# US 7,608,380 B2 · Spin bowl compatible polyamic acids/imides as wet developable polymer binders for anti-reflective coatings

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- Number: US 7,608,380 B2
- Document ID: US7608380B2
- Status: Granted
- Kind: B2
- Application number: 11/264,858
- Filed: 2005-11-02
- Published: 2006-03-23
- Granted: 2009-10-27
- Earliest claimed: 2002-01-17
- Assignees: Brewer Science Inc.
- Inventors: Robert Christian Cox; Charles J. Neef
- Web page: https://patentgrep.com/patent/US7608380B2

## CPC

- C09D 179/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G 73/10: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G 73/1025: {polymerised by radiations}
- C08G 73/1039: {comprising halogen-containing substituents}
- C08G 73/1064: {containing sulfur}
- G02B 1/111: using layers comprising organic materials
- G03F 7/038: Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021)
- G03F 7/091: {characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement}
- Y10S 430/106: Binder containing
- Y10S 430/151: Matting or other surface reflectivity altering material
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

Anti-reflective compositions and methods of using these compositions to form circuits are provided. The compositions comprise a polymer dissolved or dispersed in a solvent system. In a preferred embodiment, the polymers are copolymers of a compound having the formulas and a compound having the formula where: (1) each R is individually selected from the group consisting of —OH, —NH2, hydrogen, aliphatics, and phenyls; and (2) L is selected from the group consisting of —SO2— and —CR′2—. The resulting compositions are spin bowl compatible (i.e., they do not crosslink prior to the bake stages of the microlithographic processes or during storage at room temperature), are wet developable, and have superior optical properties.

## Claims

### Claim 1

In a composition for use in photolithographic processes wherein the composition comprises a polymer dissolved or dispersed in a solvent system, the improvement being that said composition comprises a thermal crosslinking agent and said polymer is a copolymer of a compound having the formula
and a compound having the formula
wherein:
each R is individually selected from the group consisting of —OH, —NH2, hydrogen, aliphatics, and phenyls, at least one R on each ring of(I) being —NH2, and at least one R on each ring of (I) being —OH; and
L is selected from the group consisting of —SO2— and —CR′2—, where each R′ is individually selected from the group consisting of hydrogen, aliphatics, phenyls, and —CX3, where each X is individually selected from the group consisting of the halogens,
wherein said composition can be formed into a layer that will absorb at least about 90% of light having a wavelength of about 248 nm at a thickness of about 40 nm.

### Claim 2 (depends on 1)

The composition of claim 1, wherein at least one L is —SO2—.

### Claim 3 (depends on 1)

The composition of claim 1, wherein at least one L is —CR′2—.

### Claim 4 (depends on 3)

The composition of claim 3, each R′ is —CF3.

### Claim 5

The combination of:
a substrate having a surface; and
a cured anti-reflective layer adjacent said surface, said anti-reflective layer being formed from a composition comprising a thermal crosslinking agent and a polymer dissolved or dispersed in a solvent system, said polymer being a copolymer of a compound having the formula
and a compound having the formula
wherein:
each R is individually selected from the group consisting of —OH, —NH2, hydrogen, aliphatics, and phenyls, at least one R on each ring of (I) being —NH2, and at least one R on each ring of (I) being —OH; and
L is selected from the group consisting of —SO2— and —CR′2—, where each R′ is individually selected from the group consisting of hydrogen, aliphatics, phenyls, and —CX3, where each X is individually selected from the group consisting of the halogens,
wherein said layer absorbs at least about 90% of light having a wavelength of about 248 nm at a thickness of about 40 nm.

### Claim 6 (depends on 5)

The combination of claim 5, said cured layer being wet developable.

### Claim 7 (depends on 5)

The combination of claim 5, wherein said cured layer has a percent solubility of at least about 50% when propylene glycol methyl ether acetate is the solvent.

### Claim 8 (depends on 5)

The combination of claim 5, wherein said substrate is selected from the group consisting of silicon wafers and ion implant layers.

### Claim 9 (depends on 5)

The combination of claim 5, said combination further comprising a photoresist layer adjacent said cured layer.

### Claim 10 (depends on 5)

The combination of claim 5, said cured layer being at least about 90% soluble in a base developer.

### Claim 11 (depends on 5)

The combination of claim 5, wherein at least one L is —SO2—.

### Claim 12 (depends on 5)

The combination of claim 5, wherein at least one L is —CR′2—.

### Claim 13 (depends on 12)

The combination of claim 12, wherein each R′ is —CF3.

### Claim 14

A method of using a composition in photolithographic processes, said method comprising the steps of:
applying a quantity of a composition to a substrate; and
heating said composition to induce crosslinking and form a cured layer thereon, said composition comprising a thermal crosslinking agent and a polymer dissolved or dispersed in a solvent system, said polymer being a copolymer of a compound having the formula
and a compound having the formula
wherein:
each R is individually selected from the group consisting of —OH, —NH2, hydrogen, aliphatics, and phenyls, at least one R on each ring of (I) being —NH2; and
L selected from the group consisting of —SO2— and —CR′2—, where each R′ is individually selected from the group consisting of hydrogen, aliphatics, phenyls, and —CX3, where each X is individually selected from the group consisting of the halogens,
said cured layer absorbing at least about 90% of light having a wavelength of about 248 nm at a thickness of about 40 nm.

### Claim 15 (depends on 14)

The method of claim 14, wherein said applying step comprises spin-coating said composition onto said substrate surface.

### Claim 16 (depends on 14)

The method of claim 14, wherein said substrate has a hole formed therein, said hole being defined by a bottom wall and sidewalls, and said applying step comprises applying said composition to at least a portion of said bottom wall and sidewalls.

### Claim 17 (depends on 14)

The method of claim 14, wherein said heating comprises baking said layer at a temperature of from about 100-250° C.

### Claim 18 (depends on 17)

The method of claim 17, further including the step of applying a photoresist to said cured layer.

### Claim 19 (depends on 18)

The method of claim 18, furthering including the steps of:
exposing at least a portion of said photoresist to activating radiation; and
developing said exposed photoresist.

### Claim 20 (depends on 19)

The method of claim 19, wherein said developing step results in the removal of said cured layer from areas adjacent said exposed photoresist.

### Claim 21

The combination of:
a substrate having a surface; and
an anti-reflective layer adjacent said surface, said anti-reflective layer being formed from a composition comprising a thermal crosslinking agent and a polymer dissolved or dispersed in a solvent system, said polymer being a copolymer of a compound having the formula
and a compound having the formula
wherein:
each R is individually selected from the group consisting of —OH, —NH2, hydrogen, aliphatics, and phenyls, at least one R on each ring of (I) being —NH2 and at least one R on each ring of (I) being —OH; and
L is selected from the group consisting of —SO2— and —CR′2—, where each R′ is individually selected from the group consisting of hydrogen, aliphatics, phenyls, and —CX3, where each X is individually selected from the group consisting of the halogens.

### Claim 22

A method of using a composition in photolithographic processes, said method comprising the step of applying a quantity of a composition to a substrate to form a layer thereon and heating said composition to induce crosslinking, wherein:
said composition comprises a thermal crosslinking agent and a polymer dissolved or dispersed in a solvent system, said polymer being a copolymer of a compound having the formula
and a compound having the formula
wherein:
each R is individually selected from the group consisting of —OH, —NH2, hydrogen, aliphatics, and phenyls, at least one R on each ring of (I) being —NH2; and
L is selected from the group consisting of —SO2— and —CR′2—, where each R′ is individually selected from the group consisting of hydrogen, aliphatics, phenyls, and —CX3, where each X is individually selected from the group consisting of the halogens;
said substrate has a hole formed therein, said hole being defined by a bottom wall and sidewalls; and
said applying step comprises applying said composition to at least a portion of said bottom wall and sidewalls.

### Claim 23

A method of using a composition in photolithographic processes, said method comprising the step of applying a quantity of a composition to a substrate to form a layer thereon and heating said composition to induce crosslinking, said composition comprising a thermal crosslinking agent and a polymer dissolved or dispersed in a solvent system, said polymer being a copolymer of a compound having the formula
and a compound having the formula
wherein:
each R is individually selected from the group consisting of —OH, —NH2, hydrogen, aliphatics, and phenyls, at least one R on each ring of (I) being —NH2; and
L is selected from the group consisting of —SO2— and —CR′2—, where each R′is individually selected from the group consisting of hydrogen,aliphatics, phenyls, and —CX3, where each X is individually selected from the group consisting of the halogens,
said layer absorbing at least about 90% of light having a wavelength of about 248 nm at a thickness of about 40 nm
wherein said substrate has a hole formed therein, said hole being defined by a bottom wall and sidewalls, and said applying step comprises applying said composition to at least a portion of said bottom wall and sidewalls.

### Claim 24 (depends on 23)

The method of claim 23, wherein said heating comprises baking said layer at a temperature of from about 100-250° C. to yield a cured layer, said method further including the steps of:
applying a photoresist to said cured layer;
exposing at least a portion of said photoresist to activating radiation; and
developing said exposed photoresist, wherein said developing step results in the removal of said cured layer from areas adjacent said exposed photoresist.

### Claim 25

A method of using a composition in photolithographic processes, said method comprising the steps of:
applying a quantity of a composition to a substrate to form a layer thereon, said composition comprising a thermal crosslinking agent a polymer dissolved or dispersed in a solvent system, said polymer being a copolymer of a compound having the formula
and a compound having the formula
wherein:
each R is individually selected from the group consisting of —OH, —NH2, hydrogen, aliphatics, and phenyls, at least one R on each ring of (I) being —NH2; and
L is selected from the group consisting of —SO2— and —CR′2—, where each R′is individually selected from the group consisting of hydrogen, aliphatics, phenyls, and —CX3—, where each X is individual selected form the group consisting of the halogens;
curing said layer to form a cured layer;
applying a photoresist to said cured layer;
exposing at least a portion of said photoresist to activating radiation; and
developing said exposed photoresist, wherein said developing step results in the removal of said cured layer from areas adjacent said exposed photoresist.