Method of forming dielectric films, new precursors and their use in semiconductor manufacturing

Patent metadata

Field	Value
Publication number	US-10217629-B2
Application number	US-201815882710-A
Country	US
Kind code	B2
Filing date	Jan 29, 2018
Priority date	Jun 2, 2006
Publication date	Feb 26, 2019
Grant date	Feb 26, 2019

Abstract

Method of deposition on a substrate of a dielectric film by introducing into a reaction chamber a vapor of a precursor selected from the group consisting of Zr(MeCp)(NMe 2 ) 3 , Zr(EtCp)(NMe 2 ) 3 , ZrCp(NMe 2 ) 3 , Zr(MeCp)(NEtMe) 3 , Zr(EtCp)(NEtMe) 3 , ZrCp(NEtMe) 3 , Zr(MeCp)(NEt 2 ) 3 , Zr(EtCp)(NEt 2 ) 3 , ZrCp(NEt 2 ) 3 , Zr(iPr 2 Cp)(NMe 2 ) 3 , Zr(tBu 2 Cp)(NMe 2 ) 3 , Hf(MeCp)(NMe 2 ) 3 , Hf(EtCp)(NMe 2 ) 3 , HfCp(NMe 2 ) 3 , Hf(MeCp)(NEtMe) 3 , Hf(EtCp)(NEtMe) 3 , HfCp(NEtMe) 3 , Hf(MeCp)(NEt 2 ) 3 , Hf(EtCp)(NEt 2 ) 3 , HfCp(NEt 2 ) 3 , Hf(iPr 2 Cp)(NMe 2 ) 3 , Hf(tBu 2 Cp)(NMe 2 ) 3 , and mixtures thereof; and depositing the dielectric film on the substrate.

First claim

What is claimed is:

1. A method of depositing a Group IV metal containing thin film on a substrate, the method comprising
vaporizing a M 1 containing precursor to form a gas phase M 1 source, the M 1 containing precursor having the formula:
(R t Cp) z M 1 R′ 4-z

wherein M 1 is Hf or Zr; z is 1; t is an integer from 0 to 5; Cp is a cyclopentadienyl ligand; each R is independently a C1-C4 linear or branched alkyl or alkylsilylamide; and each R′ is independently a C1-C4 linear or branched alkylamide; and
introducing the gas phase M 1 source and a reactant species into a reaction chamber containing a substrate to deposit the Group IV metal containing thin film on the substrate.

2. The method of claim 1 , wherein t=0 or 1.

3. The method of claim 2 , wherein t=0 and the M 1 containing precursor is selected from the group consisting of ZrCp(NMe 2 ) 3 , ZrCp(NEt 2 ) 3 , ZrCp(NMeEt) 3 , HfCp(NMe 2 ) 3 , HfCp(NEt 2 ) 3 , and HfCp(NMeEt) 3 .

4. The method of claim 3 , wherein the M 1 containing precursor is ZrCp(NMe 2 ) 3 or HfCp(NMe 2 ) 3 .

5. The method of claim 2 , wherein t=1 and the M 1 containing precursor is selected from the group consisting of Zr(MeCp)(NMe 2 ) 3 , Zr(MeCp)(NEt 2 ) 3 , Zr(MeCp)(NMeEt) 3 , Zr(EtCp)(NMe 2 ) 3 , Zr(EtCp)(NEt 2 ) 3 , Zr(EtCp)(NMeEt) 3 , Hf(MeCp)(NMe 2 ) 3 , Hf(MeCp)(NEt 2 ) 3 , Hf(MeCp)(NMeEt) 3 , Hf(EtCp)(NMe 2 ) 3 , Hf(EtCp)(NEt 2 ) 3 , and Hf(EtCp)(NMeEt) 3 .

6. The method of claim 2 , wherein t=1 and R is a C4 linear or branched alkyl.

7. The method of claim 6 , wherein R is a C4 branched alkyl.

8. The method of claim 7 , wherein each R′ is NMe 2 .

9. The method of claim 7 , wherein each R′ is NEt 2 .

10. The method of claim 7 , wherein each R′ is NMeEt.

11. The method of claim 2 , wherein t=1 and R is an alkylsilylamide.

12. The method of claim 11 , wherein each R′ is NMe 2 .

13. The method of claim 11 , wherein each R′ is NEt 2 .

14. The method of claim 11 , wherein each R′ is NMeEt.

15. The method of claim 2 , further comprising introducing a nitrogen-containing fluid into the reaction chamber.

16. The method of claim 15 , wherein the nitrogen-containing fluid is selected from the group consisting of N 2 , NH 3 , hydrazine and its alkyl or aryl derivatives, nitrogen-containing radicals, and mixtures thereof.

17. The method of claim 16 , wherein the nitrogen-containing fluid is NH 3 .

18. The method of claim 15 , wherein the M 1 containing precursor is ZrCp(NMe 2 ) 3 or HfCp(NMe 2 ) 3 .

19. The method of claim 15 , wherein the M 1 containing precursor is selected from the group consisting of Zr(MeCp)(NMe 2 ) 3 , Zr(MeCp)(NEt 2 ) 3 , Zr(MeCp)(NMeEt) 3 , Zr(EtCp)(NMe 2 ) 3 , Zr(EtCp)(NEt 2 ) 3 , Zr(EtCp)(NMeEt) 3 , Hf(MeCp)(NMe 2 ) 3 , Hf(MeCp)(NEt 2 ) 3 , Hf(MeCp)(NMeEt) 3 , Hf(EtCp)(NMe 2 ) 3 , Hf(EtCp)(NEt 2 ) 3 , and Hf(EtCp)(NMeEt) 3 .

20. The method of claim 1 , wherein the M 1 containing precursor is vaporized by introducing to a vaporizer a mixture containing the M 1 containing precursor and a solvent or a solvent mixture.

Assignees

• Air Liquide

Inventors

• Dussarrat Christian
• Blasco Nicolas
• Pinchart Audrey
• Lachaud Christophe

Classifications

• H10P14/69397

  the material containing two or more metal elements · CPC title

• H10P14/69396

  the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium · CPC title

• H10P14/69392

  the material containing hafnium, e.g. HfO2 · CPC title

• H10P14/6339

  deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD · CPC title

• H10P14/6334

  using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition (deposition by physical ablation of a target H10P14/6329) · CPC title