Method of forming silicon containing thin films by atomic layer deposition utilizing Si2C16 and NH3

• US 6,528,430 B2
• Filed: 05/01/2001
• Issued: 03/04/2003
• Est. Priority Date: 05/01/2001
• Status: Expired due to Term

• Current Assignee: Samsung Electronics Co. Ltd.
• Original Assignee: Samsung Electronics Co. Ltd.
• Inventors: Chan, Kim Dong, Kwan, Kim Yeong, Won, Lee Joo, Wook, Park Young
• Primary Examiner(s): Niebling, John F.
• Assistant Examiner(s): Simkovic, Viktor
• Application Number:
  US09/847,161
• Publication Number:
  US 20020164890A1
• Time in Patent Office: 672 Days
• Field of Search: 438/763, 438/971, 427/255.18, 427/255.17, 427/255.23, 427/255.28, 427/255.39, 427/255.15, 427/255.393, 117/88, 117/89, 117/93, 117/102, 117/105
• US Class Current: 438/763
• 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 16/45553 characterized by the use of precursors specially adapted for ALD
• 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 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/3185 of siliconnitrides
• CPC Class Codes: Y10S 438/971 Stoichiometric control of host substrate composition

Abstract

An atomic layer deposition (ALD) method employing Si₂Cl₆ and NH₃, or Si₂Cl₆ and activated NH₃ as reactants. In one embodiment, the invention includes the steps of (a) placing a substrate into a chamber, (b) injecting a first reactant containing Si₂Cl₆ into the chamber, (c) chemisorbing a first portion of the first reactant onto the substrate and physisorbing a second portion of the first reactant onto the substrate, d) removing the non-chemically absorbed portion of the first reactant from the chamber, (e) injecting a second reactant including NH₃ into the chamber, (f) chemically reacting a first portion of the second reactant with the chemisorbed first portion of the first reactant to form a silicon-containing solid on the substrate, and (g) removing the unreacted portion of the second reactant from the chamber. In other embodiments, the first reactant can contain two or more compounds containing Si and Cl, such as Si₂Cl₆ and SiCl₄. In another embodiment of the invention, steps b-g are repeated one or more times to increase the thickness of the layer.

Claims

1. An atomic layer deposition method of forming a solid thin film layer containing silicon comprising the steps of:

(a) placing a substrate into a chamber;

(b) injecting a first reactant containing two or more compounds into the chamber, each said compound containing Si and Cl;

(c) chemisorbing a first portion of the first reactant onto the substrate and physisorbing a second portion of the first reactant onto the substrate;

(d) removing the non-chemically absorbed second portion of the first reactant from the chamber;

(e) injecting a second reactant including NH₃ into the chamber;

(f) chemically reacting a first portion of the second reactant with the chemisorbed first portion of the first reactant to form a silicon-containing solid on the substrate; and

,

(g) removing non-reacted portions of the second reactant from the chamber.

2. A method as claimed in claim 1, wherein the silicon-containing solid formed on the substrate comprises Si₃N₄.

3. A method as claimed in claim 1, wherein the silicon-containing solid comprises a Si₃N₄ thin film.

4. A method as claimed in claim 1, wherein a component ratio of N/Si of said silicon-containing solid is between about 1-1.6 inclusive.

5. A method as claimed in claim 1, which further comprises the step of heating the substrate to between 350 and 700°

C.

6. A method as claimed in claim 1, which further comprises the step of pressurizing the chamber to an absolute pressure of 0.01-100 torr.

7. A method as claimed in claim 1, wherein a chamber pressure is maintained at a constant absolute pressure of 0.01-100 torr.

8. A method as claimed in claim 1, which further comprises the step of changing a chamber pressure during implementing at least one of said steps.

9. A method as claimed in claim 1, wherein the silicon-containing solid formed on the substrate has a dry etch selectivity with respect to a silicon material (active mask nitride).

10. A method as claimed in claim 1, wherein the silicon-containing solid formed on the substrate has a dry etch selectivity with respect to a gate material selected from the group consisting of WSix and doped poly-silicon (gate mask nitride).

11. A method as claimed in claim 1, wherein the silicon-containing solid formed on the substrate has a dry etch selectivity with respect to a conductive material selected from the group consisting of W and Ti/TiN (bit line mask nitride).

12. A method as claimed in claim 1, herein the silicon-containing material comprises a chemical mechanical polishing stopping layer.

13. A method as claimed in claim 1, wherein the silicon-containing solid formed on the substrate comprises an insulating layer having a dry etch selectivity with respect to SiO₂.

14. A method as claimed in claim 1, wherein the silicon-containing solid formed on the substrate comprises an insulating layer having an HF-containing solution wet etch selectivity with respect to SiO₂ of a semiconductor device.

15. A method as claimed in claim 1, wherein the silicon-containing solid formed on the substrate comprises a gate dielectric of a semiconductor device.

16. A method as claimed in claim 1, wherein the silicon-containing solid formed on the substrate comprises a layer formed between a Ta₂O₅ layer and a storage node of a capacitor of a semiconductor device.

17. A method as claimed in claim 1, wherein the silicon-containing solid formed on the substrate comprises a dielectric layer of a capacitor of a semiconductor device.

18. A method as claimed in claim 1, wherein the silicon-containing solid formed on the substrate comprises an STI liner of a semiconductor device.

19. A method as claimed in claim 1, wherein the second reactant containing NH₃ includes contains activated NH₃.

20. A method as claimed in claim 1, wherein the plasma power of the remote plasma method is between about 100-3000 watts inclusive.

21. An atomic layer deposition method according to claim 1, which further comprises repeating at least one of steps (b)-(f).

22. An atomic layer deposition method of forming a solid thin film layer containing silicon comprising the steps of:

(a) placing a substrate into a chamber;

(b) injecting a flow of a first reactant containing Si₂Cl₆ into the chamber;

(c) while injecting the first reactant into the chamber, adding SiCl₄ to the flow of the first reactant;

(d) chemisorbing first portions of the Si₂Cl₆ and the SiCl₄ onto the substrate;

(e) removing non-chemically absorbed portions of the second reactant from the chamber;

(f) injecting a second reactant including NH₃ into the chamber;

(g) chemically reacting a first portion of the second reactant with the respective chemisorbed portions of the Si₂Cl₆ and the SiCl₄ to form a silicon-containing solid on the substrate; and

,

(h) removing the non-reacted second portion of the second reactant from the chamber.

23. A method as claimed in claim 22 further comprising the step of repeating at least one of steps (b)-(h).

24. A method as claimed in claim 22, wherein the second reactant containing NH₃ contains activated NH₃.