Apparatuses and methods for depositing SiC/SiCN films via cross-metathesis reactions with organometallic co-reactants

• US 8,993,460 B2
• Filed: 01/10/2013
• Issued: 03/31/2015
• Est. Priority Date: 01/10/2013
• Status: Active Grant

• Current Assignee: Novellus Systems Incorporated (Lam Research Corporation)
• Original Assignee: Novellus Systems Incorporated (Lam Research Corporation)
• Inventors: LaVoie, Adrien
• Primary Examiner(s): Toledo, Fernando L
• Assistant Examiner(s): JUNGE, BRYAN R.
• Application Number:
  US13/738,851
• Publication Number:
  US 20140193983A1
• Time in Patent Office: 810 Days
• US Class Current: 438/786
• CPC Class Codes: C23C 16/325 Silicon carbide
• CPC Class Codes: C23C 16/36 Carbonitrides
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 16/45529 specially adapted for making a layer stack of alternating different compositions or gradient compositions
• CPC Class Codes: C23C 16/4554 Plasma being used non-continuously in between ALD reactions C23C16/56 takes precedence
• CPC Class Codes: C23C 16/45542 Plasma being used non-continuously during the ALD reactions
• 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 21/02167 the material being a silicon carbide not containing oxygen, e.g. SiC, SiC:H or silicon carbonitrides H01L21/02126 and H01L21/0214 take precedence
• 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 21/0226 formation by a deposition process per se C23C
• 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

Abstract

Disclosed herein are methods of forming SiC/SiCN film layers on surfaces of semiconductor substrates. The methods may include introducing a silicon-containing film-precursor and an organometallic ligand transfer reagent into a processing chamber, adsorbing the silicon-containing film-precursor, the organometallic ligand transfer reagent, or both onto a surface of a semiconductor substrate under conditions whereby either or both form an adsorption-limited layer, and reacting the silicon-containing film-precursor with the organometallic ligand transfer reagent, after either or both have formed the adsorption-limited layer. The reaction results in the forming of the film layer. In some embodiments, a byproduct is also formed which contains substantially all of the metal of the organometallic ligand transfer reagent, and the methods may further include removing the byproduct from the processing chamber. Also disclosed herein are semiconductor processing apparatuses for forming SiC/SiCN film layers.

Claims

1. A method of forming a SiC/SiCN film layer on a surface of a semiconductor substrate in a processing chamber, the method comprising:

introducing a silicon-containing film-precursor into the processing chamber;

introducing an organometallic ligand transfer reagent into the processing chamber, wherein the organometallic ligand transfer reagent is a metal alkylamine compound that does not contain a halogen atom;

adsorbing the silicon-containing film-precursor, the organometallic ligand transfer reagent, or both onto the surface under conditions whereby either or both form an adsorption-limited layer;

reacting the silicon-containing film-precursor with the organometallic ligand transfer reagent, after either or both have formed the adsorption-limited layer, to form the film layer and a byproduct which contains substantially all of the metal of the organometallic ligand transfer reagent; and

removing the byproduct from the processing chamber.

2. The method of claim 1, wherein the SiC/SiCN film layer is a conformal film layer.

3. The method of claim 2, wherein the surface of the substrate upon which the film is formed has patterned three-dimensional features.

4. The method of claim 1, wherein the silicon-containing film-precursor is a silane which does not contain a halogen atom.

5. The method of claim 4, wherein the silane comprises an alkyl group selected from the methyl, ethyl, propyl, and t-butyl functional groups.

6. The method of claim 5, wherein the silane comprises two alkyl groups selected from the methyl, ethyl, propyl, and t-butyl functional groups.

7. The method of claim 5, wherein the silane is selected from methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane, trimethylsilane, diethylsilane, di-t-butylsilane, allylsilane, sec-butylsilane, thexylsilane, isoamylsilane, t-butyldisilane, and di-t-butyldisilane.

8. The method of claim 4, wherein the silane comprises a first amine group.

9. The method of claim 8, wherein the silane further comprises a second amine group, and wherein the first amine group is substituted with an alkyl group and the second amine group is substituted with an alkyl group.

10. The method of claim 8, wherein the silane is selected from mono-aminosilane, di-aminosilane, tri-aminosilane, tetra-aminosilane, t-butylaminosilane, methylaminosilane, t-butylsilanamine, n-tert-butyltrimethylsilylamine, t-butyl silylcarbamate, SiHCH₃(N(CH₃)₂)₂, SiH(N(CH₃)₂)₃, SiHCl(N(CH₃)₂)₂, Si(CH₃)₂(NH₂)₂, N(SiH₃)₃, and (NR)₂Si(CH₃)₂ where R is selected from H, Me, Et, i-Pr, n-Pr, and t-butyl.

11. The method of claim 1, wherein the silicon-containing film-precursor forms the adsorption-limited layer prior to introducing the organometallic ligand transfer reagent into the processing chamber.

12. The method of claim 1, wherein the organometallic ligand transfer reagent forms the adsorption-limited layer prior to introducing the silicon-containing film-precursor into the processing chamber.

13. The method of claim 1, wherein the alkyl groups of the metal alkylamine compound are selected from the methyl, ethyl, propyl, and t-butyl functional groups.

14. A semiconductor processing apparatus for forming a SiC/SiCN film layer on a surface of a semiconductor substrate, the apparatus comprising:

a processing chamber having a substrate holder within the chamber;

a reactant delivery system fluidically connected to the processing chamber;

one or more vacuum pumps;

one or more gas outlets fluidically connecting the processing chamber to the one or more vacuum pumps; and

a system controller comprising a non-transitory machine readable medium comprising machine readable code, the code comprising;

instructions for operating the reactant delivery system to introduce a silicon-containing film-precursor into the processing chamber so that the silicon-containing film-precursor adsorbs onto a surface of the substrate under conditions whereby the silicon-containing film-precursor forms an adsorption-limited layer;

instructions for operating the reactant delivery system to introduce an organometallic ligand transfer reagent into the processing chamber, wherein the organometallic ligand transfer reagent is a metal alkylamine compound that does not contain a halogen atom, and wherein the organometallic ligand transfer reagent is introduced so that it reacts with the adsorbed silicon-containing film-precursor to form a film layer and a byproduct which contains substantially all of the metal; and

instructions for operating the one or more gas outlets to evacuate the byproduct from the processing chamber.

15. The apparatus of claim 14, wherein the SiC/SiCN film layer is a conformal film layer.

16. The apparatus of claim 15, wherein the surface of the substrate upon which the film is formed has patterned three-dimensional features.

17. The apparatus of claim 14, wherein the silicon-containing film-precursor is a silane which does not contain a halogen atom.

18. The apparatus of claim 17, wherein the silane comprises an alkyl group selected from the methyl, ethyl, propyl, and t-butyl functional groups.

19. The apparatus of claim 18, wherein the silane comprises two alkyl groups selected from the methyl, ethyl, propyl, and t-butyl functional groups.

20. The apparatus of claim 18, wherein the silane is selected from methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane, trimethylsilane, diethylsilane, di-t-butylsilane, allylsilane, sec-butylsilane, thexylsilane, isoamylsilane, t-butyldisilane, and di-t-butyldisilane.

21. The apparatus of claim 17, wherein the silane comprises a first amine group.

22. The apparatus of claim 21, wherein the silane further comprises a second amine group, and wherein the first amine group is substituted with an alkyl group and the second amine group is substituted with an alkyl group.

23. The apparatus of claim 14, wherein the silicon-containing film-precursor forms the adsorption-limited layer prior to introducing the organometallic ligand transfer reagent into the processing chamber.

24. The apparatus of claim 14, wherein the organometallic ligand transfer reagent forms the adsorption-limited layer prior to introducing the silicon-containing film-precursor into the processing chamber.

25. The apparatus of claim 14, wherein the alkyl groups of the metal alkylamine compound are selected from the methyl, ethyl, propyl, and t-butyl functional groups.