Precursors for Electron Beam-Induced Deposition of Gold and Silver

Abstract

Precursors are prepared and employed in electron beam induced decomposition (EBID). The EBID precursors are complexes of the formula: X-M-Y, where M is Au or Ag; X is F, Cl, Br, I, CN, OR.sup.1, O.sub.2CR.sup.2, or R.sup.3; Y is P(OR).sub.3, NR.sub.3, unsubstituted or substituted pyrrole, unsubstituted or substituted pyridine, unsubstituted or substituted pyrrolidine, or unsubstituted or substituted piperidine; and where R, R.sup.1, R.sup.2, R.sup.3, and substituents of the substituted pyrrole, pyridine, pyrrolidine, or piperidine are independently H, C.sub.1-C.sub.8 alkyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl. The decomposition of the EBID precursor results in the formation of one or more gold, silver, or any combination thereof features on a substrate.

Claims

1. An electron beam induced deposition EBID precursor, comprising a complex of the formula:
X-M-Y, where M is Au or Ag; X is F, Cl, Br, I, CN, OR.sup.1, O.sub.2CR.sup.2, or R.sup.3; Y is P(OR).sub.3, NR.sub.3, unsubstituted or substituted pyrrole, unsubstituted or substituted pyridine, unsubstituted or substituted pyrrolidine, or unsubstituted or substituted piperidine; and where R, R.sup.1, R.sup.2, R.sup.3, and substituents of the substituted pyrrole, pyridine, pyrrolidine, or piperidine are independently H, C.sub.1-C.sub.8 alkyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

2. The EBID precursor according to claim 1, wherein the complex has the formula:
X-M-P(OR).sub.3, where M=Au or Ag; X=F, Cl, Br, I or CN; R is independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

3. The EBID precursor according to claim 1, wherein the complex has the formula:
R.sup.1-M-P(OR).sub.3, where M=Au or Ag; R and R.sup.1 are independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

4. The EBID precursor according to claim 1, wherein the complex has the formula:
R.sup.2CO.sub.2-M-P(OR).sub.3, where M=Au or Ag; R and R.sup.2 are independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

5. The EBID precursor according to claim 1, wherein the complex has the formula:
R.sup.3-M-P(OR).sub.3, where M=Au or Ag; R and R.sup.3 are independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

6. The EBID precursor according to claim 1, wherein the complex has the formula:
X-M-NR.sup.4.sub.3, where M=Au or Ag; X=F, Cl, Br, I or CN; R.sup.4 is independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

7. The EBID precursor according to claim 1, wherein the complex has the formula:
R.sup.1O-M-NR.sup.4.sub.3, where M=Au or Ag; R.sup.1 and R.sup.4 are independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

8. The EBID precursor according to claim 1, wherein the complex has the formula:
R.sup.2CO.sub.2-M-NR.sup.4.sub.3, where M=Au or Ag; R.sup.2 and R.sup.4 are independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

9. The EBID precursor according to claim 1, wherein the complex has the formula:
R.sup.3-M-NR.sup.4.sub.3, where M=Au or Ag; R.sup.3 and R.sup.4 are selected from the group consisting of H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

10. The EBID precursor according to claim 1, wherein the complex has the formula: ##STR00005## where M is Au or Ag; X is F, Cl, Br, I, CN, OR.sup.1, O.sub.2CR.sup.2, or R.sup.3; and where R.sup.1, R.sup.2, R.sup.3, and R.sup.8 are independently H, C.sub.1-C.sub.8 alkyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

11. The EBID precursor according to claim 1, wherein the complex has the formula: ##STR00006## where M is Au or Ag; X is F, Cl, Br, I, CN, OR.sup.1, O.sub.2CR.sup.2, or R.sup.3; and where R.sup.1, R.sup.2, R.sup.3, and R.sup.8 are independently H, C.sub.1-C.sub.8 alkyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

12. The EBID precursor according to claim 1, wherein the complex has the formula: ##STR00007## where M is Au or Ag; X is F, Cl, Br, I, CN, OR.sup.1, O.sub.2CR.sup.2, or R.sup.3; and where R.sup.1, R.sup.2, R.sup.3, R.sup.8, and R.sup.9 are independently H, C.sub.1-C.sub.8 alkyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

13. The EBID precursor according to claim 1, wherein the complex has the formula: ##STR00008## where M is Au or Ag; X is F, Cl, Br, I, CN, OR.sup.1, O.sub.2CR.sup.2, or R.sup.3; and where R.sup.1, R.sup.2, R.sup.3, R.sup.8, and R.sup.9 are independently H, C.sub.1-C.sub.8 alkyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

14. A method of depositing a metal feature, comprising: providing a substrate; providing a focused electron beam on a portion of the surface of the substrate; introducing at least one EBID precursor according to claim 1 into a EBID device over the surface of the substrate; decomposing the EBID precursor into a metal feature at the portion of the surface of the substrate having the focused electron beam.

15. The method of claim 14, further comprising introducing with the EBID precursor one or more co-precursors selected from H.sub.2, O.sub.2, O.sub.3, N.sub.2O, NO, CO and X.sub.2 where X=F, Cl, Br or I.

Description

DETAILED DISCLOSURE

[0009] Embodiments of the invention are directed to EBID precursors that are gold and silver phosphite or amine complexes of the formula:

X-M-Y,

where M is Au or Ag; X is F, Cl, Br, I, CN, OR.sup.1, O.sub.2CR.sup.2, or R.sup.3; Y is P(OR).sub.3, NR.sub.3, unsubstituted or substituted pyrrole, unsubstituted or substituted pyridine, unsubstituted or substituted pyrrolidine, or unsubstituted or substituted piperidine; and where R, R.sup.1, R.sup.2, R.sup.3, and substituents of the substituted pyrrole, pyridine, pyrrolidine, or piperidine are independently H, C.sub.1-C.sub.8 alkyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

[0010] The gold and silver complexes display a low coordination number where the electronic properties of the ligands render the complexes suitable for deposition of metal-containing structures. The nature of the ligands should result in very low levels of contaminants relative to those from current commercially available precursors. The alkoxide, amine, carboxylate, and phosphite ligands of these complexes are unknown as Au(I) or Ag(I) EBID precursors.

[0011] In an embodiment of the invention, the complex is a gold or silver phosphite complex of the formula:

X-M-P(OR).sub.3

where M=Au or Ag; X=F, Cl, Br, I or CN; R is independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7.

[0012] In another embodiment of the invention the complex is a gold or silver phosphite complex of the formula:

R.sup.1O-M-P(OR).sub.3

where M=Au or Ag; R and R.sub.1 are independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

[0013] In another embodiment of the invention the complex is a gold or silver phosphite complex of the formula:

R.sup.2CO.sub.2-M-P(OR).sub.3

where M=Au or Ag; R and R.sup.2 are independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

[0014] In another embodiment of the invention the complex is a gold or silver phosphite complex of the formula:

R.sup.3-M-P(OR).sub.3

where M=Au or Ag; R and R.sup.3 are independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

[0015] In another embodiment of the invention the complex is a gold or silver amine complex of the formula:

X-M-NR.sup.4.sub.3

where M=Au or Ag; X=F, Cl, Br, I or CN; R.sup.4 is independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

[0016] In another embodiment of the invention the complex is a gold or silver amine complex of the formula:

R.sup.1O-M-NR.sup.4.sub.3

where M=Au or Ag; R.sup.1 and R.sup.4 are independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

[0017] In another embodiment of the invention the complex is a gold or silver amine complex of the formula:

R.sup.2CO.sub.2-M-NR.sup.4.sub.3

where M=Au or Ag; R.sup.2 and R.sup.4 are independently H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

[0018] In another embodiment of the invention the complex is a gold or silver amine complex of the formula:

R.sup.3-M-NR.sup.4.sub.3

where M=Au or Ag; R.sup.3 and R.sup.4 are selected from the group consisting of H, C.sub.1-C.sub.8 alkyl, aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and silicon-containing groups of the type SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

[0019] In another embodiment of the invention the complex is a gold or silver pyrrole complex of the formula:

##STR00001##

where M is Au or Ag; X is F, Cl, Br, I, CN, OR.sup.1, O.sub.2CR.sup.2, or R.sup.3; and where R.sup.1, R.sup.2, R.sup.3, and R.sup.8 are independently H, C.sub.1-C.sub.8 alkyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

[0020] In another embodiment of the invention the complex is a gold or silver pyridine complex of the formula:

##STR00002##

where M is Au or Ag; X is F, Cl, Br, I, CN, OR.sup.1, O.sub.2CR.sup.2, or R.sup.3; and where R.sup.1, R.sup.2, R.sup.3, and R.sup.8 are independently H, C.sub.1-C.sub.8 alkyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

[0021] In another embodiment of the invention the complex is a gold or silver pyrrolidine complex of the formula:

##STR00003##

where M is Au or Ag; X is F, Cl, Br, I, CN, OR.sup.1, O.sub.2CR.sup.2, or R.sup.3; and where R.sup.1, R.sup.2, R.sup.3, R.sup.8, and R.sup.9 are independently H, C.sub.1-C.sub.8 alkyl, C.sub.6-C.sub.10aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.1-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

[0022] In another embodiment of the invention the complex is a gold or silver piperidine complex of the formula:

##STR00004##

where M is Au or Ag; X is F, Cl, Br, I, CN, OR.sup.1, O.sub.2CR.sup.2, or R.sup.3; and where R.sup.1, R.sup.2, R.sup.3, R.sup.8, and R.sup.9 are independently H, C.sub.1-C.sub.8 alkyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.8 perfluoroalkyl, C.sub.1-C.sub.8 partially fluorinated alkyl, and SiR.sup.5R.sup.6R.sup.7 where R.sup.5, R.sup.6, and R.sup.7 are independently H, C.sub.10-C.sub.8 alkyl, or C.sub.1-C.sub.8 fluorinated alkyl.

[0023] In another embodiment of the invention, one or more of the gold and/or silver phosphite or amine complexes are introduced as a metal deposition precursor into an EBID in a gaseous state to deposit gold and/or silver metal with a desired shape and size. The electron beam induced deposition (EBID) provides a metal feature on a substrate where at least one dimension of the metal feature is 0.2 to 1,000 nanometers or more. The substrate can be any substrate that is not adversely affected by the electron beam, including semiconductors, conductors, or insulators, for example, Si or SiO.sub.2. For example the deposition can be a circuit element that has a width of 1 to 5 nm, 1 to 10 nm, 1 to 15 nm, 1 to 20 nm, 1 to 30 nm, 1 to 40 nm, 1 to 50 nm, 1 to 100 nm, 1 to 100 nm. Focused EBID (FEBID) units provide the finer features with very thin features. By applying a raster scan during deposition of the metal, larger surfaces can be covered with surface areas exceeding one square micron. The metal EBID precursors can be used alone or in combination of metal EBID precursors. In an embodiment of the invention, the gold and/or silver phosphite or amine complexes can be combined with one or more co-precursors selected from H.sub.2, O.sub.2, O.sub.3, N.sub.2O, NO, CO or X.sub.2 where X=F, Cl, Br or I.

[0024] The EBID and FEBID equipment and processes are well documented. The method can be carried out with the equipment and in the manner described in: Mulders et al., J Phys. D: Appl. Phys. 45 (2012) 475301; Utke et al., J. Vac. Sci. Technol. B 26 (4) (2008) 1197-272; Brintlinger et al., J. Vac. Sci. Technol. B 23 (6) (2005); Bresin et al., Angew. Chem. Int. Ed. 2013, 52, 8004-7; and Spencer et al., Appl. Phys. A (2014) DOI 10.1007/s00339-014-8570-5.

[0025] All publications referred to or cited herein are incorporated by reference in their entirety, including all figures and tables, to the extent they are not inconsistent with the explicit teachings of this specification.

[0026] It should be understood that the embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.