Method of making electronic materials

• US 6,566,276 B2
• Filed: 06/06/2001
• Issued: 05/20/2003
• Est. Priority Date: 06/06/2000
• Status: Expired due to Fees

• Current Assignee: Simon Fraser University
• Original Assignee: EKC Technology, Inc (DuPont de Nemours, Inc.)
• Inventors: Maloney, David J., Lee, Wai M., Roman, Jr., Paul J., Fury, Michael A., Hill, Ross H.
• Primary Examiner(s): COLEMAN, WILLIAM D
• Application Number:
  US09/875,115
• Publication Number:
  US 20020076495A1
• Time in Patent Office: 713 Days
• Field of Search: 438/758, 438/759, 430/270.14, 430/270.15, 430/270.16, 430/311, 430/312
• US Class Current: 438/758
• CPC Class Codes: G03F 7/0042 with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists G03F7/075 takes precedence
• CPC Class Codes: H01L 21/02175 characterised by the metal H01L21/02197 takes precedence
• CPC Class Codes: H01L 21/02178 the material containing aluminium, e.g. Al2O3
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02186 the material containing titanium, e.g. TiO2
• CPC Class Codes: H01L 21/02189 the material containing zirconium, e.g. ZrO2
• CPC Class Codes: H01L 21/02197 the material having a perovskite structure, e.g. BaTiO3
• CPC Class Codes: H01L 21/022 the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides adhesion layers or buffer layers H01L21/02304, H01L21/02362
• CPC Class Codes: H01L 21/02205 the layer being characterised by the precursor material for deposition
• CPC Class Codes: H01L 21/02271 deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition H01L21/02266 takes precedence
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/02282 liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
• CPC Class Codes: H01L 21/02318 post-treatment
• CPC Class Codes: H01L 21/0271 comprising organic layers
• CPC Class Codes: H01L 21/0332 characterised by their composition, e.g. multilayer masks, materials
• CPC Class Codes: H01L 21/0337 characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
• CPC Class Codes: H01L 21/0338 Process specially adapted to improve the resolution of the mask
• CPC Class Codes: H01L 21/3081 characterised by their composition, e.g. multilayer masks, materials
• CPC Class Codes: H01L 21/3086 characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
• CPC Class Codes: H01L 21/3088 Process specially adapted to improve the resolution of the mask
• CPC Class Codes: H01L 21/31144 : using masks
• CPC Class Codes: H01L 21/31691 : with perovskite structure
• CPC Class Codes: H01L 21/76807 : for dual damascene structures
• CPC Class Codes: H01L 21/76811 : involving multiple stacked pre-patterned masks
• CPC Class Codes: H01L 21/76813 : involving a partial via etch

Abstract

The present invention involves fabrication of a hard mask. An embodiment involves the conversion of a precursor into a top-surface imaging layer during a direct patterning step. Another embodiment of the present invention is a method of forming an etched pattern in a substrate. A further embodiment of the present invention is a method of forming an implanted region in a substrate. Preferred precursors are formed from a metal complex comprising at least one ligand selected from the group consisting of acac, carboxylato, alkoxy, azide, carbonyl, nitrato, amine, halide, nitro, and mixtures thereof and at least one metal selected from the group consisting of Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, Mg, and mixtures thereof.

Claims

1. A method of forming a hard mask on a substrate comprising the steps of:

selecting at least one precursor compound capable of transforming into a deposited, metal-containing layer;

optionally, forming a protective layer atop a substrate;

forming a layer comprising the at least one unconverted precursor atop the substrate or atop the protective layer;

substantially fully converting at least a portion of the precursor layer, thereby forming a pattern in the precursor layer; and

developing a portion of the precursor layer, so as to form a deposited, metal-containing patterned hard mask.

2. The method of claim 1, wherein the developing comprises removing a converted portion of the precursor layer with a developer.

3. The method of claim 2, wherein the developer is a liquid developer comprising at least one alcohol and at least one ketone, wherein the total volume of all of the alcohols present is greater than 50% of the sum of the volumes of all of the alcohols present plus the volumes of all of the ketones present in the liquid developer.

4. The method of claim 3, wherein the at least one alcohol is isopropyl alcohol, the at least one ketone is methyl isobutyl ketone, and the ratio of isopropyl alcohol:

methyl isobutyl ketone is from greater than about 1;

1 by volume to less than about 40;

1 by volume.

5. The method of claim 1, wherein the developing comprises removing a converted portion of the precursor layer with a developer.

6. The method of claim 5, wherein the developer is a liquid developer comprising at least one alcohol and at least one ketone, wherein the total volume of all of the alcohols present is greater than 50% of the sum of the volumes of all of the alcohols present plus the volumes of all of the ketones present in the liquid developer.

7. The method of claim 6, wherein the at least one alcohol is isopropyl alcohol, the at least one ketone is methyl isobutyl ketone, and the ratio of isopropyl alcohol:

methyl isobutyl ketone is from greater than about 1;

1 by volume to less than about 40;

1 by volume.

8. The method of claim 1, wherein the at least one precursor compound comprises a metal complex comprising:

at least one ligand selected from the group consisting of acac, carboxylato, alkoxy, azide, carbonyl, nitrato, amine, halide, nitro, and mixtures thereof; and

at least one metal selected from the group consisting of Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, Mg, Bi, and mixtures thereof.

9. The method of claim 1, wherein the converting is accomplished using an energy source selected from the group consisting of light, electron beam irradiation, ion beam irradiation, and mixtures thereof.

10. A method of forming an etched pattern in a substrate, comprising the method of claim 1, and further comprising forming at least one patterned etch region in the substrate by etching at least a portion of the substrate substantially uncovered by the hard mask.

11. The method of claim 10, wherein the at least one precursor compound comprises a metal complex comprising:

at least one ligand selected from the group consisting of acac, carboxylato, alkoxy, azide, carbonyl, nitrato, amine, halide, nitro, and mixtures thereof; and

at least one metal selected from the group consisting of Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, Mg, Bi, and mixtures thereof.

12. A method of forming an implanted region in a substrate, comprising the method of claim 1, and further comprising forming at least one implanted region in the substrate by implanting ions in at least a portion of the substrate substantially uncovered by the hard mask.

13. The method of claim 1, wherein the converting comprises exposing the precursor to an energy source selected from the group consisting of light, electron beam irradiation, ion beam irradiation, and mixtures thereof paramount sufficient to substantially fully convert the exposed portion.

14. The method of claim 12, wherein the implanting of ions is accomplished by exposing the uncovered substrate to an ion beam.

15. The method of claim 12, wherein the at least one precursor compound comprises a metal complex comprising:

at least one ligand selected from the group consisting of acac, carboxylato, alkoxy, azide, carbonyl, nitrato, amine, halide, nitro, and mixtures thereof; and

at least one metal selected from the group consisting of Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, Mg, Bi, and mixtures thereof.

16. The method of claim 1, further comprising transferring the pattern to the substrate, whereby a photoresist is not used in forming the pattern.

17. The method of claim 16, wherein the converting is accomplished using an energy source selected from the group consisting of light, electron beam irradiation, ion beam irradiation, thermal annealing, and mixtures thereof.

18. The method of claim 11, wherein the at least one precursor compound comprises a metal complex comprising:

at least one ligand selected from the group consisting of acac, carboxylato, alkoxy, azide, carbonyl, nitrato, amine, halide, nitro, and mixtures thereof; and

at least one metal selected from the group consisting of Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, Mg, Bi, and mixtures thereof.

19. The method of claim 1, wherein the at least one precursor compound comprises at least one metal and at least two carbon-containing ligands;

wherein the precursor is converted by exposing the fluid precursor layer to an energy source selected from the group consisting of electromagnetic radiation, electron beam irradiation, ion beam irradiation, or mixtures thereof; and

wherein the deposited metal-containing patterned hard mask is amorphous or substantially amorphous.

20. The method of claim 19, wherein the precursor compound is applied as a fluid, the fluid further comprising one or more of a chemical additive to control the photosensitivity of a subsequently deposited precursor or film;

a chemical additive to aid in the ability to deposit uniform, defect-free films onto a substrate;

a chemical additive to modify the viscosity of the solution; and

a chemical additive to aid in preventing film cracking during subsequent exposure of the deposited film.

40. The method of claim 19, wherein the precursor compound comprises a metal selected from platinum, iridium, ruthenium, ruthenium oxide, and iridium oxide.

21. A method of forming a dual damascene architecture in a dielectric layer, comprising the steps of:

forming the dielectric layer with a characteristic thickness atop a substrate;

selecting a first at least one unconverted precursor material;

forming a layer comprising the first unconverted precursor atop the dielectric layer;

forming a substantially fully converted portion of the first precursor layer by using a first converting means on at least a portion of the unconverted first precursor layer;

substantially removing at least a portion of the first unconverted precursor layer to expose at least a portion of the dielectric layer by using a first removing means to form a first pattern uncovered by the substantially fully converted first precursor layer, thereby forming a first hard mask;

forming a spin planarization layer atop the exposed portion of the dielectric layer and atop the substantially fully converted first precursor layer;

forming a layer comprising a second unconverted precursor atop the spin planarization layer;

forming a substantially fully converted portion of the second precursor layer by using a second converting means on at least a portion of the unconverted second precursor layer;

substantially removing at least a portion of the second unconverted precursor layer to expose at least a portion of the spin planarization layer by using a second removing means to form a second pattern uncovered by the substantially fully converted second precursor layer, thereby forming a second hard mask;

forming at least one second patterned region in the dielectric layer by using a first etching means on at least a portion of the dielectric layer and its overlying spin planarization layer substantially uncovered by the second hard mask such that less than the thickness of the dielectric layer in depth is removed by the first etching means;

substantially removing the remaining substantially fully converted second precursor layer and spin planarization layer by using a third removing means, thereby exposing the substantially fully converted first precursor layer;

forming at least one first patterned region in the dielectric layer by using a second etching means on at least a portion of the dielectric layer substantially uncovered by the first hard mask such that less than the thickness in depth of the dielectric layer is removed by the second etching means in the first patterned region and that substantially the entire thickness of the dielectric layer in depth is removed by the second etching means in the second patterned region, thereby uncovering at least a portion of the substrate; and

optionally, substantially removing the remaining substantially fully converted first precursor layer by using a fourth removing means.

22. The method of claim 21, wherein the dielectric layer is selected from the group consisting of low-dielectric constant dielectric materials.

23. The method of claim 21, wherein the at least one precursor material comprises a metal complex comprising:

at least one ligand selected from the group consisting of acac, carboxylato, alkoxy, azide, carbonyl, nitrato, amine, halide, nitro, and mixtures thereof; and

at least one metal selected from the group consisting of Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, Mg, Bi, and mixtures thereof.

24. The method of claim 21, wherein at least one of the first and second etching means comprises an anisotropic plasma comprising oxygen.

41. The method of claim 21, wherein the unconverted precursor material is a fluid that comprises a first precursor compound, said first precursor compound comprising at least one metal and at least two carbon-containing ligands, and wherein the deposited patterned first hard mask is a metal-containing amorphous or substantially amorphous hard mask;

wherein the second unconverted precursor is a fluid that comprises a second precursor compound, said second precursor compound comprising at least one metal and at least two carbon-containing ligands, and wherein the deposited patterned second hard mask is a metal-containing amorphous or substantially amorphous hard mask; and

wherein first and second converting means comprises exposing the first and second precursor compound, respectively, to an energy source selected from the group consisting of electromagnetic radiation, electron beam irradiation, ion beam irradiation, or mixtures thereof.

25. A method of forming patterned thin top surface, comprising the steps of:

selecting at least one unconverted precursor material comprising a metal complex;

forming a pattern transfer layer atop a substrate;

forming a layer comprising the unconverted precursor atop the pattern transfer layer;

exposing a portion of the unconverted precursor layer to an energy source through a patterned mask comprising at least one portion substantially transparent to the energy source, thereby substantially fully converting the exposed portion, and thereby forming a pattern in the precursor layer;

substantially removing at least a portion of the unconverted precursor layer, thereby uncovering at least one portion of the pattern transfer layer and thereby forming a patterned hard mask;

etching the substantially fully converted precursor and uncovered portion of the pattern transfer layer, thereby forming at least one etched portion from the uncovered pattern transfer layer; and

substantially removing the remaining substantially fully converted precursor layer and pattern transfer layer, thereby uncovering at least one portion of substrate.

26. The method of claim 25, wherein the pattern transfer layer comprises a material selected from the group consisting of a photoresist, polyimide, poly(methyl methacrylate), novolac, and epoxy.

27. The method of claim 25, wherein the at least one precursor material comprises a metal complex comprising:

at least one ligand selected from the group consisting of acac, carboxylato, alkoxy, azide, carbonyl, nitrato, amine, halide, nitro, and mixtures thereof; and

at least one metal selected from the group consisting of Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, Mg, Bi, and mixtures thereof.

28. The method of claim 25, wherein the energy source is selected from the group consisting of light, electron beam irradiation, ion beam irradiation, thermal annealing, and mixtures thereof.

29. A method of forming patterned thin top surface over a liftoff layer, comprising the steps of:

selecting at least one unconverted precursor material comprising a metal complex;

forming a release layer atop a substrate;

forming a liftoff layer atop the release layer;

forming a layer comprising the unconverted precursor atop the liftoff layer;

exposing a portion of the unconverted precursor layer to an energy source through a patterned mask comprising at least one portion substantially transparent to the energy source, thereby substantially fully converting the exposed portion, and thereby forming a pattern in the precursor layer;

substantially removing at least a portion of the unconverted precursor layer, thereby uncovering at least one portion of the liftoff layer with the remaining portion of the liftoff layer being covered by the substantially fully converted precursor layer, thereby forming a patterned hard mask;

exposing the substantially fully converted precursor and the uncovered portion of the liftoff layer to an anisotropic removing means, thereby substantially removing the uncovered portion of the liftoff layer and at least one portion of the release layer underlying the uncovered portion of the liftoff layer, and thereby exposing at least one portion of the substrate;

depositing a film of metal atop the at least one portion of the exposed substrate and atop the substantially fully converted precursor layer; and

exposing the substantially fully converted precursor, the covered portion of the liftoff layer and at least one portion of the release layer underlying the covered portion of the liftoff layer to an isotropic removing means, thereby substantially removing the metal atop the substantially fully converted precursor, thereby substantially removing the remaining substantially fully converted precursor, the liftoff layer, and the release layer, and thereby forming a pattern of metal atop the substrate.

30. The method of claim 29, wherein the at least one precursor material comprises a metal complex comprising:

at least one ligand selected from the group consisting of acac, carboxylato, alkoxy, azide, carbonyl, nitrato, amine, halide, nitro, and mixtures thereof; and

at least one metal selected from the group consisting of Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, Mg, Bi, and mixtures thereof. forming a pattern of metal atop the substrate.

31. The method of claim 29, wherein the energy source is selected from the group consisting of light, electron beam irradiation, ion beam irradiation, thermal annealing, and mixtures thereof.

32. A method of forming patterned thin top surface on a substrate, comprising the steps of:

selecting at least one precursor material comprising a metal complex;

forming a layer comprising the unconverted precursor material atop a substrate;

substantially fully converting at least a portion of the unconverted precursor layer, thereby forming a pattern in the precursor layer;

substantially removing at least a portion of the unconverted precursor layer, thereby forming inwardly-tapering sidewall profiles in the substantially fully converted precursor portion and exposing at least one portion of the substrate, and thereby forming a patterned hard mask;

depositing a film of metal atop the at least one portion of the exposed substrate and atop the substantially fully converted precursor;

substantially removing the metal atop the substantially fully converted precursor; and

substantially removing the remaining substantially fully converted precursor, thereby forming a pattern of the metal atop the substrate.

33. The method of claim 32, wherein the at least one precursor material comprises a metal complex comprising:

at least one ligand selected from the group consisting of acac, carboxylato, alkoxy, azide, carbonyl, nitrato, amine, halide, nitro, and mixtures thereof; and

at least one metal selected from the group consisting of Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, Mg, Bi, and mixtures thereof.

34. A method of forming a hard mask on a semiconductor substrate comprising the steps of:

providing a semiconductor substrate comprising a surface, wherein the substrate optionally contains a protective layer disposed on the surface;

providing an unconverted metal-organic precursor compound having a first solubility in a fluid precursor layer composition, wherein said metal-organic precursor compound is capable of transforming on exposure to an energy source comprising electromagnetic radiation, electron beam irradiation, ion beam irradiation, thermal annealing, or mixtures thereof, into a converted compound of a second solubility in the fluid precursor layer composition different from the first solubility;

forming a fluid precursor layer from the fluid precursor layer composition comprising the unconverted metal-organic precursor compound on the substrate surface and/or on the protective layer;

substantially fully converting at least a portion of the fluid precursor layer, thereby forming an amorphous pattern in the precursor layer; and

developing a portion of the metal-organic precursor layer to form a patterned layer.

35. The method of claim 34, wherein the unconverted metal-organic precursor compound consists of a metal complex comprising:

at least one ligand selected from the group consisting of acac, carboxylato, alkoxy, azide, carbonyl, nitrato, amine, halide, nitro, and mixtures thereof; and

at least one metal selected from the group consisting of Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, Mg, Bi, and mixtures thereof.

36. The method of claim 35, wherein the precursor layer formed on the substrate surface and/or on the protective layer comprises a mixture of a plurality of metal-organic precursor compounds.

37. The method of claim 34, wherein the converting consists essentially of exposing the fluid precursor layer to an energy source selected from the group consisting of electromagnetic radiation, electron beam irradiation, ion beam irradiation, or mixtures thereof.

42. The method of claim 34, wherein the unconverted metal-organic precursor compound is applied in the fluid precursor, the fluid precursor further comprising one or more of a chemical additive to control the photosensitivity of a subsequently deposited precursor or film;

a chemical additive to aid in the ability to deposit uniform, defect-free films onto a substrate;

a chemical additive to modify the viscosity of the solution; and

a chemical additive to aid in preventing film cracking during subsequent exposure of the deposited film.

43. The method of claim 34, wherein the unconverted metal-organic precursor compound comprises a metal selected from platinum, iridium, ruthenium, ruthenium oxide, and iridium oxide.

38. A method of forming a hard mask on a substrate comprising the steps of:

selecting at least one metal complex precursor compound comprising;

at least one ligand selected from the group consisting of acac, carboxylato, alkoxy, azide, carbonyl, nitrato, amine, halide, nitro, and mixtures thereof, and at least one metal selected from the group consisting of Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, Mg, Bi, and mixtures thereof;

optionally, forming a protective layer atop a substrate;

P1 forming a layer comprising the at least one unconverted metal complex precursor atop the substrate or atop the protective layer;

substantially fully converting at least a portion of the metal complex precursor layer, thereby forming a pattern in the precursor layer; and

developing a portion of the metal complex precursor layer, so as to form a patterned hard mask.

39. The method of claim 38, wherein the converting consists essentially of exposing the fluid precursor layer to an energy source selected from the group consisting of electromagnetic radiation, electron beam irradiation, ion beam irradiation, or mixtures thereof.

44. The method of claim 38, wherein the unconverted metal complex precursor compound comprises at least two carbon-containing ligands;

and wherein the patterned hard mask is metal-containing and is amorphous or substantially amorphous.

45. The method of claim 44, wherein the layer comprising the unconverted metal complex precursor compound is a fluid, the fluid further comprising one or more of a chemical additive to control the photosensitivity of a subsequently deposited precursor or film;

a chemical additive to aid in the ability to deposit uniform, defect-free films onto a substrate;

a chemical additive to modify the viscosity of the solution; and

a chemical additive to aid in preventing film cracking during subsequent exposure of the deposited film.

46. The method of claim 38, wherein the unconverted metal complex precursor compound comprises a metal selected from platinum, iridium, ruthenium, ruthenium oxide, and iridium oxide.