Process for delineating photoresist lines at pattern edges only using image reversal composition with diazoquinone

• US 4,568,631 A
• Filed: 04/30/1984
• Issued: 02/04/1986
• Est. Priority Date: 04/30/1984
• Status: Expired due to Term

• Current Assignee: International Business Machines Corporation
• Original Assignee: International Business Machines Corporation
• Inventors: Hakey, Mark C., Moritz, Holger, Badami, Dinesh A.
• Primary Examiner(s): Bowers, Jr., Charles L.
• Application Number:
  US06/605,088
• Time in Patent Office: 645 Days
• Field of Search: 430/5, 430/191, 430/192, 430/311, 430/312, 430/314, 430/315, 430/325, 430/328, 430/330, 430/323, 430/324
• US Class Current: 430/315
• CPC Class Codes: G03F 7/039 Macromolecular compounds which are photodegradable, e.g. positive electron resists G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023
• CPC Class Codes: G03F 7/20 Exposure; Apparatus therefor photographic printing apparatus for making copies G03B27/00
• CPC Class Codes: G03F 7/2022 Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
• CPC Class Codes: G03F 7/40 Treatment after imagewise removal, e.g. baking

Abstract

An optical photolithographic process in which resist lines having widths in the micron and sub-micron range are produced without the use of a fine line photomask. A positive photoresist having an additive for image reversal is applied to the surface of a semiconductor substrate. The photoresist is exposed through a photomask to ultraviolet light. The edges of the opaque sections of the mask diffract the ultraviolet light, forming partially exposed areas between the exposed and unexposed areas formed in the photoresist. After development in a solvent to remove the exposed areas, the photoresist undergoes an image reversal process. The photoresist is first baked at 100° C. for 30 minutes. During this bake step, the photoactive decomposition products present in the partially exposed areas react, freezing the solubility of the partially exposed areas with respect to that of the unexposed areas. The photoresist is then blanket exposed and developed in a solvent, leaving the partially exposed areas on the substrate. The resulting thin resist lines can be used to form narrow isolation trenches by coating the substrate with a quartz film and lifting off the resist lines.

Claims

1. A method of photolithographic mask image processing, comprising the steps of:

applying a photoresist layer onto a surface of a substrate, said photoresist layer comprising a photosensitive diazoquinone and an additive which produces image reversal;

positioning a photomask above said photoresist layer, said photomask including a plurality of first segments separated by a plurality of second segments;

optically exposing said photoresist layer with actinic radiation through said plurality of first segments of said photomask to form exposed areas, partially exposed areas, and unexposed areas in said photoresist layer;

developing said photoresist layer to remove said exposed areas and portions of said partially exposed areas;

baking said photoresist layer at an elevated temperature to harden said partially exposed areas with respect to said unexposed areas;

blanket exposing said photoresist layer with actinic radiation to cause said unexposed areas to have a higher solubility than said partially exposed areas; and

developing said photoresist layer for a time sufficient to remove portions of said photoresist layer corresponding substantially to said unexposed areas,

whereby the remaining portions of said partially exposed areas form thin resist lines on the semiconductor substrate.

2. The method as recited in claim 1, wherein each of said remaining portions of said partially exposed areas of said photoresist are approximately 0.55 to 1.2 microns in width.

3. The method as recited in claim 1, wherein said photoresist layer comprises a diazoquinone photosensitive polymer having a 1% imidazole additive for image reversal.

4. A method of photolithographic mask image processing, as recited in claim 1, additionally comprising the steps of:

applying a film onto the semiconductor substrate, said film covering said mask;

lifting off said mask to form a plurality of grooves in said film;

etching the semiconductor substrate through said plurality of grooves to form a plurality of narrow trenches in the semiconductor substrate; and

forming isolation regions within said plurality of narrow trenches of said semiconductor substrate.

5. The method as recited in claim 4, wherein said step of image reversing said photoresist layer comprises the steps of:

baking said photoresist layer, said partially exposed areas having decomposition products which react to cause said partially exposed areas to harden with respect to said unexposed areas; and

blanket exposing said photoresist layer.

6. A method of photolithographic mask image processing, comprising the steps of:

applying a photoresist layer onto a surface of a semiconductor substrate, said photoresist layer comprising a photosensitive diazoquinone and an additive which produces image reversal;

positioning a photomask of transparent segments and opaque segments above said photoresist layer;

optically exposing said photoresist layer with actinic radiation through said photomask to form exposed areas, partially exposed areas and unexposed areas in said photoresist layer, said partially exposed areas

being located between said exposed areas and said unexposed areas of said photoresist layer;

developing said photoresist layer in a solvent to remove said exposed areas and portions of said partially exposed areas of said photoresist layer;

image reversing said photoresist layer; and

developing said photoresist layer to remove a portion of said photoresist layer corresponding substantially to said unexposed areas, the remaining partially exposed areas of said photoresist layer forming a mask.

7. A method of photolithographic mask image processing, comprising the steps of:

applying a layer of positive photoresist to a surface of a substrate, said photoresist layer comprising a photosensitive diazoquinone and an additive which produces image reversal;

image-wise exposing said photoresist layer through a photomask including clear and opaque segments with actinic radiation from a light source, to produce exposed areas in said photoresist layer corresponding to said clear segments of said mask, unexposed areas in said photoresist layer corresponding to said opaque segments of said mask, and partially exposed areas in said photoresist between said exposed areas and said unexposed areas, said partially exposed areas being formed by diffraction of said actinic radiation at intersections of said clear and opaque segments of said photomask;

removing portions of said photoresist layer corresponding substantially to said exposed areas by developing said photoresist layer in a first solvent;

treating said photoresist layer to cause said partially exposed areas to become less soluble than said unexposed areas; and

removing portions of said photoresist layer corresponding substantially to said unexposed areas by developing said photoresist layer in a second solvent, the remaining portions of said partially exposed areas of said photoresist layer forming a mask.

8. A method of photolithographic mask image processing, comprising the steps of:

applying a layer of positive photoresist onto a surface of a semiconductor substrate, said photoresist layer comprising a photosensitive diazoquinone and an additive which produces image reversal;

positioning a photomask above said photoresist layer, said mask comprising a plurality of opaque segments separated by a plurality of transparent segments, said opaque segments having pattern edges;

image-wise exposing said photoresist layer through said plurality of transparent segments of said photomask with actinic radiation from a light source to form exposed areas, unexposed areas, and partially exposed areas in said photoresist layer, said exposed areas of said photoresist layer being formed beneath said plurality of transparent segments of said mask, said unexposed areas of said photoresist layer being formed beneath said plurality of opaque segments of said mask, and

said partially exposed areas of said photoresist layer being formed between said exposed areas and said unexposed areas of said photoresist layer, said partially exposed areas being formed by diffraction of said actinic radiation, said diffraction being produced by said pattern edges of said opaque segments;

developing said photoresist layer to remove said exposed areas and portions of said partially exposed areas;

baking said photoresist layer at an elevated temperature to harden said partially exposed areas with respect to said unexposed areas;

blanket exposing said photoresist layer to increase the solubility of said unexposed areas with respect to the solubility of said partially exposed areas; and

developing said photoresist layer in a second solvent to remove portions of said photoresist layer corresponding substantially to said unexposed areas of said photoresist layer, the remaining portions of said partially exposed areas of said photoresist layer forming thin resist lines on said semiconductor substrate.

9. A method of photolithographic mask image processing, comprising the steps of:

applying a layer of a photosensitive polymer to a surface of a semiconductor substrate, said photosensitive polymer comprising a photosensitive diazoquinone and an additive which produces image reversal;

providing a photomask above said photosensitive layer, said photomask comprising clear and opaque segments, each of said opaque segments having pattern edges;

image-wise exposing said photosensitive layer through said photomask with actinic radiation from a light source, said light producing exposed areas in portions of said photosensitive layer beneath said transparent segments of said photomask and unexposed areas in portions of said photosensitive layer beneath said opaque segments of said photomask, said pattern edges of said opaque segments causing light diffraction to form partially exposed areas between said exposed areas and said unexposed areas of said photosensitive layer;

developing said photosensitive layer in a solvent, said solvent dissolving regions of said photosensitive layer exposed to more than approximately 50% of the maximum intensity of said light, said solvent thus dissolving said exposed areas and portions of said partially exposed areas;

baking said photoresist layer at an elevated temperature to freeze the solubility of said partially exposed areas;

blanket exposing said photosensitive layer to increase the solubility of said unexposed areas so that they are more soluble than said partially exposed areas; and

developing said photosensitive layer in a solvent,

said solvent dissolving portions of said photoresist layer corresponding substantially to said unexposed areas,

the remaining portions of said partially exposed areas thus defining thin resist lines on the semiconductor substrate.

10. A method of photolithographic mask image processing, as recited in claim 9, additionally comprising the steps of:

applying a film onto the substrate, said film covering said mask; and

lifting off said mask to form a plurality of grooves in said film.

11. A method of photolithographic mask image processing, as recited in claim 10, additionally comprising the step of:

forming isolation regions within said plurality of narrow trenches of said semiconductor substrate.

12. The method of claim 11, wherein said resist lines are on the order of 0.5 to 2.0 microns in thickness.

13. The method of claim 11, wherein said film comprises a

layer of quartz of 80-100 Angstrom in thickness.

14. The method of claim 13, wherein said layer of quartz is sputtered onto the surface of the substrate.

15. The method of claim 9, wherein said partially exposed areas of said photosensitive layer comprise photoactive compounds which partially react to form decomposition products during said imagewise exposing step, and wherein said decomposition products react to substantially freeze the solubility of said partially exposed areas during said baking step.

16. The method of claim 15, wherein said decomposition products are carboxylate salts and where the reaction of said decomposition products during said baking step comprises a decarboxylation process.

17. The method of claim 9, wherein the shape of the thin resist lines can be controlled by varying the temperature of the solvent, the composition of the photoresist layer and the optical parameters of the light.

18. A method of photolithographic mask image processing, comprising the steps of:

applying a photoresist layer onto the surface of a substrate, said photoresist layer comprising a photosensitive diazoquinone and an additive which produces image reversal;

positioning a photomask above said photoresist layer, said photomask including a plurality of first segments separated by a plurality of second segments;

optically exposing said photoresist layer with actinic radiation through said plurality of first segments of said photomask to form exposed areas, partially exposed areas, and unexposed areas in said photoresist layer;

developing said photoresist layer to remove said exposed areas and portions of said partially exposed areas;

image reversing said photoresist layer; and

developing said photoresist layer for a time sufficient to remove portions of said photoresist layer corresponding substantially to said unexposed areas.

19. A method of photolithographic mask image processing, as recited in claim 18, wherein said step of image reversing comprises:

treating said photoresist layer to cause said partially exposed areas to become less soluble than said unexposed areas.