Oxygen-doping for non-carbon radical-component CVD films

• US 8,980,382 B2
• Filed: 07/15/2010
• Issued: 03/17/2015
• Est. Priority Date: 12/02/2009
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Ingle, Nitin, Mallick, Abhijit Basu, Solis, Earl Osman, Kovarsky, Nicolay, Lyubimova, Olga
• Primary Examiner(s): Padgett, Marianne L
• Application Number:
  US12/836,991
• Publication Number:
  US 20110129616A1
• Time in Patent Office: 1,706 Days
• Field of Search: None
• US Class Current: 427/563
• CPC Class Codes: C23C 16/308 Oxynitrides
• CPC Class Codes: C23C 16/402 Silicon dioxide
• 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 16/45565 Shower nozzles
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: H01J 37/32082 Radio frequency generated discharge H01J37/32357, H01J37/32366, H01J37/32394 and H01J37/32403 take precedence
• CPC Class Codes: H01J 37/32357 Generation remote from the workpiece, e.g. down-stream
• CPC Class Codes: H01J 37/32449 Gas control, e.g. control of the gas flow

Abstract

Methods of forming silicon oxide layers are described. The methods include the steps of concurrently combining both a radical precursor and a radical-oxygen precursor with a carbon-free silicon-containing precursor. One of the radical precursor and the silicon-containing precursor contain nitrogen. The methods result in depositing a silicon-oxygen-and-nitrogen-containing layer on a substrate. The oxygen content of the silicon-oxygen-and-nitrogen-containing layer is then increased to form a silicon oxide layer which may contain very little nitrogen. The radical-oxygen precursor and the radical precursor may be produced in separate plasmas or the same plasma. The increase in oxygen content may be brought about by annealing the layer in the presence of an oxygen-containing atmosphere and the density of the film may be increased further by raising the temperature even higher in an inert environment.

Claims

1. A method of forming a silicon oxide layer on a patterned substrate having a trench in a plasma-free substrate processing region in a substrate processing chamber, the method comprising:

flowing a hydrogen-containing precursor into a first plasma region to produce a radical precursor while flowing an oxygen-containing precursor into a second plasma region to produce a radical-oxygen precursor;

concurrently combining the radical precursor and the radical-oxygen precursor with a carbon-free silicon-containing precursor in the plasma-free substrate processing region, wherein the carbon-free silicon-containing precursor contains nitrogen;

depositing a flowable silicon-oxygen-and-nitrogen-containing layer on the substrate, wherein the flowable silicon-oxygen-and-nitrogen-containing layer flows into the trench on a deposition surface of the patterned substrate as the flowable silicon-oxygen-and-nitrogen-containing layer deposits; and

annealing the silicon-oxygen-and-nitrogen-containing layer at an annealing temperature in an oxygen-containing atmosphere to increase the oxygen-content and decrease the nitrogen-content to form a silicon oxide layer.

2. The method of claim 1 wherein the annealing temperature is between about 500°

C. and about 1100°

C. and the oxygen-containing atmosphere comprises at least one of O₂, O₃, H₂O, H₂O₂, NO, NO₂, N₂O and radical species derived therefrom.

3. The method of claim 1 wherein the first plasma region is the second plasma region so the radical precursor and the radical-oxygen precursor are produced in the same plasma.

4. The method of claim 1 wherein the second plasma region is in a remote plasma system (RPS) located outside the substrate processing chamber and the radical-oxygen precursor enters the plasma-free substrate processing region without passing through the first plasma region.

5. The method of claim 1 wherein the second plasma region is in a remote plasma system (RPS) located outside the substrate processing chamber and the radical-oxygen precursor enters the second plasma region where it is further excited before entering the plasma-free substrate processing region through channels also used by the radical precursor.

6. The method of claim 1 wherein a deposition rate of the flowable silicon-oxygen-and-nitrogen-containing layer is greater than or about 2000 {acute over (Å

)}/min.

7. The method of claim 1 wherein a deposition rate of the flowable silicon-oxygen-and-nitrogen-containing layer is greater than or about 3000 {acute over (Å

)}/min.

8. The method of claim 1 wherein a deposition rate of the flowable silicon-oxygen-and-nitrogen-containing layer is greater than or about 4000 {acute over (Å

)}/min.

9. The method of claim 1 wherein the flowable silicon-oxygen-and-nitrogen-containing layer comprises a carbon-free Si—

O—

N—

H layer.

10. The method of claim 1 wherein the oxygen-containing precursor comprises at least one of O₂, O₃, H₂O, H₂O₂, NO, NO₂, N₂O and radical species derived therefrom.

11. The method of claim 1 wherein a dielectric constant of the silicon oxide film is more consistent across the film compared with a film grown under otherwise similar conditions but without the radical-oxygen precursor.

12. The method of claim 1 wherein the trench has a width of about 50 nm or less and the flowable silicon-oxygen-and-nitrogen-containing layer is flowable during deposition and fills the trench.

13. The method of claim 12 wherein the silicon oxide layer in the trench is substantially void-free.

14. The method of claim 1 wherein the first plasma region is in a remote plasma system (RPS) located outside the substrate processing chamber.

15. The method of claim 1 wherein the first plasma region is a partitioned portion of the substrate processing chamber separated from the plasma-free substrate processing region by a showerhead.

16. The method of claim 1 further comprising an operation of curing the film in an ozone-containing atmosphere while maintaining a temperature below about 400°

C.