Positive working resist compositions process of exposing, stripping developing

Claim 2

A process for forming a positive photoresist on a surface which comprises: a. applying to said surface the surface of a solid, unexposed, photosensitive layer having a thickness of at least 8 microns, said layer comprised of (a) a polymer chosen from the group consisting of compositions having a polymer backbone and pendant acid-labile groups which are bound directly or indirectly to the polymer backbone, said pendant acid-labile groups represented by the formula: ##STR5## where n=0-4; R 1 is hydrogen or lower alkyl; R 2 is lower alkyl; and R 3 and R 4 independently are hydrogen or lower alkyl where the definition of lower alkyl includes the joining of R 1 and R 2 or R 1 and either R 3 or R 4 , or R 2 and either R 3 or R 4 to form a 5-, 6-, or 7-membered ring; (b) an initiator system that forms a catalytic amount of strong acid upon exposure to actinic radiation having a wavelength between about 3000 Å and about 9000 Å; and the other surface of the layer having adhered thereto with low to moderate adherence a thin, flexible, polymeric film support; then b. exposing the layer, imagewise, to actinic radiation to form an image, c. stripping the film support from the resulting image-bearing layer; and then, d. washing away the exposed areas of the layer to form a positive resist image, e. permanently modifying the adjacent areas on the substrate surface which are unprotected by the resist image by using a reagent capable of etching said areas or depositing a material on said areas; and f. blank exposing the resist image and stripping it from the resist in aqueous alkali.

Claim 3

The process of claim 1 wherein the photosensitive layer contains a plasticizer.

Claim 4

The process of claim 1 wherein the photosensitive layer contains a colorant.

Claim 5

The process of claim 1 wherein the photosensitive layer contains an adhesion promoter.

Claim 6

The process of claim 1 wherein the photosensitive layer contains a surfactant.

Claim 7

The process of claim 1 wherein the polymer is selected from a homopolymer, copolymer, terpolymer and block polymer.

Claim 8

The process of claim 6 wherein the polymer is a copolymer benzyl methacrylate and tetrahydropyranyl methacrylate.

Claim 9

The process of claim 6 where an acid labile monomer used to form said polymer is selected from the group comprising: 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate 1-butoxyethyl methacrylate, 1-butoxyethyl acrylate, 1-ethoxy-1-propyl methacrylate, 1-ethoxy-1-propyl acrylate, tetrahydropyranyl methacrylate, tetrahydropyranyl acrylate, tetrahydropyranyl p-vinylbenzoate, 1-ethoxy-1-propyl-p-vinylbenzoate, 4-(2-tetrahydropyranyloxy)benzyl methacrylate, 4-(2-tetrahydropyranyloxy)benzyl acrylate, 4-(1-butoxyethoxy)benzyl methacrylate, and 4-(1-butoxyethoxy)benzyl acrylate.

Claim 10

The process of claim 6 wherein the polymer contains one or more comonomers having no pendant acid-labile groups.

Claim 11

The process of claim 9 wherein the polymer having no pendant acid-labile groups is selected from the group comprising: methyl methacrylate, butyl methacrylate, benzyl methacrylate, benzyl acrylate, styrene, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate.

Claim 12

The process of claim 6 wherein the polymer is prepared by group transfer polymerization.

Claim 13

The process of claim 6 wherein the polymer is prepared by free radical polymerization.

Claim 14

The process of claim 6 wherein the initiator system contains an acid generator selected from diazonium, phosphonium, sulfonium, iodonium salts, halogen compounds, organometal/organohalogen combinations, benzoin esters and o-nitrobenzyl esters of strong acids, and N-hydroxyamide and N-hydroxyimide sulfonates, and aryl naphthoquinonediazide-4-sulfonates.

Claim 15

The process of claim 6 wherein the acid generator comprises about 0.1% to about 10% by weight of the photoresist composition.

Claim 16

A process for forming a positive resist on a surface which process comprises: a. applying to said surface the surface of a solid, unexposed, photosensitive layer having a thickness of about 8 microns, said layer comprised of (a) a polymer chosen from the group consisting of compositions having a polymer backbone and pendant acid-labile groups which are bound directly or indirectly to the polymer backbone, said pendant acid-labile groups represented by the formula: ##STR6## where n=0-4; R 1 is hydrogen or lower alkyl; R 2 is lower alkyl; and R 3 and R 4 independently are hydrogen or lower alkyl where the definition of lower alkyl include the joining of R 1 and R 2 or R 1 and either R 3 or R 4 , or R 2 and either R 3 or R 4 to form a 5-, 6-, or 7-membered ring; (b) an initiator system that forms a catalytic amount of strong acid upon exposure to actinic radiation having a wavelength between about 3000 Å to about 9000 Å, and the other surface of the layer having adhered thereto with low to moderate adherence a thin, flexible, polymer film support; then: b. exposing the layer, imagewise, to actinic radiation to form an image; c. stripping the film support from the resulting image-bearing layer; and then; d. washing away the exposed areas of the layer to form a positive resist image; e. permanently modifying the adjacent areas on the substrate surface which are unprotected by the resist image by using a reagent capable of etching said areas or depositing a material on said area, and, without the need to apply a second coating of photosensitive material; f. imagewise exposing the resist layer again to form a second latent image; g. washing away the exposed areas of the layer to form a positive resist image; h. permanently modifying the adjacent areas as in step e; i. solubilizing the resist and stripping from the substrate.

Claim 17

A process for forming a positive resist on a surface which process comprises: a. applying to said surface the surface of a solid, unexposed, photosensitive layer having a thickness of about 8 microns, said layer comprised of (a) a polymer chosen from the group consisting of compositions having a polymer backbone and pendant acid-labile groups which are bound directly or indirectly to the polymer backbone, said pendant acid-labile groups represented by the formula: ##STR6## where n=0-4; R 1 is hydrogen or lower alkyl; R 2 is lower alkyl; and R 3 and R 4 independently are hydrogen or lower alkyl where the definition of lower alkyl include the joining of R 1 and R 2 or R 1 and either R 3 or R 4 , or R 2 and either R 3 or R 4 to form a 5-, 6-, or 7-membered ring; (b) an initiator system that forms a catalytic amount of strong acid upon exposure to actinic radiation having a wavelength between about 3000 Å to about 9000 Å, and the other surface of the layer having adhered thereto with low to moderate adherence a thin, flexible, polymer film support; then: b. exposing the layer, imagewise, to actinic radiation to form an image; c. stripping the film support from the resulting image-bearing layer; and then; d. washing away the exposed areas of the layer to form a positive resist image; e. permanently modifying the adjacent areas on the substrate surface which are unprotected by the resist image by using a reagent capable of etching said areas or depositing a material on said area, and, without the need to apply a second coating of photosensitive material; f. imagewise exposing the resist layer again to form a second latent image; g. washing away the exposed areas of the layer to form a positive resist image; h. permanently modifying the adjacent areas as in step e; i. solubilizing the resist and stripping from the substrate.

Claim 18

The process of claim 15 wherein the photosensitive layer contains a plasticizer.

Claim 19

The process of claim 15 wherein the photosensitive layer contains a colorant.

Claim 20

The process of claim 15 wherein the sensitive layer contains an adhesion promoter.

Claim 21

The process of claim 15 wherein the photosensitive layer contains a surfactant.

Claim 22

The process of claim 15 wherein the polymer is selected from a homopolymer, copolymer, terpolymer and block polymer.

Claim 23

The process of claim 20 wherein the polymer is a copolymer benzyl methacrylate and tetrahydropyranyl methacrylate.

Claim 24

The process of claim 20 where a monomer used to form said polymer is selected from the group comprising: 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-butoxyethyl methacrylate, 1-butoxyethyl acrylate, 1-ethoxy-1-propyl methacrylate, 1-ethoxy-1-propyl acrylate, tetrahydropyranyl methacrylate, tetrahydropyranyl acrylate, tetrahydropyranyl p-vinylbenzoate, 1-ethoxy-1-propyl-p-vinylbenzoate, 4-(2-tetrahydropyranyloxy)benzyl methacrylate, 4-(2-tetrahydropyranyloxy)benzyl acrylate, 4-(1-butoxyethoxy)benzyl methacrylate, and 4-(1-butoxyethoxy)benzyl acrylate.

Claim 25

The process of claim 15 wherein the polymer contains one or more comonomers having no pendant acid-labile groups.

Claim 26

The process of claim 23 wherein the polymer having no pendant acid-labile groups is selected from the group comprising: methyl methacrylate, butyl methacrylate, benzyl methacrylate, benzyl acrylate, styrene, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate.

Claim 27

The process of claim 15 wherein the polymer is prepared by group transfer polymerization.

Claim 28

The process of claim 15 wherein the polymer is prepared by free radical polymerization.

Claim 29

The process of claim 15 wherein the initiator system contains an acid generator selected from diazonium, phosphonium, sulfonium, iodonium salts, halogen compounds, organometal/organohalogen combinations, benzoin esters and o-nitrobenzyl esters of strong acids, and N-hydroxyamide and N-hydroxyimide sulfonates, and aryl naphthoquinonediazide-4-sulfonates.

Claim 30

The process of claim 15 wherein the acid generator comprises about 0.1% to about 10% by weight of the photoresist composition.