Method for depositing a chlorine-free conformal sin film

• US 8,592,328 B2
• Filed: 03/07/2012
• Issued: 11/26/2013
• Est. Priority Date: 01/20/2012
• Status: Active Grant

• Current Assignee: Novellus Systems Incorporated (Lam Research Corporation)
• Original Assignee: Novellus Systems Incorporated (Lam Research Corporation)
• Inventors: Hausmann, Dennis, Henri, Jon, van Schravendijk, Bart, Srinivasan, Easwar
• Primary Examiner(s): WILCZEWSKI, MARY A
• Application Number:
  US13/414,619
• Publication Number:
  US 20130189854A1
• Time in Patent Office: 629 Days
• Field of Search: 438/792, 427/579, 148/DIG.114, 257/E21.293
• US Class Current: 438/792
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: C23C 16/45542 Plasma being used non-continuously during the ALD reactions
• CPC Class Codes: C23C 16/45544 characterized by the apparatus
• CPC Class Codes: C23C 16/45557 Pulsed pressure or control pressure
• CPC Class Codes: C23C 16/505 using radio frequency discharges
• CPC Class Codes: C23C 16/52 Controlling or regulating the coating process C23C16/45557, C23C16/279 take precedence
• CPC Class Codes: C23C 16/54 Apparatus specially adapted for continuous coating
• CPC Class Codes: H01L 21/0217 the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz H01L21/02126 and H01L21/0214 take precedence
• CPC Class Codes: H01L 21/02219 the compound comprising silicon and nitrogen
• 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 29/7843 the means being an applied insulating layer

Abstract

Described are methods of making silicon nitride (SiN) materials on substrates. Improved SiN films made by the methods are also included. One aspect relates to depositing chlorine (Cl)-free conformal SiN films. In some embodiments, the SiN films are Cl-free and carbon (C)-free. Another aspect relates to methods of tuning the stress and/or wet etch rate of conformal SiN films. Another aspect relates to low-temperature methods of depositing high quality conformal SiN films. In some embodiments, the methods involve using trisilylamine (TSA) as a silicon-containing precursor.

Claims

1. A method of forming a silicon nitride material on a substrate in a reaction chamber, comprising:

periodically exposing the substrate to a vapor phase flow of a halogen-free silicon-containing reactant wherein the halogen-free silicon containing reactant is adsorbed onto the surface of the substrate;

exposing the substrate to a vapor phase flow of a first nitrogen-containing reactant wherein the nitrogen-containing reactant is adsorbed onto the surface of the substrate;

exposing the substrate to a vapor phase flow of a second nitrogen-containing reactant that is different from the first nitrogen-containing reactant, wherein the first nitrogen-containing reactant is carbon-free and the second nitrogen-containing reactant contains carbon; and

periodically igniting a plasma in the reaction chamber when vapor phase nitrogen-containing reactant is present in the reaction chamber and the vapor phase flow of the halogen-free silicon-containing reactant has ceased.

2. The method of claim 1, wherein the halogen-free silicon containing reactant is trisilylamine (TSA).

3. The method of claim 1, wherein the first nitrogen-containing reactant is ammonia, hydrazine, or hydroxylamine.

4. The method of claim 1, wherein the second nitrogen-containing reactant is C_1-10 alkyl amine.

5. The method of claim 4, wherein the second nitrogen-containing reactant is tert-butyl amine.

6. The method of claim 4, wherein the volumetric flow ratio of the first nitrogen-containing reactant to the second nitrogen-containing reactant is between about 1:

1 and 10;

1.

7. The method of claim 6, wherein the volumetric flow ratio of the first nitrogen-containing reactant to the second nitrogen-containing reactant is between about 1:

1 and 4;

1.

8. The method of claim 4, wherein the volumetric flow ratio of the first nitrogen-containing reactant to the second nitrogen-containing reactant is between about 1:

10 and 1;

1.

9. The method of claim 8, wherein the volumetric flow ratio of the first nitrogen-containing reactant to the second nitrogen-containing reactant is between about 1:

4 and 1;

1.

10. The method of claim 1, wherein the substrate includes a germanium-tellurium-antimony alloy.

11. The method of claim 1, wherein the substrate includes a metal surface on which the silicon nitride material is formed.

12. The method of claim 1, wherein the substrate includes an oxide surface on which the silicon nitride material is formed.

13. The method of claim 1, wherein the pressure in the reaction chamber is cycled such that it is higher during the vapor phase flow of the silicon-containing reactant.

14. The method of claim 13, wherein the pressure in the reaction chamber is cycled between a first pressure and a second pressure, the first pressure being between about 5 and 50 Torr and the second pressure between about 1 and 5 Torr.

15. The method of claim 1, wherein the substrate is continuously exposed to the vapor phase flow of the first nitrogen-containing reactant throughout the method.

16. A method of forming a silicon nitride material on a substrate in a reaction chamber, comprising:

periodically exposing the substrate to a vapor phase flow of a silicon-containing reactant wherein the silicon containing reactant is adsorbed onto the surface of the substrate;

exposing the substrate to a vapor phase flow of a first nitrogen-containing reactant wherein the nitrogen-containing reactant is adsorbed onto the surface of the substrate;

exposing the substrate to a vapor phase flow of a second nitrogen-containing reactant that is different from the first nitrogen-containing reactant, wherein the first nitrogen-containing reactant is carbon-free and the second nitrogen-containing reactant contains carbon; and

periodically igniting a plasma in the reaction chamber when vapor phase nitrogen-containing reactant is present in the reaction chamber and the vapor phase flow of the silicon-containing reactant has ceased.

17. The method of claim 16, wherein the plasma is a RF plasma having a power between about 0.15 W/cm² and 0.5 W/cm².

18. The method of claim 16, wherein the plasma is a RF plasma having a power between about 1 W/cm² and 3 W/cm².

19. The method of claim 16, wherein the plasma is a HF-only RF plasma.

20. The method of claim 16, wherein the substrate is periodically exposed to the vapor phase flow of the first nitrogen-containing reactant.