Method of making electronic materials

• US 20020076495A1
• Filed: 06/06/2001
• Published: 06/20/2002
• Est. Priority Date: 06/06/2000
• Status: Active Grant

• Current Assignee: Simon Fraser University
• Original Assignee: EKC Technology, Inc (DuPont de Nemours, Inc.)
• Inventors: Roman, Paul J. Jr., Maloney, David J., Fury, Michael A., Hill, Ross H., Lee, Wai M.
• Granted Patent: US 6,566,276 B2
• Time in Patent Office: Days
• US Class Current: 427/272
• 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 21/02186 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 21/02282 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 material;

forming a layer comprising the precursor atop a substrate;

converting at least a portion of the precursor layer;

developing the precursor layer thereby forming a pattern in the precursor layer; and

transferring the pattern to the substrate, whereby a photoresist is not used in forming the pattern.

2. The method of claim 1, further comprising developing away an unconverted 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, further comprising developing away 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, further comprising selecting the at least one precursor material 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.

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

selecting at least one precursor material;

optionally, forming a protective layer atop a substrate;

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

converting at least a portion of the unconverted precursor layer;

substantially removing at least a portion of the unconverted precursor layer to form a patterned hard mask.

10. The method of claim 9, further comprising converting with an energy source selected from light, electron beam irradiation, ion beam irradiation, and mixtures thereof.

11. The method of claim 9, further comprising substantially removing at least a portion of the unconverted precursor layer by using a developer.

12. The method of claim 9, further comprising selecting the at least one precursor material 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.

14. The method of claim 13, further comprising selecting the at least one precursor material 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.

16. The method of claim 15, further comprising forming the hard mask by converting with an energy source selected from light, electron beam irradiation, ion beam irradiation, and mixtures thereof.

17. The method of claim 15, further comprising implanting ions by exposing the uncovered substrate to an ion beam.

18. The method of claim 15, further comprising selecting the at least one precursor material 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.

20. The method of claim 19, further comprising selecting the dielectric layer from the group consisting of low-dielectric constant dielectric materials.

21. The method of claim 19, further comprising selecting the at least one precursor material 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.

22. The method of claim 19, further comprising selecting at least one of the first and second etching means as an anisotropic plasma comprising oxygen.

13. A method of forming an etched pattern in a substrate, comprising the steps of:

selecting at least one precursor material;

forming a layer comprising the unconverted precursor atop a substrate;

converting at least a portion of the unconverted precursor layer;

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

forming at least one patterned region in the substrate by etching at least a portion of the substrate substantially uncovered by the hard mask.

15. A method of forming an implanted region in a substrate, comprising the steps of:

selecting at least one precursor material;

optionally, forming a protective layer atop the substrate;

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

converting at least a portion of the precursor layer;

substantially removing at least a portion of the unconverted precursor layer by using a developer to form a patterned hard mask; and

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.

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

selecting at least one precursor material;

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

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

forming a 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 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 converted first precursor layer;

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

forming a 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 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 converted second precursor layer and spin planarization layer by using a third removing means, thereby exposing the 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 converted first precursor layer by using a fourth removing means.