ALD of metal-containing films using cyclopentadienyl compounds

• US 20080102205A1
• Filed: 10/27/2006
• Published: 05/01/2008
• Est. Priority Date: 10/27/2006
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM IP Holding B.V. (ASM International NV)
• Inventors: Barry, Sean T., Wasslen, Yamile A.M., Rahtu, Antti H.
• Granted Patent: US 8,795,771 B2
• Time in Patent Office: Days
• US Class Current: 427/250
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/32 Carbides
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 16/45527 characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
• CPC Class Codes: C23C 16/45536 Use of plasma, radiation or electromagnetic fields
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: C23C 16/513 using plasma jets

Abstract

Atomic layer deposition (ALD) type processes for producing metal containing thin films comprise feeding into a reaction space vapor phase pulses of metal containing cyclopentadienyl precursors as a metal source material. In preferred embodiments the metal containing cyclopentadienyl reactant comprises a metal atom that is not directly bonded to an oxygen or halide atom. In other embodiments the metal atom is bonded to a cyclopentadienyl compound and separately bonded to at least one ligand via a nitrogen atom. In still other embodiments the metal containing cyclopentadienyl compound comprises a nitrogen-bridged ligand.

Claims

1. An atomic layer deposition (ALD) process for producing metal containing thin films comprising alternately and sequentially contacting a substrate in a reaction space with vapor phase pulses of at least one metal containing cyclopentadienyl compound and a second reactant, wherein said cyclopentadienyl compound does not contain a metal directly bonded to a halide or oxygen atom.

2. The process according to claim 1, wherein the metal containing cyclopentadienyl compound does not comprise halide or oxygen atoms.

3. The process according to claim 1, wherein the metal containing cyclopentadienyl compound comprises at least one ligand that is bonded to the metal via nitrogen.

4. The process according to claim 1, wherein the metal containing cyclopentadienyl compound has the formula (R¹R²R³R⁴R⁵Cp)_x-MR⁰_z(R⁶)_y

wherein M is a metal selected from the group consisting of Al, Ga, In, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo, Tc, Ru, Rh, La, Hf, Ta, W, Re, Os, and Ir;

wherein each R¹, R², R³, R⁴, R⁵, and R⁰ is independently selected from;

(i) hydrogen;

(ii) linear and branched C₁-C₂₀ alkyl, alkenyl and alkynyl groups, which are independently substituted or unsubstituted;

(iii) carbocyclic groups, such as aryl, phenyl, cyclopentadienyl, alkylaryl, and halogenated carbocyclic groups; and

(iv) heterocyclic groups;

wherein each R⁶ is independently selected from;

(i) hydrogen;

(ii) linear and branched C₁-C₂₀ alkyl, alkenyl and alkynyl groups, which are independently substituted or unsubstituted;

(iii) carbocyclic groups, such as aryl, preferably phenyl, cyclopentadienyl, alkylaryl, and halogenated carbocyclic groups;

(iv) heterocyclic groups; and

(v) NR¹R²; and

wherein both x and y are ≧

1 and z≧

0.

5. The process according to claim 1, wherein the metal containing cyclopentadienyl compound has the formula:

(R¹R²R³R⁴R⁵Cp)_x-MR⁰_z—

(NR¹R²)_y

wherein M is selected from the group consisting of Al, Ga, In, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo, Tc, Ru, Rh, La, Hf, Ta, W, Re, Os, and Ir;

wherein each R¹, R², R³, R⁴, R⁵, and R⁰ is independently selected from;

(i) hydrogen;

(ii) linear and branched C₁-C₂₀ alkyl, alkenyl and alkynyl groups, which are independently substituted or unsubstituted;

(iii) carbocyclic groups, such as aryl, phenyl, cyclopentadienyl, alkylaryl, and halogenated carbocyclic groups; and

(iv) heterocyclic groups; and

wherein both x and y are ≧

1 and z≧

0.

6. The process according to claim 1, wherein the metal containing cyclopentadienyl compound is depicted by the formula (R¹R²R³R⁴R⁵Cp)_x-MR⁰_z(NR¹NR²R)_y

wherein M is selected from the group consisting of Al, Ga, In, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo, Tc, Ru, Rh, La, Hf, Ta, W, Re, Os, and Ir;

wherein R can be any linear and branched C₁-C₂₀ alkyl, alkenyl, and alkynyl groups, which are independently substituted or unsubstituted and R can be bonded to two bridging nitrogen atoms at any point of alkyl, alkenyl and alkynyl groups;

wherein each R¹, R², R³, R⁴, R⁵, and R⁰ is independently selected from;

(i) hydrogen;

(ii) linear and branched C₁-C₂₀ alkyl, alkenyl and alkynyl groups, which are independently substituted or unsubstituted;

(iii) carbocyclic groups, such as aryl, phenyl, cyclopentadienyl, alkylaryl, and halogenated carbocyclic groups; and

(iv) heterocyclic groups; and

wherein both x and y are ≧

1 and z≧

0.

7. The process according to claims 1, wherein the metal containing cyclopentadienyl compound has the formula (R¹R²R³R⁴R⁵Cp)_x-MR⁰_z—

[(NR¹NR²)CNR³]_y

wherein M is selected from the group consisting of Al, Ga, In, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo, Tc, Ru, Rh, La, Hf, Ta, W, Re, Os, and Ir;

wherein each R¹, R², R³, R⁴, R⁵, and R¹ is independently selected from;

(i) hydrogen;

(ii) linear and branched C₁-C₂₀ alkyl, alkenyl and alkynyl groups, which are independently substituted or unsubstituted;

(iii) carbocyclic groups, such as aryl, phenyl, cyclopentadienyl, alkylaryl, and halogenated carbocyclic groups; and

(iv) heterocyclic groups; and

wherein both x and y are ≧

1 and z≧

0.

8. The process according to claim 1, wherein the metal containing cyclopentadienyl compound is depicted by the formula:

(R¹R²R³R⁴R⁵Cp)_x-MR⁰_z—

[(NR¹NR²)CNR³R⁴]_y

wherein M is selected from the group consisting of Al, Ga, In, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo, Tc, Ru, Rh, La, Hf, Ta, W, Re, Os, and Ir;

wherein each R¹, R², R³, R⁴, R⁵, and R⁰ is independently selected from;

(i) hydrogen;

(ii) linear and branched C₁-C₂₀ alkyl, alkenyl and alkynyl groups, which are independently substituted or unsubstituted;

(iii) carbocyclic groups, such as aryl, phenyl, cyclopentadienyl, alkylaryl, and halogenated carbocyclic groups; and

(iv) heterocyclic groups; and

wherein both x and y are ≧

1 and z≧

0.

9. The process according to claim 1, wherein the metal containing cyclopentadienyl compound is biscyclopentadienyl triisopropylguanidinato titanium (III).

10. The process according to claim 1, wherein the metal containing cyclopentadienyl compound comprises a metal selected from the group consisting of Ti, Zr, Hf, Ta, W, Nb, and Mo.

11. The process according to claim 1, wherein the metal containing cyclopentadienyl compound comprises a metal with a trivalent oxidation state.

12. The process according to claim 1, wherein the metal containing cyclopentadienyl compound comprises a modified cyclopentadienyl group.

13. A process according claim 12, wherein the metal containing cyclopentadienyl compound comprises a modified cyclopentadienyl group selected from the group consisting of Me₅ Cp, MeCp, EtCp, and Me₃SiCp.

14. The process according to claim 1, wherein the metal containing cyclopentadienyl compound further comprises a dianionic guanidinate ligand.

15. The process according to claim 1, wherein the metal containing cyclopentadienyl compound is a titanium cyclopentadienyl compound.

16. The process according to claim 1, wherein the second reactive precursor is a nitrogen containing compound.

17. The process according to claim 16, wherein the nitrogen containing compound is selected from a group consisting of NH₃, N₂ plasma, N₂/H₂ plasma, hydrazine, and/or hydrazine derivatives.

18. An ALD process for producing a metal thin film comprising:

feeding a vapor phase pulse of a first reactant into the reaction chamber, wherein the first reactant is a metal containing cyclopentadienyl compound selected from the group consisting of a) a metal containing cyclopentadienyl compound wherein the metal is not bonded to a halide or oxygen atom;

b) a biscyclopentdienyl triisopropylguanidanato metal compound;

c) a metal containing cyclopentadienyl compound comprising a guanidanato or bidentate ligand and d) a metal cyclopentadienyl compound comprising a nitrogen bridged ligand;

removing the first reactant from the reaction chamber with the aid of an inert gas;

feeding a second reactant into the reaction space;

removing excess second reactant from the reaction chamber with the aid of an inert gas.

19. The process according to claim 19, wherein the metal containing cyclopentadienyl compound is a titanium cyclopentadienyl compound.

20. The process according to claim 19, wherein the second reactant is selected from hydrogen gas or hydrogen plasma.

21. The process according to claim 19, wherein the second reactant is a nitrogen containing compound and the metal thin film is a metal nitride thin film.

22. The process of claim 21, wherein the nitrogen containing compound is selected from the group consisting of ammonia, nitrogen plasma, nitrogen and hydrogen plasma, ammonia plasma, hydrazine, and/or hydrazine derivatives.

23. The process of claim 19, wherein the metal thin film is an elemental metal thin film.

24. The process of claim 23, wherein the second reactant is hydrogen or hydrogen plasma.

25. The process according to claim 19, wherein the second reactant is a reactive carbon containing compound and the metal thin film is a metal carbide thin film.

26. The process according to claim 25, wherein the carbon containing compound is a hydrocarbon.

27. The process according to claim 26, wherein the hydrocarbon is selected from the group consisting of alkanes, alkenes, and alkynes.

28. The process according to claim 25, wherein the carbon containing compound has a central atom selected from the group consisting of elements in group B, Al, Ga, In, Si, Ge, Sn, P, As, or S.

29. The process of claim 19, wherein the thin film is a multicomponent thin film.

30. The process of claim 29 additionally comprising:

a) contacting a substrate with a vapor phase pulse of a third reactant, wherein the third reactant is a metal precursor;

b) removing excess third reactant;

c) contacting the said substrate with a vapor pulse of a fourth reactant; and

d) removing excess fourth reactant.

31. An atomic layer deposition process for deposing a thin film comprising titanium, the process comprising contacting a surface with alternate and sequential vapor phase pulses of a titanium cyclopentadienyl precursor that does not contain a metal directly bonded to halide or oxygen atoms, and a reactant source material.