Formation of etch-resistant resists through preferential permeation

Claim 2

Method of creating etch-resistant polymeric films for use in the production of micron and submicron dimension patterns and fine lines, comprising: (a) applying a layer of polymeric resist material to a substrate; (b) exposing said layer of polymeric resist material to at least one kind of patterned radiation capable of altering the permeability of said polymeric resist material; and (c) preferentially permeating/diffusing an organometallic material into the surface of said polymeric resist material, to provide etch resistance within the portion of said polymeric resist material within which significant permeation of said organometallic material occurs.

Claim 3

Method of claim 1, wherein exposure of said polymeric resist material to said patterned radiation decreases the permeability of said resist material within said irradiated areas.

Claim 4

Method of claim 1, wherein exposure of said polymeric resist material to said patterned radiation increases the permeability of said resist material within said irradiated areas.

Claim 5

Method of claim 1, wherein said organometallic material reacts with at least portions of said polymeric resist material.

Claim 6

Method of claims 1, 2 or 3, wherein said etch-resistant portion, and any polymeric material protected by such etch-resistant portion, is dry developed using plasma or reactive ion etching, wherein the active plasma/etchant is oxygen or a combination of oxygen with a halogen-containing compound.

Claim 7

Method of claims 1, 2 or 3, wherein said polymeric resist material comprises a material selected from the group consisting of photodegradable polymers which undergo chain scission or fragmentation upon irradiation, mixtures of photoactive compound and polymeric material, and combinations thereof, wherein said polymeric resist material may or may not comprise functional groups capable of reacting with an organometallic material.

Claim 8

Method of claims 1, 2 or 3, wherein said polymeric resist material comprises a material selected from the group consisting of photocrosslinkable polymers, mixtures of polymeric resins with crosslinkable polyfunctional reagents, mixtures of polymeric resins with sensitizers/photoinitia- tors, and combinations thereof, wherein said polymeric resist material may or may not comprise functional groups capable of reacting with an organometallic material.

Claim 9

Method of creating positive tone etch-resistant polymeric films for use in the production of micron and submicron dimension patterns and fine lines, comprising: (a) applying a layer of polymeric resist material to a substrate, wherein said polymeric resist material comprises a photocrosslinkable polymer or a combination of a photoactive compound and at least one polymer; (b) exposing said layer of polymeric resist material to patterned radiation, wherein said radiation induces crosslinking of said polymeric material as the dominant reaction; and (c) preferentially permeating/diffusing an organometallic material into the surface of said polymeric resist material, to provide an etch-resistant latent image within said polymeric resist material, wherein said etch-resistance occurs within the portion of said polymeric resist material which has not been irradiated; and (d) developing said etch-resistant latent image into a patterned resist using dry etching techniques such as plasma or reactive ion etching.

Claim 10

Method of creating positive tone etch-resistant polymeric films for use in the production of micron and submicron dimension patterns and fine lines, comprising: (a) applying a layer of polymeric resist material to a substrate, wherein said polymeric resist material comprises a photocrosslinkable polymer or a combination of a photoactive compound and at least one polymer; (b) exposing said layer of polymeric resist material to patterned radiation, wherein said radiation induces crosslinking of said polymeric material as the dominant reaction; and (c) preferentially permeating/diffusing an organometallic material into the surface of said polymeric resist material, to provide an etch-resistant latent image within said polymeric resist material, wherein said etch-resistance occurs within the portion of said polymeric resist material which has not been irradiated; and (d) developing said etch-resistant latent image into a patterned resist using dry etching techniques such as plasma or reactive ion etching.

Claim 11

Method of claim 8, wherein said photocrosslinkable polymer contains functional groups capable of reacting with an organometallic material selected from the group consisting of hydroxy, carboxyl, phenol, amine and imide NH.

Claim 12

Method of claim 8, wherein said photocrosslinkable polymer is selected from the group consisting of novolak resins, resoles, polyvinyl phenol, and polymers comprising azido groups and that at least one polymer is selected from the group consisting of unsaturated polymeric resins, polymeric resins combined with unsaturated monomers, branched monomers such as polyfunctional acrylates, epoxides, novolak resins, resoles, polyvinyl phenol, and polymers comprising azido groups.

Claim 13

Method of claim 8, wherein said photoactive compound is a sensitizer/photoinitiator selected from the group consisting of naphthothiazoline, nitrophenyl derivatives, azides, quinones, and onium salts.

Claim 14

Method of claims 8 and 11, wherein said photoactive compound comprises at least one azide of the general structure: where R may be alkyl, aryl, acyl, or sulfonyl, or an azide group incorporated as a polymer side chain, and wherein said azide is selected from the group consisting of di-(p-azidophenyl)sulfide, di-(m-azidophenyl)sulfone and 3,3'-diazidobenzophenone.

Claim 15

Method of claim 10, wherein said at least one polymer is selected from predominantly scission/fragmentation polymers such as copolymers containing methacrylic acid or methacrylic esters, and wherein the radiation source used will not degrade the polymer to the extent that the crosslinking reactions initiated by said photoactive compound are not the dominant reactions.

Claim 16

Method of creating negative tone etch-resistant polymeric films for use in the production of micron and submicron dimension patterns and fine lines, comprising: (a) applying a layer of polymeric resist material to a substrate, wherein said polymeric resist material is comprised of at least one photodegradable polymer which undergoes chain scission or fragmentation upon irradiation, or of a combination of a photoactive compound and at least one polymer, wherein said at least one polymer may or may not be photodegradable; (b) exposing said layer of polymeric resist material to patterned radiation, wherein said radiation induces chain scission or fragmentation of said at least one photodegradable polymer as the dominant reaction; and (c) preferentially permeating an organometallic material into the surface of said polymeric resist material, to provide an etch-resistant latent image within said polymeric resist material, wherein said etch-resistance occurs in the irradiated areas of said polymeric resist, and (d) developing said etch-resistant latent image into a patterned resist using dry etching techniques such as oxygen reactive ion etching, and plasma and ion etching.

Claim 17

Method of creating negative tone etch-resistant polymeric films for use in the production of micron and submicron dimension patterns and fine lines, comprising: (a) applying a layer of polymeric resist material to a substrate, wherein said polymeric resist material is comprised of at least one photodegradable polymer which undergoes chain scission or fragmentation upon irradiation, or of a combination of a photoactive compound and at least one polymer, wherein said at least one polymer may or may not be photodegradable; (b) exposing said layer of polymeric resist material to patterned radiation, wherein said radiation induces chain scission or fragmentation of said at least one photodegradable polymer as the dominant reaction; and (c) preferentially permeating an organometallic material into the surface of said polymeric resist material, to provide an etch-resistant latent image within said polymeric resist material, wherein said etch-resistance occurs in the irradiated areas of said polymeric resist, and (d) developing said etch-resistant latent image into a patterned resist using dry etching techniques such as oxygen reactive ion etching, and plasma and ion etching.

Claim 18

Method of claim 14, wherein said at least one photodegradable polymer or at least one polymer contains functional groups capable of reacting with an organometallic material selected from the group consisting of hydroxy, carboxyl, phenol, amine and imide NH.

Claim 19

Method of claim 14, wherein said at least one photodegradable polymer is selected from the group consisting of copolymers of methyl methacrylate and methacrylic acid, terpolymers of methyl methacrylate, methacrylic acid, and methacrylic anhydride, copolymers containing 2,4-dimethylglutarimide, copolymers containing maleimide, poly (2,4-dimethylglutarimide), copolymers containing methacrylic acid, terpolymers containing methacrylic acid, copolymers containing esterified methacrylates, terpolymers containing esterified methacrylates, copolymers containing a methyl styrene, and terpolymers containing a methyl styrene.

Claim 20

Method of claim 14, wherein said at least one polymer is selected from the group consisting of copolymers of methyl methacrylate and methacrylic acid, terpolymers of methyl methacrylate, methacrylic acid and methacrylic anhydride, copolymers containing 2,4-dimethylglutarimide, copolymers containing maleimide, poly(2,4-dimethylglutarimide), copolymers containing methacrylic acid, terpolymers containing methacrylic acid, copolymers of esterified methacrylates, terpolymers containing esterified methacrylates, copolymers of styrene, terpolymers of styrene, copolymers of substituted styrenes, terpolymers of substituted styrenes, novolak resins, resoles, polyvinylphenols, polyimides including polyamic acid, polyisoimide, and polyvinylpyrrolidone.

Claim 21

Method of claim 14, wherein said photoactive compound is selected from the group consisting of compounds comprising at least one of the following general structures where R 1 , R 2 can be H, alkyl, aryl, halogen, alkoxyl, or esterified sulfo groups; R 3 , R 4 represent alkyl, aryl, part of cyclic or heterocyclic groups.

Claim 22

Method of claim 14, wherein said photoactive compound is poly(alkenesulfone).