precursor having a general formula:

In[R 1 R 2 R 3 R 4 CpL 1 ] or

In[CpL 1 L 2 y ]

wherein Cp represents a cyclopentadienyl ligand; R 1 to R 4 are each independently H, C 1 -C 4 linear, branched or cyclic alkyls; L 1 and L 2 are each independently a substituent bonded to the Cp ligand and consisting of an alkyl chain containing at least one heteroatom selected from Si, Ge, Sn, N, P, B, Al, Ga, In, O, S, Se, Te, F, Cl, Br, I; and y=1-4; and

depositing at least part of the heteroalkylcyclopentadienyl Indium(I) precursor onto the substrate to form the Indium-containing film using a vapor deposition method.

2. The method of claim 1 , wherein the vapor deposition method is ALD, CVD or a combination thereof.

3. The method of claim 1 , wherein L 1 and L 2 are each independently a —(C k H l -ER m ) group, wherein —C k H l is a linear, cyclic or branched alkyl chain; k=0-6; l=0-11; E=Si, Ge, Sn, N, P, B, Al, Ga, In, O, S, Se, Te, F, Cl, Br, I; R is H, a C 1 -C 5 linear, cyclic or branched alkyl.

4. The method of claim 1 , wherein the heteroalkylcyclopentadienyl Indium(I) precursor is selected from the group consisting of

wherein n and n′ are each independently 0 to 6, representing C 0 to C 6 linear, cyclic or branched alkyl chain; E and ‘E’ are each independently Si, Ge, Sn, N, P, B, Al, Ga, In, O, S, Se, Te, F, Cl, Br, I; R=H, a C 1 to C 5 linear, branched or cyclic alkyl, or a heteroalkyl; R 1 to R 4 are independently H, C 1 -C 4 linear, branched or cyclic alkyls; m=0 to 4; y=1 to 4.

5. The method of claim 1 , wherein the heteroalkylcyclopentadienyl Indium(I) precursor is In(Cp(CH 2 ) 3 NMe 2 ).

6. The method of claim 1 , wherein the heteroalkylcyclopentadienyl Indium(I) precursor is In(CpPiPr 2 ).

7. The method of claim 1 , further comprising the step of delivering into the reactor a co-reactant.

8. The method of claim 7 , wherein the co-reactant is an oxidizing agent selected from O 2 , O 3 , H 2 O, H 2 O 2 , NO, N 2 O, NO 2 , O radicals, alcohol, silanols, aminoalcohols, carboxylic acids, para-formaldehyde, or mixtures thereof.

9. The method of claim 7 , wherein the co-reactant is O 3 or O 2 .

10. The method of claim 7 , wherein the co-reactant is a nitrogen-containing reducing agent selected from NH 3 , N 2 , H 2 , N 2 /H 2 , H 2 and NH 3 , N 2 and NH 3 , NH 3 and N 2 H 4 , NO, N 2 O, amines, diamines, cyanides, di-imines, hydrazines, organic amines, pyrazoline, pyridine, primary amines such as methylamine, ethylamine, primary amines; secondary amines; tertiaryamines, or mixture thereof.

11. The method of claim 7 , wherein the co-reactant is NH 3 .

12. The method of claim 1 , wherein the Indium-containing film is In x O y , InSnO (ITO), InGaZnO (IGZO), InN, InP, InAs, InSb or In 2 S 3 .

13. The method of claim 1 , wherein the Indium-containing film contains a second element selected from P, N, S, Ga, As, B, Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co, Zn, one or more lanthanides, or combinations thereof.

14. The method of claim 1 , wherein the substrate is a powder comprising one or more of NMC (Lithium Nickel Manganese Cobalt Oxide), LCO (Lithium Cobalt Oxide), LFP (Lithium Iron Phosphate), and other battery cathode materials.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 27, 2020
From: BRUNEAU, ANTOINE; ONO, TAKASHI; DUSSARRAT, CHRISTIAN
To: L'AIR LIQUIDE, SOCIÉTÉ ANONYME POUR L'ETUDE ET L'EXPLOITATION DES PROCÉDÉS GEORGES CLAUDE
Reel/Frame 053618/0739 →
Continuity (1)
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