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US 6,790,587 B1Granted
Fluorinated polymers, photoresists and processes for microlithography
AssigneeE. I. Du Pont de Nemours and Company
InventorsAndrew Edward Feiring, Jerald Feldman, Frank Leonard Schadt, III
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Abstract
Fluorinated polymers, photoresists and associated processes for microlithography are described. These polymers and photoresists are comprised of a fluoroalcohol functional group which simultaneously imparts high ultraviolet (UV) transparency and developability in basic media to these materials. The materials of this invention have high UV transparecy, particularly at short wavelengths, e.g., 157 nm, which makes them highly useful for lithography at these short wavelengths.
Claims66
A photoresist comprising:
- (a) a fluorine-containing polymer comprising a repeat unit derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group having the structure:
- —C(Rf)(Rf′)OH
- wherein Rf and Rf′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10;
- and
- (b) at least one photoactive component;
- wherein the fluorine-containing polymer has an absorption coefficient of less than 2.5 μm−1 at a wavelength of 157 nm.
3 more elements
A process for preparing a photoresist image on a substrate comprising, in order:
- (W) applying a photoresist composition on a substrate, wherein the photoresist composition comprises:
- (a) a fluorine-containing polymer comprising a repeat unit derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group having the structure:
- —C(Rf)(Rf′)OH
- wherein Rf and Rf′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10, and wherein the fluorine-containing polymer has an absorption coefficient of less than 2.5 μm−1 at a wavelength of 157 nm;
- (b) at least one photoactive component;
- and
- (c) a solvent;
- (X) drying the photoresist composition to substantially remove the solvent and thereby form a photoresist layer on the substrate;
- (Y) imagewise exposing the photoresist layer to form imaged and non-imaged areas;
- and
- (Z) developing the exposed photoresist layer having imaged and non-imaged areas to form the relief image on the substrate.
8 more elements
A fluorine-containing copolymer comprising a repeat unit derived from at least one ethylenically unsaturated compound characterized in that at least one ethylenically unsaturated compound is cyclic or polycyclic, at least one ethylenically unsaturated compound contains at least one fluorine atom covalently attached to an ethylenically unsaturated carbon atom, and at least one ethylenically unsaturated compound is comprised of a fluoroalcohol functional group having the structure:
- —C(Rf)(Rf′)OH
- wherein Rf and Rf′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10.
A photoresist comprising:
- (a) a fluorine-containing copolymer comprising a repeat unit derived from at least one ethylenically unsaturated compound characterized in that at least one ethylenically unsaturated compound is cyclic or polycyclic, at least one ethylenically unsaturated compound contains at least one fluorine atom covalently attached to an ethylenically unsaturated carbon atom, and at least one ethylenically unsaturated compound is comprised of a fluoroalcohol functional group having the structure:
- —C(Rf)(Rf′)OH
- wherein Rf and Rf′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10;
- and
- (b) at least one photoactive component;
- wherein the fluorine-containing copolymer contains sufficient functionality to render the photoresist developable so as to produce a relief image upon imagewise exposure to ultraviolet radiation having wavelength of <365 nm.
3 more elements
A process for preparing a photoresist image on a substrate comprising, in order:
- (W) applying a photoresist composition on a substrate, wherein the photoresist comprises:
- (a) a fluorine-containing copolymer comprising a repeat unit derived from at least one ethylenically unsaturated compound characterized in that at least one ethylenically unsaturated compound is cyclic or polycyclic, at least one ethylenically unsaturated compound contains at least one fluorine atom covalently attached to an ethylenically unsaturated carbon atom, and at least one ethylenically unsaturated compound is comprised of a fluoroalcohol functional group having the structure:
- —C(Rf)(Rf′)OH
- wherein Rf and Rf′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10;
- (b) at least one photoactive component;
- and
- (c) a solvent;
- wherein the fluorine-containing copolymer contains sufficient functionality to render the photoresist developable so as to produce a relief image upon imagewise exposure to ultraviolet radiation having wavelength of <365 nm;
- (X) drying the photoresist composition to substantially remove the solvent and thereby form a photoresist layer on the substrate;
- (Y) imagewise exposing the photoresist layer to form imaged and non-imaged areas;
- and
- (Z) developing the exposed photoresist layer having imaged and non-imaged areas to form the relief image on the substrate.
9 more elements
A photoresist comprising:
- (a) a fluorine-containing copolymer comprising a repeat unit derived from at least one ethylenically unsaturated compound containing at least three fluorine atoms covalently attached to two ethylenically unsaturated carbon atoms and a repeat unit derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group having the structure:
- —C(Rf)(Rf′)OH
- wherein Rf and Rf′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10;
- and
- (b) at least one photoactive component;
- wherein the fluorine-containing copolymer contains sufficient functionality to render the photoresist developable so as to produce a relief image upon imagewise exposure to ultraviolet radiation having wavelength of <365 nm.
3 more elements
A process for preparing a photoresist image on a substrate comprising, in order:
- (W) applying a photoresist composition on a substrate, wherein the photoresist composition comprises:
- (a) a fluorine-containing copolymer comprising a repeat unit derived from at least one ethylenically unsaturated compound containing at least three fluorine atoms covalently attached to two ethylenically unsaturated carbon atoms and a repeat unit derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group having the structure:
- —C(Rf)(Rf′)OH
- wherein Rf and Rf′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10;
- and
- (b) at least one photoactive component;
- and
- (c) a solvent;
- (X) drying the photoresist composition to substantially remove the solvent and thereby form a photoresist layer on the substrate;
- (Y) imagewise exposing the photoresist layer to form imaged and non-imaged areas;
- and
- (Z) developing the exposed photoresist layer having imaged and non-imaged areas to form the relief image on the substrate.
9 more elements
A photoresist comprising:
- (a) a fluorine-containing polymer comprising a repeat unit derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group having the structure:
- —XCH2C(Rf)(Rf′)OH
- wherein Rf and Rf′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10;
- and X is selected from the group consisting of sulfur, oxygen, nitrogen, phosphorous, other Group Va element, and other Group VIa element;
- and
- (b) at least one photoactive component;
- wherein the fluorine-containing polymer contains sufficient functionality to render the photoresist developable so as to produce a relief image upon imagewise exposure to ultraviolet radiation having wavelength of <365 nm.
4 more elements
A process for preparing a photoresist image on a substrate comprising, in order:
- (W) applying a photoresist composition on a substrate, wherein the photoresist composition comprises:
- (a) a fluorine-containing polymer comprising a repeat unit derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group having the structure:
- —XCH2C(Rf)(Rf′)OH
- wherein Rf and Rf′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10;
- and X is selected from the group consisting of sulfur, oxygen, nitrogen, phosphorous, other Group Va element, and other Group VIa element;
- and
- (b) at least one photoactive component;
- wherein the fluorine-containing polymer contains sufficient functionality to render the photoresist developable so as to produce a relief image upon imagewise exposure to ultraviolet radiation having wavelength <365 nm;
- (c) at least one photoactive component;
- and
- (d) a solvent;
- (X) drying the photoresist composition to substantially remove the solvent and thereby form a photoresist layer on the substrate;
- (Y) imagewise exposing the photoresist layer to form imaged and non-imaged areas;
- and
- (Z) developing the exposed photoresist layer having imaged and non-imaged areas to form the relief image on the substrate.
12 more elements
A fluorine-containing polymer comprising the structure:
- wherein each of R1, R2, R3, and R4 independently is hydrogen, a halogen atom, a hydrocarbon group containing from 1 to 10 carbon atoms, a substituted hydrocarbon group, an alkoxy group, a carboxylic acid, a carboxylic acid ester, or a functional group containing the structure:
- —C(Rf)(Rf′)ORb
- wherein Rf and Rf′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10;
- Rb is hydrogen or an acid- or base-labile protecting group;
- p is the number of repeat units in the polymer;
- r is 0-4;
- at least one of the repeat units has a structure whereby at least one of R1, R2, R3, and R4 contains the structure C(Rf)(Rf′)ORb;
- and wherein the fluorine-containing polymer has an absorption coefficient of less than 4.0 μm−1 at a wavelength of 157 nm.
5 more elements
A photoresist comprising:
- (a) a fluorine-containing polymer comprising the structure:
- wherein each of R1, R2, R3, and R4 independently is hydrogen, a halogen atom, a hydrocarbon group containing from 1 to 10 carbon atoms, a substituted hydrocarbon group, an alkoxy group, a carboxylic acid, a carboxylic acid ester, or a functional group containing the structure:
- —C(Rf)(Rf′)ORb
- wherein Rf and Rf′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10;
- Rb is hydrogen or an acid- or base-labile protecting group;
- p is the number of repeat units in the polymer;
- r is 0-4;
- at least one of the repeating units has a structure whereby at least one of R1, R2, R3, and R4 contains the structure C(Rf)(Rf′)ORb;
- and wherein the fluorine-containing polymer has an absorption coefficient of less than 4.0 μm−1 at a wavelength of 157 nm;
- and
- (b) at least one photoactive component.
8 more elements
A process for preparing a photoresist image on a substrate comprising, in order:
- (W) applying a photoresist composition on a substrate, wherein photoresist composition comprises:
- (a) a fluorine-containing polymer comprising the structure:
- wherein each of R1, R2, R3, and R4 independently is hydrogen, a halogen atom, a hydrocarbon group containing from 1 to 10 carbon atoms, a substituted hydrocarbon group, an alkoxy group, a carboxylic acid, a carboxylic acid ester, or functional group containing the structure:
- —C(Rf)(Rf′)ORb
- wherein Rf and Rf′ are the same or different fluoroalkyl groups of from 1 to 10 carbon atoms or taken together are (CF2)n wherein n is 2 to 10;
- Rb is hydrogen or an acid- or base-labile protecting group;
- p is the number of repeat units in the polymer;
- r is 0-4;
- at least one of the repeat units has a structure whereby at least one of R1, R2, R3, and R4 contains the structure C(Rf)(Rf′)ORb;
- and wherein the fluorine-containing polymer has an absorption coefficient of less than 4.0 μm−1 at a wavelength of 157 nm;
- (b) at least one photoactive component;
- and
- (c) a solvent;
- (X) drying the photoresist composition to substantially remove the solvent and thereby form a photoresist layer on the substrate;
- (Y) imagewise exposing the photoresist layer to form imaged and non-imaged areas;
- and
- (Z) developing the exposed photoresist layer having imaged and non-imaged areas to form the relief image on the substrate.
14 more elements
Dependencies are inferred from the claim text.