Process for producing zirconium oxide thin films

• US 7,754,621 B2
• Filed: 09/28/2007
• Issued: 07/13/2010
• Est. Priority Date: 04/14/2000
• Status: Expired due to Fees

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM International NV
• Inventors: Putkonen, Matti
• Primary Examiner(s): WILCZEWSKI, MARY A
• Application Number:
  US11/864,663
• Publication Number:
  US 20080014762A1
• Time in Patent Office: 1,019 Days
• Field of Search: 438/778, 438/785, 427/255.19, 427/255.28, 427/255.31, 427/255.36
• US Class Current: 438/785
• 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
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01L 21/02189 the material containing zirconium, e.g. ZrO2
• CPC Class Codes: H01L 21/02192 the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium
• CPC Class Codes: H01L 21/02194 the material containing more than one metal element
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/28167 on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
• CPC Class Codes: H01L 21/28194 by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition H01L21/28202 takes precedence
• CPC Class Codes: H01L 21/28211 in a gaseous ambient using an oxygen or a water vapour, e.g. RTO, possibly through a layer H01L21/28194 and H01L21/28202 take precedence
• CPC Class Codes: H01L 21/3141 Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/31604 Deposition from a gas or vapour H01L21/31691, H01L21/31695 take precedence
• CPC Class Codes: H01L 21/31641 Deposition of Zirconium oxides, e.g. ZrO2
• CPC Class Codes: H01L 29/517 the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate H01L29/518 takes precedence
• CPC Class Codes: H01M 8/1253 the electrolyte containing zirconium oxide
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

This invention concerns a process for producing oxide thin film on a substrate by an ALD type process. According to the process, alternating vapor-phase pulses of at least one metal source material, and at least one oxygen source material are fed into a reaction space and contacted with the substrate. According to the invention, an yttrium source material and a zirconium source material are alternately used as the metal source material so as to form an yttrium-stabilized zirconium oxide (YSZ) thin film on a substrate.

Claims

1. An atomic layer deposition method for forming a film on a substrate, comprising:

providing the substrate in a reaction space;

depositing a zirconium oxide film on the substrate by exposing the substrate in the reaction space to temporally separated pulses of a zirconium-containing material and an oxygen-containing material, wherein the zirconium source material comprises a ligand selected from the group consisting of a cyclopentadienyl and a cyclopentadienyl derivative; and

maintaining the substrate at a temperature below a decomposition temperature of the zirconium-containing material during depositing the zirconium oxide film.

2. The method of claim 1, wherein the zirconium-containing material comprises two or more ligands selected from the group consisting of a cyclopentadienyl and a cyclopentadienyl derivative.

3. The method of claim 2, wherein the zirconium-containing material comprises zirconium with R and X groups as ligands, wherein

R is selected from the group consisting of a cyclopentadienyl and a cyclopentadienyl derivative;

and

X is selected from the group consisting of F, Cl, Br, I, H, a linear alkyl group, a branched alkyl group, a linear alkoxide, a branched alkoxide, an amine and an acetate.

4. The method of claim 3, wherein the linear or branched alkyl groups comprise a 1-10 carbon hydrocarbon chain.

5. The method of claim 3, wherein the linear alkoxide is a methoxy group.

6. The method of claim 3, wherein the linear alkyl group is a methyl group.

7. The method of claim 3, wherein the zirconium-containing material comprises two different X groups.

8. The method of claim 7, wherein a first X group is a methyl group and a second X group is a methoxy group.

9. The method of claim 3, wherein the ligands R are bridged together.

10. The method of claim 9, wherein the ligands R are bridged together with a bridge selected from the group consisting of a methyl group, an alkyl group, and a substituted hydrocarbon.

11. The method of claim 3, wherein the cyclopentadienyl derivative has the general formula C₅H_5-yR′

″

_y, wherein

R′

″

is selected from the group consisting of a linear alkyl group, a branched alkyl group, an alkoxy group, an aryl group, an amino group, a cyano group, and a silyl group; and

y is an integer between 1 and 5.

12. The method of claim 11, wherein the linear or branched alkyl groups comprise a 1-10 carbon hydrocarbon chain.

13. The method of claim 11, wherein the linear alkyl group is a methyl group.

14. The method of claim 3, wherein the cyclopentadienyl derivative comprises a ligand R′

″

, wherein R′

″

is selected from the group consisting of a linear alkyl or a branched alkyl group.

15. The method of claim 14, wherein the linear alkyl group is a methyl group.

16. The method of claim 1, wherein the oxygen-containing material comprises O₃.

17. The method of claim 1, wherein the oxygen-containing material comprises H₂O.

18. The method of claim 1, wherein the oxygen-containing material is one or more precursors selected from the group consisting of an oxide of nitrogen, a halide-oxygen compound, a peracid, an alkoxide, an alcohol and an oxygen-containing radical.

19. The method of claim 18, wherein the oxygen-containing radical is an oxygen radical or a hydroxyl radical.

20. The method of claim 1, wherein depositing the zirconium oxide film is performed at a deposition temperature in a range between 250 and 500°

C.

21. The method of claim 20, wherein depositing the zirconium oxide film is performed at a deposition temperature in a range between 275°

C. and 325°

C.

22. The method of claim 1, further comprising exposing the substrate to pulses of a yttrium-containing material to form a yttrium-stabilized zirconium oxide film.

23. The method of the claim 22, wherein exposing the substrate in the reaction space to temporally separated pulses of the zirconium-containing material, the oxygen-containing material and the yttrium-containing material constitute a cycle, further comprising performing a plurality of cycles.