Methods for forming a silicon oxide layer over a substrate

• US 7,943,531 B2
• Filed: 10/22/2007
• Issued: 05/17/2011
• Est. Priority Date: 10/22/2007
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Yieh, Ellie Y., Mallick, Abhijit Basu, Nemani, Srinivas D.
• Primary Examiner(s): Lee; Hsien-ming
• Assistant Examiner(s): PARENDO, KEVIN A
• Application Number:
  US11/876,664
• Publication Number:
  US 20090104791A1
• Time in Patent Office: 1,303 Days
• Field of Search: 438787-790, 257E21277-E21278
• US Class Current: 438/787
• CPC Class Codes: C23C 16/045 Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/452 by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: H01L 21/02126 the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
• CPC Class Codes: H01L 21/02164 the material being a silicon oxide, e.g. SiO2
• CPC Class Codes: H01L 21/02216 the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
• CPC Class Codes: H01L 21/02219 the compound comprising silicon and nitrogen
• CPC Class Codes: H01L 21/02222 the compound being a silazane
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/02337 treatment by exposure to a gas or vapour
• CPC Class Codes: H01L 21/3122 layers comprising polysiloxane compounds
• CPC Class Codes: H01L 21/31612 on a silicon body
• CPC Class Codes: H01L 21/31633 Deposition of carbon doped silicon oxide, e.g. SiOC

Abstract

A method of depositing a silicon oxide layer over a substrate includes providing a substrate to a deposition chamber. A first silicon-containing precursor, a second silicon-containing precursor and a NH₃ plasma are reacted to form a silicon oxide layer. The first silicon-containing precursor includes at least one of Si—H bond and Si—Si bond. The second silicon-containing precursor includes at least one Si—N bond. The deposited silicon oxide layer is annealed.

Claims

1. A method of depositing a flowable silicon oxide layer on a substrate, the method comprising:

providing the substrate to a deposition chamber;

dissociating an ozone-containing precursor to form a mixture comprising atomic oxygen, wherein dissociating the ozone-containing precursor comprises introducing the ozone-containing precursor into a remote plasma generating chamber and striking a plasma in the remote plasma generating chamber;

transferring the mixture comprising atomic oxygen from the remote plasma generating chamber into the deposition chamber;

introducing a silicon-and-halogen-containing precursor to the deposition chamber, the silicon-and-halogen-containing precursor having a C;

Si atom ratio of about 8 or less, the silicon-and-halogen-containing precursor and the mixture comprising atomic oxygen being first mixed in the deposition chamber;

reacting the silicon-and-halogen-containing precursor and the mixture comprising atomic oxygen to form the flowable silicon oxide layer on the substrate; and

annealing the flowable silicon oxide layer;

wherein a molar ratio of the silicon-and-halogen-containing precursor to the mixture comprising atomic oxygen is between about 1;

10 and about 100;

1.

2. The method of claim 1, wherein the ozone-containing precursor comprises a mixture-of ozone and oxygen, wherein the mixture of ozone and oxygen comprises between about 6% and about 20% ozone by weight.

3. The method of claim 2, wherein the ozone is generated from the oxygen.

4. The method of claim 3, wherein a flow rate of the oxygen is between about 3 standard liters per minute (slm) and about 20 slm.

5. The method of claim 1, wherein reacting the silicon precursor and the atomic oxygen precursor has a process pressure between about 100 Torr and about 760 Torr.

6. The method of claim 1, wherein reacting the silicon precursor and the atomic oxygen precursor has a process temperature between about −

10°

C. and about 200°

C.

7. The method of claim 1, wherein the silicon precursor has an O:

Si ratio of about 3 or more.

8. The method of claim 1, wherein the silicon precursor includes at least one of siloxane, silazoxane and halogenated siloxane.

9. The method of claim 8, wherein the siloxane is selected from the group consisting of triethoxysiloxane, tetramethoxysiloxane, trimethoxysiloxane, hexamethoxydisiloxane, octamethoxytrisiloxane, octamethosydodecasiloxane and octamethoxydodecasiloxane.

10. The method of claim 8, wherein the silazoxane is selected from the group consisting of hexamethoxydisilazoxane, methyl hexamethoxydisilazoxane, chlorohexamethoxydisilazoxane, hexaethoxydislazoxane, octamethoxycyclicsilazoxane, and nonamethoxytrisilazoxane.

11. The method of claim 8, wherein the halogenated siloxane is selected from the group consisting of dichlorodiethoxysiloxane, chlorotriethoxysiloxane, hexachlorodisiloxane, and octachlorotrisiloxane.

12. The method of claim 1, wherein the silicon precursor comprises an aminosilane, an alkyl disilane, an alkoxy disilane, an alkoxy-alkyl disilane, an alkoxy-acetoxy disilane, or a cyclosilane.

13. The method of claim 12, wherein the amionsilane is selected from the group consisting of trisilylamine (TSA), hexamethyldisilazane (HMDS), silatrane, tetrakis(dimethylamino)silane, bis(diethylamino)silane, bis-tert-butylaminosilane;

bis-dimethylaminosilane (BDMAS), tris(dimethylamino)chlorosilane and methylsilatrane.

14. The method of claim 1, wherein annealing the deposited silicon oxide layer comprises at least one of a steam anneal, a thermal anneal, an inductively coupled plasma (ICP) anneal, an ultraviolet light anneal, an e-beam anneal, an acid vapor catalysis anneal, a base vapor catalysis anneal and a microwave anneal.

15. The method of claim 1, wherein the silicon-and-halogen-cotaining precursor includes tetrachlorosilane.

16. A method of depositing a flowable silicon oxide layer on a substrate, the method comprising:

providing a substrate to a deposition chamber;

dissociating a mixture of ozone and oxygen to form a mixture comprising atomic oxygen, wherein dissociating the mixture of ozone and oxygen comprises introducing the mixture into a remote plasma generating chamber and striking a plasma in the remote plasma generating chamber located outside the deposition chamber;

transferring the mixture comprising atomic oxygen from the remote plasma generating chamber into the deposition chamber;

introducing a silicon-and-halogen-containing precursor to the deposition chamber, the silicon precursor having a C;

Si atom ratio of about 8 or less, the silicon-and-halogen-containing precursor and the mixture comprising atomic oxygen being first mixed in the deposition chamber;

reacting the silicon-and-halogen-containing precursor and the mixture comprising atomic oxygen at a process pressure between about 100 Torr and about 760 Torr to form the flowable silicon oxide layer on the substrate; and

annealing the flowable silicon oxide layer.

17. The method of claim 16, wherein the mixture of ozone and oxygen comprises between about 6% and about 20% ozone by weight.

18. The method of claim 17, wherein a flow rate of the oxygen is between about 3 standard liters per minute (slm) and about 20 slm.

19. The method of claim 16, wherein a molar ratio of the silicon-and-halogen-containing precursor to the mixture comprising atomic oxygen is between about 1:

10 and about 100;

1.

20. The method of claim 16, wherein reacting the silicon-and-halogen-containing precursor and the mixture comprising atomic oxygen has a process temperature between about −

10°

C. and about 200°

C.

21. The method of claim 16, wherein the silicon-and-halogen-containing precursor includes at least one of a halogenated silazoxane and a halogenated siloxane.

22. The method of claim 16, wherein the silicon-and-halogen-containing precursor comprises a chlorinated siloxane.

23. The method of claim 16, wherein the silicon-and-halogen-containing precursor comprises a halogenated siloxane selected from the group consisting of tetrachlorosiloxane, dichlorodiethoxysiloxane, chlorotriethoxysiloxane, hexachlorodisiloxane, and octachlorotrisiloxane.

24. The method of claim 16, wherein the silicon-and-halogen-containing precursor comprises an aminosilane, an alkyl disilane, an alkoxy disilane, an alkoxy-alkyl disilane, an alkoxy-acetoxy disilane, or a cyclosilane.

25. The method of claim 24, wherein the aminosilane is selected from the group consisting of trisilylamine (TSA), hexamethyldisilazane (HMDS), silatrane, tetrakis(dimethylamino)silane, bis(diethylamino)silane, bis-tert-butylaminosilane;

bis-dimethylaminosilane (BDMAS), tris(dimethylamino)chlorosilane and methylsilatrane.

26. The method of claim 16, wherein annealing the flowable silicon oxide layer comprises at least one of a steam anneal, a thermal anneal, an inductively coupled plasma (ICP) anneal, an ultraviolet light anneal, an e-beam anneal, an acid vapor catalysis anneal, a base vapor catalysis anneal and a microwave anneal.