ALD of metal silicate films

• US 8,563,444 B2
• Filed: 07/01/2011
• Issued: 10/22/2013
• Est. Priority Date: 10/05/2006
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM America Incorporated (ASM International NV)
• Inventors: Wang, Chang-Gong, Shero, Eric, Wilk, Glen
• Primary Examiner(s): STARK, JARRETT J
• Application Number:
  US13/175,204
• Publication Number:
  US 20110256735A1
• Time in Patent Office: 844 Days
• Field of Search: 438/786, 438/785, 257/E21.625, 257/E21.639
• US Class Current: 438/785
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions

Abstract

Methods for forming metal silicate films are provided. The methods comprise contacting a substrate with alternating and sequential vapor phase pulses of a silicon source chemical, metal source chemical, and an oxidizing agent, wherein the metal source chemical is the next reactant provided after the silicon source chemical. Methods according to some embodiments can be used to form silicon-rich hafnium silicate and zirconium silicate films with substantially uniform film coverages on substrate surface.

Claims

1. An atomic layer deposition (ALD) method for forming a metal silicate film on a substrate in a reaction space, comprising:

a first deposition cycle comprising;

contacting the substrate with a vapor phase pulse of an oxidizing agent;

removing excess oxidizing agent from the reaction space;

contacting the substrate with a vapor phase pulse of a metal halide, wherein the metal comprises hafnium and/or zirconium; and

removing excess metal halide from the reaction space; and

a second deposition cycle comprising;

contacting the substrate with a vapor phase pulse of an oxidizing agent;

removing excess oxidizing agent from the reaction space;

contacting the substrate with a vapor phase pulse of a silicon halide; and

removing excess silicon halide from the reaction space;

wherein the first and second deposition cycles are repeated according to a predetermined ratio to achieve a metal-rich metal silicate film.

2. The method of claim 1, wherein the first and second deposition cycles together comprise a metal silicate deposition cycle.

3. The method of claim 2, further comprising repeating the metal silicate deposition cycle until a film of a desired thickness is achieved.

4. The method of claim 1, wherein the oxidizing agent comprises an agent selected from the group consisting of isopropyl alcohol, methanol, ethanol, a small molecular weight alcohol, NO, N₂O, N₂O₅, oxygen-containing radicals, H₂O, H₂O₂, O₂, O₃, D₂O, and D₂O₂.

5. The method of claim 1, wherein the oxidizing agent comprises water.

6. The method of claim 1, wherein the metal halide is HfCl₄.

7. The method of claim 1, wherein the silicon halide is SiCl₄.

8. The method of claim 1, wherein a ratio between the number of first and second deposition cycles is selected to deposit a metal silicate film with a desired composition.

9. The method claim 1, wherein the silicon halide comprises SiF₄, SiCl₄, SiBr₄, SiI₄, or combinations thereof.

10. The method of claim 1, wherein the metal silicate film is formed at a substrate temperature of about 150°

C. to about 500°

C.

11. The method of claim 1, wherein the metal silicate film is formed at a substrate temperature of about 200°

C. to about 450°

C.

12. The method of claim 1, wherein the metal silicate film is used in a dynamic random access memory (DRAM) device.

13. The method of claim 1, wherein the metal silicate film is used as a gate dielectric in a complementary metal oxide semiconductor (CMOS) device.

14. The method of claim 1, further comprising providing an initial surface termination on the substrate prior to contacting the substrate.

15. An atomic layer deposition (ALD) method for forming a silicon-rich metal silicate film, the method comprising a plurality of cycles, each cycle comprising contacting a substrate in a reaction space with spatially and temporally separated vapor phase pulses of a silicon halide source chemical, a metal source chemical, and an oxidizing agent, wherein the metal source chemical is the next reactant provided after the silicon halide source chemical.