FILM FORMING METHOD

• US 20120114869A1
• Filed: 01/13/2012
• Published: 05/10/2012
• Est. Priority Date: 07/14/2009
• Status: Active Grant

• Current Assignee: Tokyo Electron Limited
• Original Assignee: Tokyo Electron Limited
• Inventors: MIYOSHI, Hidenori, Hara, Masamichi
• Granted Patent: US 9,293,417 B2
• Time in Patent Office: Days
• US Class Current: 427/489
• CPC Class Codes: C23C 16/02 Pretreatment of the material to be coated C23C16/04 takes precedence
• CPC Class Codes: C23C 16/0236 by etching with a reactive gas
• CPC Class Codes: C23C 16/04 Coating on selected surface areas, e.g. using masks
• CPC Class Codes: C23C 16/042 using masks
• CPC Class Codes: C23C 16/16 from metal carbonyl compounds
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: H01L 21/28556 by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD H01L21/28518 - H01L21/28537 and H01L21/28568 take precedence
• CPC Class Codes: H01L 21/76849 the layer being positioned on top of the main fill metal
• CPC Class Codes: H01L 23/53238 Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

Disclosed is a film-forming method wherein a manganese-containing film is formed on a substrate having a surface to which an insulating film and a copper wiring line are exposed. The film-forming method includes forming a manganese-containing film on the copper wiring line by a CVD method which uses a manganese compound.

Claims

1. A film-forming method for forming a manganese-containing film on a substrate having a surface to which an insulating film and a copper wiring line are exposed, the film-forming method comprising:

(1) forming a manganese-containing film on the copper wiring line by a CVD method using a manganese compound.

2. The film-forming method of claim 1, wherein the manganese compound is at least one selected from the group consisting of:

(EtCp)₂Mn[═

Mn(C₂H₅C₅H₄)₂];

Cp₂Mn[═

Mn(C₅H₅)₂];

(MeCp)₂Mn[═

Mn(CH₃C₅H₄)₂];

(i-PrCp)₂Mn[═

Mn(C₃H₇C₅H₄)₂];

MeCpMn(CO)₃[═

(CH₃C₅H₄)Mn(CO)₃];

(t-BuCp)₂Mn[═

Mn(C₄H₉C₅H₄)₂];

Mn(DMPD)(EtCp)[=Mn(C₇H₁₁C₂H₅C₅H₄)], and

((CH₃)₅CP)₂Mn[═

Mn((CH₃)₅C₅H₄)₂].

3. The film-forming method of claim 1, wherein the surface of the insulating film is non-hydrophilic.

4. The film-forming method of claim 2, wherein the surface of the insulating film is non-hydrophilic.

5. The film-forming method of claim 1, further comprising, before the step (1), (2) making the surface of the insulating film non-hydrophilic.

6. The film-forming method of claim 2, further comprising, before the step (1), (2) making the surface of the insulating film non-hydrophilic.

7. The film-forming method of claim 5, wherein the step (2) includes hydrophobizing the surface of the insulating film by using a hydrophobic material which allows the surface of the insulating film to have a hydrophobic property and/or dehydrating the insulating film.

8. The film-forming method of claim 7, wherein, when the step (2) includes the hydrophobizing, the hydrophobic material is at least one selected from the group consisting of:

HMDS (Hexamethyldisilazane);

TMDS (1,1,3,3-Tetramethyldisilazane);

TMSDMA (Dimethylaminotrimethylsilane);

DMSDMA (Dimethylsilyldimethylamine);

TMMAS (Trimethylmethylaminosilane);

TMICS (Trimethyl(isocyanato)silane);

TMSA (Trimethylsilylacetylene);

TMSC (Trimethylsilylcyanide);

1,3,5,7-tetramethylcyclotetrasiloxane;

Dimethylsilane;

Tetraethylcyclotetrasiloxane;

1,2,3-triethyl-2,4,6-trimethylcyclotrisilazane;

1,2,3,4,5,6-hexamethylcyclotrisilazane;

Monomethylsilane;

Hexamethyldisilane;

Hexamethylsiloxane;

Trimethylsilane;

Tetramethysilane;

Dimethyldimethoxysilane;

Octamethylcyclotetrasiloxane;

Trimethoxymethylsilane;

Hexaethyldisilazane;

hexaphenyldisilazane;

heptamethyldisilazane;

dipropyl-tetramethyldisilazane;

di-n-butyl-tetramethyldisilazane;

di-n-octyl-tetramethyldisilazane;

divinyl-tetramethyldisilazane;

1,1,3,3,5,5-hexamethylcyclotrisilazane;

Hexaethylcyclotrisilazane;

Hexaphenylcyclotrisilazane;

Octamethylcyclotetrasilazane;

Octaethylcyclotetrasilazane;

tetraethyl-tetramethylcyclotetrasilazane;

tetraphenyldimethyldisilazane;

diphenyl-tetramethyldisilazane;

trivinyl-trimethylcyclotrisilazane; and

tetravinyl-tetramethylcyclotetrasilazane.

9. The film forming method of claim 5, further comprising, after the step (2), (3) removing the hydrophobic material and/or the oxide from the surface of the copper wiring line while maintaining the non-hydrophilic property of the surface of the insulating film.

10. The film forming method of claim 9, wherein the hydrophobic material and/or the oxide is removed by using an organic compound.

11. The film forming method of claim 10, wherein the organic compound is at least one selected from the group consisting of:

alcohol;

aldehyde;

carboxylic acid;

anhydrous carboxylic acid;

ester; and

ketone.

12. The film forming method of claim 9, wherein the steps (1) to (3) are performed in separate processing chambers, and the steps (1) to (3) are consecutively performed without exposing the substrate to the atmosphere.

13. The film forming method of claim 1, wherein the surface of the insulating film is hydrophilic.

14. The film-forming method of claim 2, wherein the surface of the insulating film is hydrophilic.

15. The film-forming method of claim 1, further comprising, before the step (1), (4) hydrophilizing the surface of the insulating film.

16. The film-forming method of claim 2, further comprising, before the step (1), (4) hydrophilizing the surface of the insulating film.

17. The film-forming method of claim 15, wherein the step (4) includes one of steps of performing a plasma process on the surface of the insulating film, performing a UV ozone process on the surface of the insulating film, and allowing moisture to be absorbed on the surface of the insulating film.

18. The film-forming method of claim 17, further comprising, after the step (4), (5) removing an oxide from the surface of the copper wiring line while maintaining the hydrophilic property of the surface of the insulating film.

19. The film-forming method of claim 18, wherein the oxide is removed by a cleaning method using an organic compound, a hydrogen annealing method, or an ultra low oxygen partial pressure method.