Synthesis and use of precursors for ALD of tellurium and selenium thin films

Patent metadata

Field	Value
Publication number	US-10308673-B2
Application number	US-201715711690-A
Country	US
Kind code	B2
Filing date	Sep 21, 2017
Priority date	Apr 25, 2008
Publication date	Jun 4, 2019
Grant date	Jun 4, 2019

Abstract

Atomic layer deposition (ALD) processes for forming Te-containing thin films, such as Sb—Te, Ge—Te, Ge—Sb—Te, Bi—Te, and Zn—Te thin films are provided. ALD processes are also provided for forming Se-containing thin films, such as Sb—Se, Ge—Se, Ge—Sb—Se, Bi—Se, and Zn—Se thin films are also provided. Te and Se precursors of the formula (Te,Se)(SiR 1 R 2 R 3 ) 2 are preferably used, wherein R 1 , R 2 , and R 3 are alkyl groups. Methods are also provided for synthesizing these Te and Se precursors. Methods are also provided for using the Te and Se thin films in phase change memory devices.

First claim

We claim:

1. A process for forming a Te and/or Se containing thin film on a substrate in a reaction chamber comprising a plurality of deposition cycles, each cycle comprising in order:
contacting the substrate with a first vapor phase reactant comprising a metal halide, wherein the metal in the metal halide is selected from the group consisting of Sb, Ge, Bi, Zn, Cu, In, Ag, Au, Pb, Cd, and Hg;
removing excess first reactant with the aid of a purge gas;
contacting the substrate with a second vapor phase reactant, wherein the second reactant comprises Te(SiR 1 R 2 R 3 ) 2 or Se(SiR 1 R 2 R 3 ), wherein R 1 , R 2 , and R 3 are alkyl groups with one or more carbon atoms; and
removing excess second reactant with the aid of a purge gas.

2. The method of claim 1 , wherein the first reactant comprises SbCl 3 .

3. The method of claim 1 , wherein the first reactant comprises GeBr 2 or GeCl 2 —C 4 H 8 O 2 .

4. The method of claim 1 , wherein the first reactant comprises GeX 2 , wherein X is a halogen.

5. The method of claim 1 , wherein the second reactant is Te(SiEt 3 ) 2 , Te(SiMe 3 ) 2 , Se(SiEt 3 ) 2 , or Se(SiMe 3 ) 2 .

6. The method of claim 1 , wherein the Te or Se in the second reactant has an oxidation state of −2.

7. The method of claim 1 , wherein the thin film comprises one or more of Sb—Te, Ge—Te, Ge—Sb—Te, Bi—Te, or Zn—Te doped with one or more dopants comprising O, N, Si, S, In, Ag, Sn, Au, As, Bi, Zn, Se, Te, Ge, Sb, and Mn.

8. The method of claim 1 , wherein the thin film comprises Sb—Te.

9. The method of claim 8 , wherein the plurality of deposition cycles comprises a plurality of Sb—Te deposition cycles in which the first reactant comprises Sb and the second reactant comprises Te.

10. The method of claim 1 , wherein the thin film comprises Ge—Te.

11. The method of claim 1 , wherein the plurality of deposition cycles comprises a plurality of Ge—Te deposition cycles in which the first reactant comprises Ge and the second reactant comprises Te.

12. The method of claim 1 , wherein the thin film comprises Ge—Sb—Te.

13. The method of claim 12 , wherein the plurality of deposition cycles comprises a plurality of Sb—Te deposition cycles in which the first reactant comprises Sb and the second reactant comprises Te and a plurality of Ge—Te deposition cycles in which the first reactant comprises Ge and the second reactant comprises Te.

14. The method of claim 13 , wherein the Ge—Te deposition cycles and Sb—Te deposition cycles are performed at a 1:1 ratio.

15. The method of claim 1 , wherein the first reactant comprises Bi and the deposited film comprises Bi—Te.

16. The method of claim 1 , wherein the first reactant comprises Zn and the deposited film comprises Zn—Te.

17. The method of claim 1 , wherein the first reactant comprises Bi and the deposited film comprises Bi—Se.

18. The method of claim 1 , wherein the first reactant comprises Cu and the deposited film comprises Cu—Se.

19. The method of claim 1 , wherein the thin film is part of a phase change memory device.

20. The method of claim 1 , wherein the thin film forms part of a solar cell absorber.

Assignees

• Asm Int Nv

Inventors

• Pore Viljami
• Hatanpaa Timo
• Ritala Mikko
• Leskelä Markku

Classifications

• H10P14/3432

  Tellurides · CPC title

• H10P14/3431

  Selenides · CPC title

• H10P14/24 Primary

  using chemical vapour deposition [CVD] · CPC title

• C07F11/005 Primary

  compounds without a metal-carbon linkage · CPC title

• C23C16/306 Primary

  AII BVI compounds, where A is Zn, Cd or Hg and B is S, Se or Te · CPC title