Area selective deposition of metal containing films

Patent metadata

Field	Value
Publication number	US-11319449-B2
Application number	US-201916723771-A
Country	US
Kind code	B2
Filing date	Dec 20, 2019
Priority date	Dec 20, 2019
Publication date	May 3, 2022
Grant date	May 3, 2022

Abstract

Processes of selectively depositing a metal-containing film comprise: providing a surface having a plurality of materials exposed thereon simultaneously, and exposing the surface to a vapor of a metal-containing film-forming composition that contains a precursor having the formula:LxM(—N(R)—(CR′2)n—NR″2)wherein M is a Group 12, Group 13, Group 14, Group 15, Group IV or Group V element; x+1 is the oxidation state of the M; L is an anionic ligand, independently selected from dialkylamine, alkoxy, alkylimine, bis(trialkylsilylamine), amidinate, betadiketonate, keto-imine, halide, or the like; R, R″ each are independently a C1-C10 linear, branched or cyclic alkyl, alkenyl, or trialkylsilyl group; R′ is H or a C1-C10 linear, branched or cyclic alkyl, alkenyl or trialkylsilyl group; n=1-4,wherein at least one of the materials is at least partially blocked by a blocking agent from the deposition of the metal-containing film through a vapor deposition process.

First claim

What is claimed is:

1. A process of selectively depositing a metal-containing film, the process comprising the steps of:
a) providing a surface having a plurality of materials exposed thereon simultaneously; and
b) exposing the surface to a vapor of a metal-containing film-forming composition that contains a precursor having the formula:
L x M(-N(R)—(CR′ 2 ) n —NR″ 2 )

wherein M is a Group 12, Group 13, Group 14, Group 15, Group IV or Group V element; x+1 is the oxidation state of the M; L is an anionic ligand; R, R″ each are independently a C 1 -C 10 linear, branched or cyclic alkyl, alkenyl, or trialkylsilyl group; R′ is H or a C 1 -C 10 linear, branched or cyclic alkyl, alkenyl or trialkylsilyl group; n=1-4; and

c) preferentially or selectively depositing a film on one or more of, but less than all of, the plurality of materials on the surface in a vapor deposition process,
wherein at least one of the materials on the surface is at least partially blocked by a blocking agent thereby reducing or preventing a deposition of the metal-containing film on said blocked material.

2. The process of claim 1 , wherein the vapor deposition process is an ALD process.

3. The process of claim 1 , further comprising
exposing the surface to a co-reactant selected from an oxidizer agent or a nitrigen agent.

4. The process of claim 3 , further comprising the steps of
repeating the exposing to the vapor of the metal-containing film-forming composition and the exposing to the co-reactant until a desired thickness of the metal-containing film is formed; and
purging excess vapor of the metal-containing film-forming composition and excess co-reactant using an inert gas, respectively, to separate each exposure, wherein the inert gas is N 2 , Ar, Kr or Xe.

5. The process of claim 3 , wherein the co-reactant is selected from O 3 , O 2 , H 2 O, H 2 O 2 , D 2 O, ROH wherein R═C 1 -C 10 linear or branched hydrocarbon, NH 3 , NO, N 2 O, hydrazines, amines or combinations thereof.

6. The process of claim 3 , wherein the co-reactant is H 2 O.

7. The process of claim 1 , wherein the blocking agent forms a SAM layer on the at least one of the materials by dipping the surface in the blocking agent or vapor spraying the surface with the blocking agent.

8. The process of claim 1 , wherein the plurality of the materials include at least a dielectric material and at least a metal material on the surface.

9. The process of claim 8 , wherein the metal-containing film is deposited on the dielectric film but not deposited on the metal material by blocking the reactivity of the metal film by a metal blocking agent.

10. The process of claim 9 , wherein the metal blocking agent is selected from a alkyl or fluoroalkyl compounds having a surface reactive chemical function group selected from phosphonic acids, carboxylic acids, thiols, or triazoles.

11. The process of claim 8 , wherein the metal-containing film is deposited on the metal material but not deposited on the dielectric material by blocking the reactivity of the dielectric material by a dielectric blocking agent.

12. The process of claim 11 , wherein the dielectric blocking agent is a compound having the formula R 4-a SiX a , wherein each X are independently a surface hydroxyl reactive group (halide, alkylamino, alkoxy, acetamide, etc.), and each R are selected from H, a C 1 -C 20 alkyl or fluoroalkyl group or mixture thereof.

13. The process of claim 1 , wherein the surface is exposed to the precursor at a temperature raging from room temperature to approximately 500° C.

14. The process of claim 1 , wherein the precursor is (NMe 2 ) 2 Al(-NEt-(CH 2 ) 2 -NEt 2 ).

15. The process of claim 14 , wherein the metal-containing film is an Al 2 O 3 film.

16. A composition for selective deposition of a metal-containing film comprising a precursor having the formula:
L x M(-N(R)—(CR′ 2 ) n —NR″ 2 )

wherein M is a Group 12, Group 13, Group 14, Group 15, Group IV or Group V element; x+1 is the oxidation state of the M; L is an anionic ligand, independently selected from dialkylamine, alkoxy, alkylimine, bis(trialkylsilylamine), amidinate, betadiketonate, keto-imine, halide, or the like; R, R″ each are independently a C 1 -C 10 linear, branched or cyclic alkyl, alkenyl, or trialkylsilyl group; R′ is H or a C 1 -C 10 linear, branched or cyclic alkyl, alkenyl or trialkylsilyl group; n=1-4.

17. The composition of claim 16 , wherein the precursor is (NMe 2 ) 2 Al(-NEt-(CH 2 ) 2 -NEt 2 ).

18. The composition of claim 16 , wherein the composition comprises between approximately 95% w/w and approximately 100.0% w/w of the precursor.

19. The composition of claim 16 , wherein the composition comprises between approximately 0.0% w/w and approximately 5.0% w/w impurities.

20. A process of selectively depositing Al 2 O 3 film, the process comprising the steps of:
a) providing a surface having at least one dielectric material and at least one metal material exposed thereon simultaneously;
b) exposing the surface to a vapor of (NMe 2 ) 2 Al(-NEt-(CH 2 ) 2 -NEt 2 ); and
c) exposing the surface to a co-reactant H 2 O, wherein the at least one dielectric material is at least partially blocked by a blocking agent dimethyldichlorosilane (DMDCS) from the deposition of the Al 2 O 3 film through an ALD process.

Assignees

• Air Liquide

Inventors

• Noh Wontae
• Lee Jooho
• Girard Jean-Marc

Classifications

• H10P14/668

  the materials being characterised by the deposition precursor materials · CPC title

• H10P14/6339 Primary

  deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD · CPC title

• H10P95/00

  Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass · CPC title

• H10P14/69391

  the material containing aluminium, e.g. Al2O3 · CPC title

• H10P14/61 Primary

  using masks · CPC title