Method of plasma activated deposition of a conformal film on a substrate surface

• US 8,728,955 B2
• Filed: 03/01/2012
• Issued: 05/20/2014
• Est. Priority Date: 02/14/2012
• Status: Active Grant

• Current Assignee: Novellus Systems Incorporated (Lam Research Corporation)
• Original Assignee: Novellus Systems Incorporated (Lam Research Corporation)
• Inventors: LaVoie, Adrien, Saly, Mark J., Moser, Daniel, Odedra, Rajesh, Konjolia, Ravi
• Primary Examiner(s): Smith, Zandra
• Assistant Examiner(s): DUONG, KHANH B
• Application Number:
  US13/409,212
• Publication Number:
  US 20130210241A1
• Time in Patent Office: 810 Days
• Field of Search: None
• US Class Current: 438/765
• CPC Class Codes: C23C 16/045 Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: C23C 16/4554 Plasma being used non-continuously in between ALD reactions C23C16/56 takes precedence
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: C23C 16/52 Controlling or regulating the coating process C23C16/45557, C23C16/279 take precedence
• CPC Class Codes: H01L 21/02164 the material being a silicon oxide, e.g. SiO2
• 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 21/02211 the compound being a silane, e.g. disilane, methylsilane or chlorosilane
• 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 21/0234 treatment by exposure to a plasma
• CPC Class Codes: H01L 21/02348 treatment by exposure to UV light
• CPC Class Codes: H01L 21/31116 by dry-etching
• CPC Class Codes: H01L 21/76826 by contacting the layer with gases, liquids or plasmas
• CPC Class Codes: H01L 21/76829 characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
• CPC Class Codes: H01L 21/76837 Filling up the space between adjacent conductive structures; Gap-filling properties of dielectrics
• CPC Class Codes: H01L 21/76898 formed through a semiconductor substrate

Abstract

A method of depositing a film on a substrate surface includes providing a substrate in a reaction chamber; selecting a silicon-containing reactant from a precursor group consisting of di-tert-butyl diazidosilane, bis(ethylmethylamido)silane, bis(diisopropylamino)silane, bis(tert-butylhydrazido)diethylsilane, tris(dimethylamido)silylazide, tris(dimethylamido)silylamide, ethylsilicon triazide, diisopropylaminosilane, and hexakis(dimethylamido)disilazane; introducing the silicon-containing reactant in vapor phase into the reaction chamber under conditions allowing the silicon-containing reactant to adsorb onto the substrate surface; introducing a second reactant in vapor phase into the reaction chamber while the silicon-containing reactant is adsorbed on the substrate surface, and wherein the second reactant is introduced without first sweeping the silicon-containing reactant out of the reaction chamber; and exposing the substrate surface to plasma to drive a reaction between the silicon-containing reactant and the second reactant on the substrate surface to form the film.

Claims

1. A method of depositing a film on a substrate surface, comprising:

providing a substrate in a reaction chamber;

selecting a silicon-containing reactant from a precursor group consisting of di-tert-butyl diazidosilane, tris(dimethylamido)silylazide, and bis(tert-butylhydrazido)diethylsilane;

introducing the silicon-containing reactant in vapor phase into the reaction chamber; and

introducing a second reactant in vapor phase into the reaction chamber.

2. The method of claim 1, further comprising:

introducing the silicon-containing reactant under conditions allowing the silicon-containing reactant to adsorb onto the substrate surface; and

exposing the substrate surface to plasma to drive a reaction between the silicon-containing reactant and the second reactant on the substrate surface to form the film.

3. The method of claim 1, further comprising introducing the second reactant into the reaction chamber while the silicon-containing reactant is adsorbed on the substrate surface and without first sweeping the silicon-containing reactant out of the reaction chamber.

4. The method of claim 1, further comprising flowing the second reactant to the substrate surface at one of a constant flow rate, a non-constant flow rate and an intermittent flow rate.

5. The method of claim 1, wherein:

the film comprises SiN;

the film forms a conformal structure; and

deposition of the film is performed at a temperature less than or equal to 400°

C.

6. A method of depositing a film on a substrate surface, comprising:

(a) providing a substrate in a reaction chamber,

(b) selecting a silicon-containing reactant from a precursor group consisting of di-tert-butyl diazidosilane, bis(ethylmethylamido)silane, bis(diisopropylamino)silane, bis(tert-butylhydrazido)diethylsilane, tris(dimethylamido)silylazide, tris(dimethylamido)silylamide, ethylsilicon triazide, diisopropylaminosilane, and hexakis(dimethylamido)disilazane;

(c) introducing the silicon-containing reactant in vapor phase into the reaction chamber under conditions allowing the silicon-containing reactant to adsorb onto the substrate surface;

(d) introducing a second reactant in vapor phase into the reaction chamber while the silicon-containing reactant is adsorbed on the substrate surface, wherein the second reactant is introduced without first sweeping the silicon-containing reactant out of the reaction chamber;

(e) exposing the substrate surface to plasma to drive a reaction between the silicon-containing reactant and the second reactant on the substrate surface to form the film; and

(f) sweeping out the second reactant in vapor phase prior to (e).

7. The method of claim 6, wherein the plasma is ignited while at least one of the silicon-containing reactant and the second reactant is in a gas phase while being exposed to the substrate.

8. The method of claim 6, wherein the silicon-containing reactant and the second reactant do not react with one another in the vapor phase.

9. The method of claim 6, wherein:

the film comprises SiN film; and

deposition of the film is performed at a temperature less than or equal to 400°

C.

10. The method of claim 6, further comprising flowing the second reactant to the substrate surface at a non-constant flow rate during (d).

11. The method of claim 6, wherein the silicon-containing reactant and the second reactant co-exist in vapor phase, and wherein the silicon-containing reactant and the second reactant do not appreciably react with one another until exposure to plasma in (e).

12. The method of claim 6, wherein the film formed in (e) forms a conformal structure.

13. The method of claim 6, further comprising, after (e), depositing additional film directly on a portion of the film by chemical vapor deposition.

14. The method of claim 6, further comprising flowing the second reactant to the substrate surface at one of a constant flow rate, a non-constant flow rate and an intermittent flow rate.

15. A method of depositing a film on a substrate surface, comprising:

(a) providing a substrate in a reaction chamber;

(b) selecting a silicon-containing reactant from a precursor group consisting of di-tert-butyl diazidosilane, bis(ethylmethylamido)silane, bis(diisopropylamino)silane, bis(tert-butylhydrazido)diethylsilane, tris(dimethylamido)silylazide, tris(dimethylamido)silylamide, ethylsilicon triazide, diisopropylaminosilane, and hexakis(dimethylamido)disilazane;

(c) introducing the silicon-containing reactant in vapor phase into the reaction chamber under conditions allowing the silicon-containing reactant to adsorb onto the substrate surface;

(d) introducing a second reactant in vapor phase into the reaction chamber while the silicon-containing reactant is adsorbed on the substrate surface;

(e) exposing the substrate surface to plasma to drive a reaction between the silicon-containing reactant and the second reactant on the substrate surface to form the film; and

(f) exposing the substrate surface to the second reactant after sweeping the silicon-containing reactant out of the reaction chamber but prior to (e).