Tellurium precursors for film deposition

• US 8,802,194 B2
• Filed: 06/24/2011
• Issued: 08/12/2014
• Est. Priority Date: 05/29/2008
• Status: Active Grant

• Current Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Original Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Inventors: Ishii, Hana, Gatineau, Julien
• Primary Examiner(s): TUROCY, DAVID P
• Application Number:
  US13/168,535
• Publication Number:
  US 20120021590A1
• Time in Patent Office: 1,145 Days
• Field of Search: 427/255.29, 427/58, 427/96.8
• US Class Current: 427/255.29
• CPC Class Codes: C23C 14/0623 Sulfides, selenides or tellurides
• CPC Class Codes: C23C 16/305 Sulfides, selenides, or tellurides
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions

Abstract

Methods and compositions for depositing a tellurium-containing film on a substrate are disclosed. A reactor and at least one substrate disposed in the reactor are provided. A tellurium-containing precursor is provided and introduced into the reactor, which is maintained at a temperature ranging from approximately 20° C. to approximately 100° C. Tellurium is deposited on to the substrate through a deposition process to form a thin film on the substrate.

Claims

1. A method of forming a tellurium-containing film on a substrate, comprising:

a) providing a reactor and at least one substrate disposed therein;

b) introducing a tellurium-containing precursor into the reactor, wherein the tellurium-containing precursor is selected from the group consisting of (Me₃Ge)₂Te, (Et₃Ge)₂Te, (iPr₃Ge)₂Te, (tBu₃Ge)₂Te, (Me₂tBuGe)₂Te, ((Me₃Si)₃Ge)₂Te, (Me₃Ge)Te(Si(SiMe₃)₃), and ((Me₃Si)₃Ge)₂Te;

c) Maintaining the reactor at a temperature ranging from approximately 20°

C. to approximately 100°

C.; and

d) Depositing at least part of the tellurium-containing precursor onto the substrate to form a tellurium-containing film by a vapor deposition method.

2. The method of claim 1, wherein the tellurium-containing precursor is (Me₃Ge)₂Te.

3. The method of claim 1, further comprising introducing at least on reducing gas into the reactor, wherein the reducing gas is selected from the group consisting of:

H₂, NH₃, SiH₄, Si₂H₆, Si₃H₈, plasma excited radicals thereof, and mixtures thereof.

4. The method of claim 1, further comprising introducing a second precursor and depositing at least part of the second precursor onto the substrate, the second precursor comprising an element selected from Group 13 to 16 of the Periodic Table, wherein the tellurium-containing film further comprises the element.

5. The method of claim 4, wherein the element is selected from the group consisting of Ge, Sb, Se, S, O, As, P, N, Sn, Si, In, Ga, Al, and B.

6. The method of claim 5, wherein the second precursor is selected from the group consisting of SbCl₃, SbCl₅, Sb(OMe)₃, Sb(OEt)₃, Sb(NMe₂)₃, Sb(NEt₂)₃, Sb(NMeEt)₃, (Me₃Si)₃Sb, and (Et₃Si)₃Sb.

7. The method of claim 5, wherein the second precursor is selected from the group consisting of GeCl₂-dioxane, GeCl₂-adducts, Ge(OMe₂)₄, Ge(OEt)₄, Ge(NMe₂)₄, Ge(NEt₂)₄, and Ge(NMeEt)₄.

8. The method of claim 4, wherein the vapor deposition method is atomic layer deposition or chemical vapor deposition.

9. The method of claim 4, further comprising introducing a third precursor and depositing at least part of the third precursor onto the substrate, the third precursor comprising an element selected from Group 13 to 16 of the Period Table, wherein the tellurium-containing film further comprises the element of the second precursor and the element of the third precursor.

10. The method of claim 9, wherein the element of the third precursor is selected from the group consisting of Ge, Sb, Se, S, O, As, P, N, Sn, Si, In, Ga, Al, and B.

11. The method of claim 9, wherein the vapor deposition method is atomic layer deposition or chemical vapor deposition.

12. The method of claim 11, wherein the vapor deposition method is atomic layer deposition (ALD) and one of the second precursor or the third precursor is a Ge-containing precursor, the method further comprising increasing a Ge content in the tellurium-containing film by introducing a second pulse of the Ge-containing precursor during one ALD cycle.

13. The method of claim 12, where in the Ge-containing precursor is selected from the group consisting GeCl₂-dioxane, GeCl₂-adducts, Ge(OMe₂)₄, Ge(OEt)₄, Ge(NMe₂)₄, Ge(NEt₂)₄, and Ge(NMeEt)₄.

14. The method of claim 1, further comprising annealing the tellurium-containing film.

15. A method of forming a GST film on a substrate, the method comprising introducing into an ALD reactor containing a substrate sequential pulses of a Sb-containing precursor, a Ge-containing precursor, and a Te-containing precursor, each ALD cycle comprising one pulse of the Sb-containing precursor and the Ge-containing precursor and at least two pulses of the Te containing precursor, wherein the Te-containing precursor is selected from the group consisting of (Me₃Ge)₂Te, (Et₃Ge)₂Te, (iPr₃Ge)₂Te, (tBu₃Ge)₂Te, (Me₂tBuGe)₂Te, ((Me₃Si)₃Ge)₂Te, (Me₃Ge)Te(Si(SiMe₃)₃), and ((Me₃Si)₃Ge)₂Te.

16. The method of claim 15, wherein the Sb-containing precursor is selected from the group consisting of SbCl₃, SbCl₅, Sb(OMe)₃, Sb(OEt)₃, Sb(NMe₂)₃, Sb(NEt₂)₃, Sb(NMeEt)₃, (Me₃Si)₃Sb, and (Et₃Si)₃Sb.

17. The method of claim 15, wherein the Ge-containing precursor is selected from the group consisting of GeCl₂-dioxane, GeCl₂-adducts, Ge(OMe₂)₄, Ge(OEt)₄, Ge(NMe₂)₄, Ge(NEt₂)₄, and Ge(NMeEt)₄.

18. The method of claim 15, the GST film comprising between approximately 45 atomic % and approximately 55 atomic % Te, between approximately 15 atomic % and approximately 20 atomic % Sb, and between approximately 10 atomic % and approximately 20 atomic % Ge.

19. The method of claim 15, wherein one ALD cycle further comprises a second pulse of the Ge-containing precursor.

20. The method of claim 15, wherein the tellurium-containing precursor is (Me₃Ge)₂Te.