Tellurium precursors for GST deposition

• US 8,454,928 B2
• Filed: 09/17/2008
• Issued: 06/04/2013
• Est. Priority Date: 09/17/2007
• Status: Expired due to Fees

• 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: Dussarrat, Christian
• Primary Examiner(s): Li, Jun
• Application Number:
  US12/212,350
• Publication Number:
  US 20090074652A1
• Time in Patent Office: 1,721 Days
• Field of Search: 438/680, 423/508
• US Class Current: 423/508
• CPC Class Codes: C23C 16/305 Sulfides, selenides, or tellurides
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H10N 70/023 by chemical vapor deposition, e.g. MOCVD, ALD
• CPC Class Codes: H10N 70/231 based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
• CPC Class Codes: H10N 70/8828 Tellurides, e.g. GeSbTe

Abstract

A process for depositing a tellurium-containing film on a substrate is disclosed, including (a) providing a substrate in a reactor; (b) introducing into the reactor at least one tellurium-containing precursor having the formula TeL_n or cyclic LTe(-L-)₂TeL, wherein at least one L contains a N bonded to one said Te, “n” is between 2-6, inclusive, and each “L,” is independently selected from certain alkyl and aryl groups. The process further includes (c) optionally, introducing at least one M-containing source, wherein M is Si, Ge, Sb, Sn, Pb, Bi, In, Ag or Se, or a combination of any of those; (d) optionally, introducing a hydrogen-containing fluid; (e) optionally, introducing an oxygen-containing fluid; (f) optionally, introducing a nitrogen-containing fluid; (g) reacting the precursor(s) and M-containing source(s), if any, in the reactor with the hydrogen-, oxygen- and/or nitrogen-containing fluid, if any; and (h) depositing a tellurium-containing film onto the substrate.

Claims

1. A process for depositing a tellurium-containing film on a substrate, comprising:

(a) providing a substrate in a reactor configured for chemical vapor deposition or for atomic layer deposition;

(b) introducing into the reactor at least one tellurium-containing precursor selected from the group consisting of;

Me₂Te=NtBu;

Me₂Te(-NtBu-)₂TeMe₂;

Te(NiPr-CiPr—

NiPr)₂;

MeTe(NiPr-CiPr—

NiPr);

MeTe(NiPr—

C(—

NMe₂)-NiPr);

Te(MeN—

CH₂—

CH₂—

NMe₂);

TeMe(MeN—

CH₂—

CH₂—

NMe₂);

Te(EtN—

CH₂—

CH₂—

NMe₂);

TeMe(EtN—

CH₂—

CH₂—

NMe₂);

Te(MeN—

CMe₂—

CH₂—

NMe₂);

TeMe(MeN—

CMe₂-CH₂—

NMe₂);

Te(MeN—

CH₂—

CH₂—

OMe);

TeMe(MeN—

CH₂—

CH₂—

OMe);

(tBuN═

)Te(-NtBu-)₂Te(=NtBu); and

(iPrN═

)Te(-NiPr-)₂Te(=NiPr);

(c) optionally, introducing at least one M-containing source, wherein M is Si, Ge, Sb, Sn, Pb, Bi, In, Ag or Se, or a combination of any of those, into said reactor;

(d) optionally, introducing a hydrogen-containing fluid into the reactor;

(e) optionally, introducing an oxygen-containing fluid into the reactor;

(f) optionally, introducing a nitrogen-containing fluid into the reactor;

(g) reacting the precursor(s) and M-containing source(s), if any, in the reactor with the hydrogen-, and/or oxygen- and/or nitrogen-containing fluid(s), if any; and

(h) depositing a tellurium-containing film onto the substrate.

2. The process of claim 1, wherein, in (h), said depositing is carried out at a temperature between 200°

C. and 600°

C.

3. The process of claim 1, wherein, in (h), said depositing is carried out at a pressure between 1 Pa and 100000 Pa.

4. The process of claim 1, wherein at least one said tellurium-containing precursor has a melting point below 100°

C.

5. The process of claim 1, wherein at least one said tellurium-containing precursor has a melting point below 50°

C.

6. The process of claim 1, wherein at least one said tellurium-containing precursor is liquid at room temperature.

7. The process of claim 1, wherein, in (b), said introducing comprises mixing together at least two of said tellurium-containing precursors to provide a precursor mixture, and introducing said mixture into the reactor.

8. The process of claim 1, wherein, (c) comprises introducing into said reactor at least one germanium source selected from the group consisting of trigermylamine, germane, digermane, and aminogermane compounds of the formula GeR_x(NR¹R²)_4-x, wherein x is between 0 and 4, inclusive, and R, R¹ and R² are independently H or a linear, branched or cyclic C₁-C₆ carbon chain.

9. The process of claim 8, wherein said germanium source is selected from the group consisting of tetrakis(dimethylamino)germane (Ge(NMe₂)₄), tris(dimethylamino)germane (GeH(NMe₂)₃), bis(diethylamino)germane (GeH₂(NEt₂)₂) and mixtures of any of those.

10. The process of claim 1, wherein (c) comprises introducing into said reactor at least one antimony source selected from the group consisting of trimethylantimony, dimethylantimony hydride, SbCl₃, SbCl₅, and amidoantimony compounds of the formula SbR_x(NR¹R²)₃, wherein x is between 0 and 3, inclusive, and R¹ and R² are independently H or a linear, branched or cyclic C₁-C₆ carbon chain, and mixtures of any of those.

11. The process of claim 1, wherein (c) comprises introducing into said reactor at least one bismuth source selected from the group consisting of BiCl₃, Bi(NMe₂)₃, Bi(NEt₂)₃, Bi(NEt₂)₃, and Bi(═

NR¹)(NR²R³)₃, wherein each R¹ and R² are independently H or a linear, branched or cyclic C₁-C₆ carbon chain, and mixtures of any of those.

12. The process of claim 1, wherein (c) comprises introducing into said reactor at least one tin source selected from the group consisting of stannane, SnCl₄ and aminotin compounds having the formula SnR_x(NR¹R²)_4-x wherein x is between 0 and 4, inclusive, and R, R¹ and R² are independently H or a linear, branched or cyclic C₁-C₆ carbon chain, and mixtures of any of those.

13. The process of claim 12, wherein one said tin source is selected from the group consisting of tetrakis(dimethylamino)tin (Sn(NMe₂)₄), tris(dimethylamino)tin (SnH(NMe₂)₃) and mixtures thereof.

14. The process of claim 1, wherein (c) comprises introducing into said reactor at least one silicon source selected from the group consisting of trisilylamine, silane, disilane, trisilane, aminosilanes of the formula SiR_x(NR¹R²)_4-x wherein x is between 0 and 4, inclusive, and R, R¹ and R² are independently H or a linear, branched or cyclic C₁-C₆ carbon chain.

15. The process of claim 14, wherein one said silicon source is selected from the group consisting of tetrakis(dimethylamino)silane (Si(NMe₂)₄), tris(dimethylamino)silane (SiH(NMe₂)₃), bis(diethylamino)silane (SiH₂(NEt₂)₂) and mixtures of any of those.

16. The process of claim 1, wherein, in (d), said hydrogen-containing fluid is selected from the group consisting of H₂, NH₃, hydrazine and its alkyl or aryl derivatives, H⁺, NH⁺, and NH₂⁺ radicals, and mixtures of any of those.

17. The process of claim 1, wherein in (f), said nitrogen-containing fluid is selected from the group consisting of N₂, NH₃, hydrazine and its alkyl or aryl derivatives, N⁺, NH⁺ and NH₂⁺ radicals, and mixtures of any of those.

18. The process of claim 1, wherein (h) comprises depositing said tellurium-containing film onto the substrate at a temperature between 350°

C. and 550°

C.

19. The process of claim 1, wherein said introducing comprises performing (b) and (c)-(f), simultaneously, and said reactor is configured for chemical vapor deposition.

20. The process of claim 1, wherein said introducing comprises performing (b) and (c)-(f), sequentially, and said reactor is configured for atomic layer deposition.

21. The process of claim 1, wherein (b) and (c) are performed together in one pulse and (d) is performed in a separate pulse, for modified atomic layer deposition.

22. The process of claim 1, wherein, in (d), hydrogen gas is continuously introduced and (b) and (c) comprise introducing said tellurium or M-containing source by pulsing, for pulsed chemical vapor deposition.