Methods and apparatus for forming rhodium-containing layers

• US 7,393,785 B2
• Filed: 04/25/2007
• Issued: 07/01/2008
• Est. Priority Date: 08/26/1998
• Status: Expired due to Fees

• Current Assignee: Micron Technology, Inc.
• Original Assignee: Micron Technology, Inc.
• Inventors: Uhlenbrock, Stefan, Marsh, Eugene P.
• Primary Examiner(s): Le; Thao X.
• Assistant Examiner(s): Tran; Thanh Y
• Application Number:
  US11/789,787
• Publication Number:
  US 20070197031A1
• Time in Patent Office: 433 Days
• Field of Search: 438/681, 438/650, 438/686, 438/575, 438762-763, 438/FOR.347, 438/FOR.361, 427/250, 427/255.17, 427/427, 427/255.18
• US Class Current: 438/681
• CPC Class Codes: C23C 16/16 from metal carbonyl compounds
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: H01L 21/28556 by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD H01L21/28518 - H01L21/28537 and H01L21/28568 take precedence
• CPC Class Codes: H01L 21/28568 the conductive layers comprising transition metals H01L21/28518 takes precedence
• CPC Class Codes: H01L 21/32051 Deposition of metallic or metal-silicide layers
• CPC Class Codes: H01L 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/7687 Thin films associated with contacts of capacitors
• CPC Class Codes: H01L 28/55 with a dielectric comprising a perovskite structure material
• CPC Class Codes: H01L 28/65 comprising a noble metal or a noble metal oxide, e.g. platinum (Pt), ruthenium (Ru), ruthenium dioxide (RuO2), iridium (Ir), iridium dioxide (IrO2)
• CPC Class Codes: H01L 28/75 comprising two or more layers, e.g. comprising a barrier layer and a metal layer
• CPC Class Codes: H10B 12/0335 Making a connection between the transistor and the capacitor, e.g. plug
• CPC Class Codes: H10B 12/312 with a bit line higher than the capacitor

Abstract

A method of forming a rhodium-containing layer on a substrate, such as a semiconductor wafer, using complexes of the formula L_yRhY_z is provided. Also provided is a chemical vapor co-deposited platinum-rhodium alloy barriers and electrodes for cell dielectrics for integrated circuits, particularly for DRAM cell capacitors. The alloy barriers protect surrounding materials from oxidation during oxidative recrystallization steps and protect cell dielectrics from loss of oxygen during high temperature processing steps. Also provided are methods for CVD co-deposition of platinum-rhodium alloy diffusion barriers.

Claims

1. A method of forming a layer on a substrate, the method comprising:

contacting a precursor composition with a surface of a substrate, wherein the precursor composition comprises one or more complexes of the formula;

L_yRhY_z,

wherein;

each L group is independently a neutral or anionic ligand;

each Y group is independently a pi bonding ligand selected from the group of CO, NO, CN, CS, N₂, PX₃, PR₃, P(OR)₃, AsX₃, AsR₃, As(OR)₃, SbX₃, SbR₃, Sb(OR)₃, NH_xR_3-x, CNR, and RCN, wherein R is an organic group, X is a halide, and x=0 to 3;

with the proviso that L is not cyclopentadienyl when Y is CO;

y=1 to 4; and

z=1 to 4.

2. The method of claim 1 wherein the method forms a rhodium-containing layer on the surface of the substrate.

3. The method of claim 2 wherein the rhodium-containing layer is a single transition metal or alloy layer.

4. The method of claim 1 wherein the substrate is a semiconductor substrate or substrate assembly.

5. The method of claim 4 wherein the semiconductor substrate comprises a silicon wafer or a gallium arsenide wafer.

6. The method of claim 1 wherein contacting further comprises vaporizing the precursor composition.

7. The method of claim 6 wherein vaporizing comprises vaporizing in the presence of an inert carrier gas.

8. The method of claim 6 wherein contacting further comprises directing the vaporized precursor composition toward the surface of the substrate using a chemical vapor deposition technique.

9. The method of claim 8 wherein the chemical vapor deposition technique comprises flash vaporization, bubbling, microdroplet formation, or combinations thereof.

10. A method of forming a layer on a substrate, the method comprising:

directing a precursor composition toward a surface of a substrate; and

directing a nonhydrogen reaction gas toward the surface of the substrate,

wherein the precursor composition comprises one or more complexes of the formula;

L_yRhY_z,

wherein;

each L group is independently a neutral or anionic ligand;

each Y group is independently a pi bonding ligand selected from the group of CO, NO, CN, CS, N₂, PX₃, PR₃, P(OR)₃, AsX₃, AsR₃, As(OR)₃, SbX₃, SbR₃, Sb(OR)₃, NH_xR_3-x, CNR, and RCN, wherein R is an organic group, X is a halide, and x=0 to 3;

with the proviso that L is not cyclopentadienyl when Y is CO;

y=1 to 4; and

z=1 to 4.

11. The method of claim 10 wherein the nonhydrogen reaction gas is an oxidizing gas selected from the group of organic peroxides, O₂, O₃, SO₃, H₂O, H₂O₂, nitrogen oxides, RuO₄, and combinations thereof.

12. The method of claim 10 wherein the nonhydrogen reaction gas is a reducing gas selected from the group of NH₃, N₂H₄, and combinations thereof.

13. The method of claim 10 wherein the nonhydrogen reaction gas is selected from the group of SiH₄, Si₂H₆, H₂S, H₂Se, H₂Te, and combinations thereof.

14. A method of manufacturing a semiconductor structure, the method comprising:

directing a vapor of a precursor composition toward a surface of a semiconductor substrate or substrate assembly; and

directing a nonhydrogen reaction gas toward the surface of the semiconductor substrate or substrate assembly,

wherein the precursor composition comprises one or more complexes of the formula;

L_yRhY_z,

wherein;

each L group is independently a neutral or anionic ligand;

each Y group is independently a pi bonding ligand selected from the group of CO, NO, CN, CS, N₂, PX₃, PR₃, P(OR)₃, AsX₃, AsR₃, As(OR)₃, SbX₃, SbR₃, Sb(OR)₃, NH_xR_3-x, CNR, and RCN, wherein R is an organic group, X is a halide, and x=0 to 3;

with the proviso that L is not cyclopentadienyl when Y is CO;

y=1 to 4; and

z=1 to 4.

15. The method of claim 14 wherein each R group is a C₁-C₈ organic group.

16. The method of claim 14 wherein z=1 to 4.

17. The method of claim 14 wherein the precursor composition is a liquid.

18. The method of claim 17 wherein the liquid precursor composition comprises a solid dissolved in a solvent.

19. A chemical vapor deposition apparatus comprising:

a deposition chamber having a substrate positioned therein;

a vessel containing a precursor composition comprising one or more complexes of the formula;

L_yRhY_z,

wherein;

each L group is independently a neutral or anionic ligand;

each Y group is independently a pi bonding ligand selected from the group of CO, NO, CN, CS, N₂, PX₃, PR₃, P(OR)₃, AsX₃, AsR₃, As(OR)₃, SbX₃, SbR₃, Sb(OR)₃, NH_xR_3-x, CNR, and RCN, wherein R is an organic group, X is a halide, and x=0 to 3;

y=1 to 4; and

z=0 to 4;

a source of an inert carrier gas for transferring the precursor composition to the chemical vapor deposition chamber; and

a source of a nonhydrogen reaction gas.

20. A chemical vapor deposition system comprising:

a deposition chamber; and

a vessel containing a precursor composition comprising one or more complexes of the formula;

L_yRhY_z,

wherein;

each L group is independently a neutral or anionic ligand;

each Y group is independently a pi bonding ligand selected from the group of CO, NO, CN, CS, N₂, PX₃, PR₃, P(OR)₃, AsX₃, AsR₃, As(OR)₃, SbX₃, SbR₃, Sb(OR)₃, NH_xR_3-x, CNR, and RCN, wherein R is an organic group, X is a halide, and x=0 to 3;

y=1 to 4; and

z=0 to 4.