Controlled nano-doping of ultra thin films

• US 7,544,398 B1
• Filed: 04/26/2006
• Issued: 06/09/2009
• Est. Priority Date: 04/26/2005
• Status: Expired due to Fees

• Current Assignee: Novellus Systems Incorporated (Lam Research Corporation)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Lesser, Karl, Chang, Jane P., Van, Trinh Tu, Deshpandey, Chandra, Chiang, Tony
• Primary Examiner(s): CHEN, BRET P
• Application Number:
  US11/411,425
• Time in Patent Office: 1,140 Days
• Field of Search: 427/250, 427/535, 427/537, 427/539, 117/84, 117/103, 117/108
• US Class Current: 427/537
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/452 by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions

Abstract

The invention relates to methods for producing doped thin layers on substrates comprising the steps of depositing a dopant precursor on the substrate via an atomic layer deposition technique; and exposing the deposited dopant precursor to radicals. The methods can further comprise depositing a compound adjacent the dopant metal via an atomic layer deposition technique; and exposing the deposited compound to radicals, thereby providing a host. The invention relates to articles comprising approximately atomically thin layers of metals or metal oxides doped with at least one different metal or metal oxide. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention.

Claims

1. A method comprising the steps of:

a. depositing a dopant precursor comprising M^DL on a substrate via an atomic layer deposition technique; and

b. exposing the deposited dopant precursor to reductive radicals, thereby providing a dopant metal by removing substantially all L and reducing substantially all M^D to M^D(0),

wherein M^D is a dopant metal ion, and

wherein L comprises at least one anionic ligand with a total valence sufficient to render M^DL neutral.

2. The method of claim 1, wherein M^D is a divalent metal ion and L comprises two anionic ligands, L^A and L^B, which can be the same or different.

3. The method of claim 2, wherein M^DL^AL^B comprises the structure:

4. The method of claim 1, wherein M^D is Mg²⁺, Mn²⁺, Ca²⁺, Cd²⁺, Hg²⁺, Ni²⁺, Sr²⁺, or Zn²⁺.

5. The method of claim 1, further comprising the steps of:

c. depositing a compound comprising ML via an atomic layer deposition technique; and

d. exposing the deposited compound to reductive radicals, thereby providing a host metal by removing substantially all L and reducing substantially all M to M(0),

wherein M is a host metal ion, and

wherein L comprises one or more anionic ligands with a total valence sufficient to render ML neutral.

6. The method of claim 5, wherein M is a divalent metal ion and L comprises two anionic ligands, L^A and L^B, which can be the same or different.

7. The method of claim 6, wherein M is Mg²⁺, Mn²⁺, Ca²⁺, Cd²⁺, Hg²⁺, Ni²⁺, Sr²⁺, W²⁺, Ti²⁺, Ta²⁺, or Zn²⁺.

8. The method of claim 6, wherein M is Cu²⁺.

9. The method of claim 6, wherein ML^AL^B comprises the structure:

10. A method comprising the steps of:

a. depositing a dopant precursor comprising the structure;

11. The method of claim 10, wherein CuL comprises the structure:

12. A method comprising the steps of:

a. depositing a compound comprising ML onto a substrate via an atomic layer deposition technique, wherein L comprises at least one anionic ligand;

b. exposing the deposited compound to reductive radicals, thereby providing reduced metal by removing substantially all L and reducing substantially all M to M(0); and

c. electrodepositing M(0) onto the deposited reduced metal.

13. The method of claim 12, wherein M is copper.

14. A method comprising the steps of:

a. depositing a dopant precursor comprising M^DL on a substrate via an atomic layer deposition technique; and

b. exposing the deposited dopant precursor to oxidative radicals, thereby providing a dopant metal oxide by removing substantially all L and producing an oxide of M^D,

wherein MD is a dopant metal ion, and

wherein L comprises at least one anionic ligand with a total valence sufficient to render M^DL neutral.

15. The method of claim 14, wherein M^D is a trivalent metal and L comprises three anionic ligands, L^A, L^B, and L^C, which can be the same or different.

16. The method of claim 15, wherein M^D is Er³⁺, Pr³⁺, Sm³⁺, Eu³⁺, Tb³⁺, or Dy³⁺.

17. The method of claim 15, wherein the oxide of M^D is Er₂O₃.

18. The method of claim 15, wherein the dopant precursor comprises at least one of tris(2,2,6,6-tetramethyl-3,5-heptanedionato)erbium, erbium tris(acetylacetonate), or erbium tris(hexafluoroacetylacetonate) or a mixture thereof.

19. The method of claim 15, wherein M^DL^AL^BL^C comprises the structure:

20. The method of claim 14, further comprising the steps of:

c. depositing a compound comprising ML via an atomic layer deposition technique; and

d. exposing the deposited compound to oxidative radicals, thereby providing a host metal oxide by removing substantially all L and producing an oxide of M,

wherein L comprises at least one anionic organic ligand with a total valence sufficient to render ML neutral.

21. The method of claim 20, wherein M is a trivalent metal and L comprises three anionic ligands, L^A, L^B, and L^C, which can be the same or different.

22. The method of claim 20, wherein M comprises at least one of Y, Si, or Al.

23. The method of claim 20, wherein the oxide of M is at least one of Y₂O₃, Al₂O₃, or SiO₂.

24. A method comprising the steps of:

a. depositing a dopant precursor comprising the structure;

25. The method of claim 24, wherein YL^AL^BL^C comprises the structure: