Activated chemical process for enhancing material properties of dielectric films

1. A method for restoring a dielectric constant of a layer of a silicon-containing dielectric material having a first dielectric constant and at least one surface, wherein the first dielectric constant of the layer of silicon-containing dielectric material has increased to a second dielectric constant, the method comprising the steps of:

contacting the at least one surface of the layer of silicon-containing dielectric material with a silicon-containing fluid; and

exposing the at least one surface of the layer of silicon-containing dielectric material to an energy source selected from the group consisting of: UV radiation, heat, and an electron beam, wherein the layer of silicon-containing dielectric material has a third dielectric constant that is lower than the second dielectric constant after exposing the layer of silicon-containing dielectric material to the energy source.

2. The method of claim 1 further comprising the step of removing a first portion of the silicon-containing fluid such that a second portion of the silicon-containing fluid remains in contact with the at least one surface of the layer of silicon-containing dielectric material, wherein the removing step occurs between the contacting step and the exposing step.

3. The method of claim 1 further comprising the step of exposing the layer of silicon-containing dielectric material to a low-energy plasma source prior to exposing the layer of silicon-containing dielectric material to the energy source.

4. The method of claim 3 wherein the layer of silicon-containing dielectric material is exposed concurrently to the plasma energy source and at least one energy source selected from the group consisting of: UV radiation, thermal energy, and an electron beam.

5. The method of claim 3 wherein the layer of silicon-containing dielectric material is exposed to the plasma energy source before it is exposed to the at least one energy source selected from the group consisting of: UV radiation, thermal energy, and an electron beam.

6. The method of claim 1 wherein the energy source comprises UV radiation.

7. The method of claim 6 wherein the energy source further includes thermal energy.

8. The method of claim 6 wherein the UV radiation is monochromatic UV radiation.

9. The method of claim 1 wherein the contacting step is performed by a chemical vapor deposition process.

10. The method of claim 9 wherein the silicon-containing fluid is at least one selected from the group consisting of: methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethoxymethylsilane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane, 2,2,4,6,6-pentamethyl-2,4,6-trisila-heptane, 1,methyl-1-ethoxy-silacyclopentane, 1,1,3,3-tetramethyl-1,3-disilacyclobutane, 1,3-dimethyl-1,3-diethoxy-1,3-disilacyclobutane, bis(trimethylsilylmethyl)benzene, (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, bis(dimethoxymethylsilyl)methane, bis(diethoxymethylsilyl)methane, bis(dimethoxyphenylsilyl)methane, bis(diethoxyphenylsilyl)methane, bis(methoxydimethylsilyl)methane, bis(ethoxydimethylsilyl)methane, bis(methoxydiphenylsilyl)methane, bis(ethoxydiphenylsilyl)methane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisialzane, octamethylcyclotetrasilazane, nonamethyltrisilazane, dimethylcyclosilazane, acetoxytrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, bis(dimethylamino)dimethylsilane, dimethylaminotrimethylsilane, aminomethyltrimethylsilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, methyltriacetoxysilane, methylethoxysilacyclopropane, hexamethylsilabutane, dimethyldiacetoxysilane, and di-tert-butoxydiacetoxysilane.

11. The method of claim 10 wherein the silicon-containing fluid is at least one selected from the group consisting of: hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, octamethylcyclotetrasilazane, nonamethyltrisilazane, dimethylcyclosilazane, acetoxytrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, bis(dimethylamino)dimethylsilane, dimethylaminotrimethylsilane, aminomethyltrimethylsilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasilane, dodecamethylcyclohexasilane, 2,2,4,6,6-pentamethyl-2,4,6-trisila-heptane, 1,methyl-1-ethoxy-silacyclopentane, 1,1,3,3-tetramethyl-1,3-disilacyclobutane, 1,3-dimethyl-1,3-diethoxy-1,3-disilacyclobutane, bis(trimethylsilylmethyl)benzene, dimethydimethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, and (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane.

12. The method of claim 11 wherein the silicon-containing fluid is at least one selected from the group consisting of: diethoxymethylsilane, dimethyldiacetoxysilane, methyltriacetoxysilane, di-tert-butoxydiacetoxysilane, dimethyldimethoxysilane, and methyltriethoxysilane.

13. The method of claim 10 wherein the silicon-containing fluid comprises at least one of octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane.

14. The method of claim 12 wherein the silicon-containing fluid comprises dimethyldiacetoxysilane, methyltriacetoxysilane, and acetoxytrimethylsilane.

15. The method of claim 1 wherein the contacting step is performed by a spin-on deposition process.

16. The method of claim 1 wherein the layer of silicon-containing dielectric material is porous.

17. The method of claim 1 wherein the first dielectric constant is from about 1.5 to about 3.5, the second dielectric constant is from about 5% to about 200% higher than the first dielectric constant and the third dielectric constant is from about 10% to about 150% restored relative to the second dielectric constant.

18. The method of claim 17 wherein the first dielectric constant is from about 1.5 to about 2.8.

19. The method of claim 18 wherein the first dielectric constant is from about 1.8 to about 2.7.

20. The method of claim 1 wherein the layer of silicon-containing dielectric material has a dielectric constant that is within 10% of the third dielectric constant after exposure to a temperature of at least 400° C.

21. The method of claim 1 wherein the silicon-containing fluid comprises at least one selected from the group consisting of: a linear silazane, a cyclic silazane, a cyclic organosiloxane, an organosiloxane, an alkylalkoxysilane, an alkylacetoxysilane, an alkylchlorosilane, a carbosilane, an aminoalkylsilane, an alkylaminoalkylsilane, and an aminoalkylalkoxysilane.

22. The method of claim 21 wherein the silicon-containing fluid comprises an alkylacetoxysilane.

23. A method for restoring a dielectric constant of a layer of a silicon-containing dielectric material having a first dielectric constant and at least one surface, wherein the first dielectric constant of the layer of silicon-containing dielectric material has increased to a second dielectric constant, the method comprising the steps of:

contacting the at least one surface of the layer of silicon-containing dielectric material with a silicon-containing fluid;

removing a first portion of the silicon-containing fluid such that a second portion of the silicon-containing fluid remains in contact with the at least one surface of the layer of silicon-containing dielectric material; and

exposing the at least one surface of the layer of silicon-containing dielectric material to UV radiation and thermal energy, wherein the layer of silicon-containing dielectric material has a third dielectric constant that is lower than the second dielectric constant after exposing the layer of silicon-containing dielectric material to the energy source.

24. The method of claim 23 further comprising the step of exposing the layer of silicon-containing dielectric material to a low-energy plasma source prior to exposing the layer of silicon-containing dielectric material to the energy source.

25. The method of claim 23 wherein the UV radiation is monochromatic UV radiation.

26. The method of claim 23 wherein the contacting step is performed by a chemical vapor deposition process.

27. The method of claim 26 wherein the silicon-containing fluid is at least one selected from the group consisting of: methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethoxymethylsilane, 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane, 1,1,3,3-tetramethoxy-1,3-diphenyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, 1,3-dimethoxy-1,1,3,3-tetraphenyldisiloxane, 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane, 2,2,4,6,6-pentamethyl-2,4,6-trisila-heptane, 1,methyl-1-ethoxy-silacyclopentane, 1,1,3,3-tetramethyl-1,3-disilacyclobutane, 1,3-dimethyl-1,3-diethoxy-1,3-disilacyclobutane, bis(trimethylsilylmethyl)benzene, (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, bis(dimethoxymethylsilyl)methane, bis(diethoxymethylsilyl)methane, bis(dimethoxyphenylsilyl)methane, bis(diethoxyphenylsilyl)methane, bis(methoxydimethylsilyl)methane, bis(ethoxydimethylsilyl)methane, bis(methoxydiphenylsilyl)methane, bis(ethoxydiphenylsilyl)methane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, octamethylcyclotetrasilazane, nonamethyltrisilazane, dimethylcyclosilazane, acetoxytrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, bis(dimethylamino)dimethylsilane, dimethylaminotrimethylsilane, aminomethyltrimethylsilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, methyltriacetoxysilane, methylethoxysilacyclopropane, hexamethylsilabutane, dimethyldiacetoxysilane, and di-tert-butoxydiacetoxysilane.

28. The method of claim 27 wherein the silicon-containing fluid is at least one selected from the group consisting of: hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, octamethylcyclotetrasilazane, nonamethyltrisilazane, dimethylcyclosilazane, acetoxytrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, bis(dimethylamino)dimethylsilane, dimethylaminotrimethylsilane, aminomethyltrimethylsilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasilane, dodecamethylcyclohexasilane, 2,2,4,6,6-pentamethyl-2,4,6-trisila-heptane, 1,methyl-1-ethoxy-silacyclopentane, 1,1,3,3-tetramethyl-1,3-disilacyclobutane, 1,3-dimethyl-1,3-diethoxy-1,3-disilacyclobutane, bis(trimethylsilylmethyl)benzene, dimethydimethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, and (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane.

29. The method of claim 28 wherein the silicon-containing fluid is at least one selected from the group consisting of: diethoxymethylsilane, dimethyldiacetoxysilane, methyltriacetoxysilane, di-tert-butoxydiacetoxysilane, dimethyldimethoxysilane, and methyltriethoxysilane.

30. The method of claim 29 wherein the silicon-containing fluid comprises at least one of acetoxytrimethylsilane, methyltriacetoxysilane, and dimethyldiacetoxysilane.

31. The method of claim 23 wherein the layer of silicon-containing dielectric material is porous.

32. The method of claim 23 wherein the first dielectric constant is from about 1.5 to about 3.5, the second dielectric constant is from about 5% to about 150% higher than the first dielectric constant and the third dielectric constant is from about 10% to about 150% recovered relative to the second dielectric constant.

33. The method of claim 32 wherein the first dielectric constant is from about 1.5 to about 2.8.

34. The method of claim 33 wherein the first dielectric constant is from about 1.8 to about 2.7.

35. The method of claim 23 wherein the layer of silicon-containing dielectric material has a dielectric constant that is within 10% of the third dielectric constant after exposure to a temperature of at least 400° C.

36. The method of claim 23 wherein the silicon-containing fluid comprises at least one selected from the group consisting of: a linear silazane, a cyclic silazane, a cyclic organosiloxane, an organosiloxane, an alkylalkoxysilane, an alkylacetoxysilane, an alkylchlorosilane, a carbosilane, an aminoalkylsilane, an alkylaminoalkylsilane, and an aminoalkylalkoxysilane.

37. The method of claim 36 wherein the silicon-containing fluid comprises an alkylacetoxysilane.

38. A method for restoring a dielectric constant of a layer of a silicon-containing dielectric material having a first dielectric constant and at least one surface, wherein the first dielectric constant of the layer of silicon-containing dielectric material has increased to a second dielectric constant, the method comprising the steps of:

contacting the at least one surface of the layer of silicon-containing dielectric material with a silicon-containing fluid comprising an alkylalkoxysilane;

removing a first portion of the silicon-containing fluid such that a second portion of the silicon-containing fluid remains in contact with the at least one surface of the layer of silicon-containing dielectric material; and

exposing the at least one surface of the layer of silicon-containing dielectric material to UV radiation and thermal energy, wherein the layer of silicon-containing dielectric material has a third dielectric constant that is lower than the second dielectric constant after exposing the layer of silicon-containing dielectric material to the energy source.

39. The method of claim 38 wherein the alkylalkoxysilane is at least one selected from the group consisting of: methyltriethoxysilane, methyltrimethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, trimethylmethoxysilane, trimethylethoxysilane, and trimethylpropoxysilane.

40. The method of claim 39 wherein the alkylalkoxysilane is methyltriethoxysilane.

41. The method of claim 39 wherein the alkylalkoxysilane is dimethyldimethoxysilane.

42. The method of claim 38 wherein the layer of silicon-containing dielectric material is porous.

43. The method of claim 42 wherein the first dielectric constant is from about 1.5 to about 3.5, the second dielectric constant is from about 5% to about 150% higher than the first dielectric constant and the third dielectric constant is from about 10% to about 150% recovered relative to the second dielectric constant.

44. The method of claim 43 wherein the first dielectric constant is from about 1.5 to about 2.8.

45. The method of claim 44 wherein the first dielectric constant is from about 1.8 to about 2.7.

46. The method of claim 38 wherein the layer of silicon-containing dielectric material has a dielectric constant that is within 10% of the third dielectric constant after exposure to a temperature of at least 400° C.