Process using radiation curable epoxy containing resist and resultant product

Claim 2

Article including a substrate provided with an intimately contacting coating of a radiation-sensitive negative resist material, said material consisting essentially of a polymer, said polymer comprising a carbonaceous chain with substituent branches at least some of which contain epoxy groupings which cross-link responsive to impinging radiation, characterized in that the said polymer is substantially ethylenically saturated; that the said polymer has a weight average molecular weight of about 10 3 to 10 6 ; that the said epoxy groupings: ##STR5## are connected to the main polymer chain through at least one branch atom; and that the molecular weight distribution of the said polymer defined as M w /M n , in which M w is the weight average molecular weight and M n is the number average molecular weight, is numerically equal to a value of less than 5.

Claim 3

Article of claim 1 in which the said polymer contains epoxy-containing branches in number at least equal to one such branch for every ten carbon atoms in the main polymer chain.

Claim 4

Article of claim 1 in which the temperature range defining the thermal glass transition T g has a lower temperature limit which is below the lowest temperature to be attained by the said article at any time prior to exposure to cross-linking radiation.

Claim 5

Article of claim 1 in which the said polymer is an addition polymer.

Claim 6

Article of claim 4 in which the said polymer is the polymerization product of monomer units at least some of which are substituted or unsubstituted glycidyl acrylate.

Claim 7

Article of claim 5 in which the said polymer is a copolymer and in which at least some of the monomer units are glycidyl methacrylate.

Claim 8

Article of claim 6 in which at least some of the monomers are ethyl acrylate.

Claim 9

Article of claim 1 in which the said polymer is a homopolymer.

Claim 10

Article of claim 1 in which the said polymer is a copolymer which may be regarded as being the polymerization product of at least two types of monomer at least one of which contains the epoxy-containing substituent branches as defined.

Claim 11

Article of claim 1 in which any non-glycidyl comonomers as polymerized are characterized by a glass transition temperature range T g which is lower than that of a homopolymer of any glycidyl monomer.

Claim 12

Article of claim 1 in which the low temperature limit of the thermal T g range of the said polymer is below 22° C.

Claim 13

Article of claim 1 in which the said substrate comprises a semiconducting material.

Claim 14

Article of claim 12 in which the said semiconducting material is elemental.

Claim 15

Article of claim 13 in which the said elemental material is silicon.

Claim 16

Article of claim 12 in which the said semiconducting material is a compound semiconductor.

Claim 17

Article of claim 15 in which the said compound semiconductor is a binary intermetallic compound of a Group III and a Group V element in accordance with the periodic table of Mendelyeev.

Claim 18

Article of claim 1 in which at least a portion of the substrate surface with which the negative resist material makes intimate contact is oxidic.

Claim 19

Article of claim 17 in which at least a portion of the said substrate surface is an oxide of silicon.

Claim 20

Article of claim 1 in which at least a portion of the substrate surface with which the said negative resist material makes intimate contact is metallic.

Claim 21

Article of claim 1 in which the said polymer contains substituent groupings which increase the absorption for X-ray radiation.

Claim 22

Article of claim 20 in which the said substituent groupings contain ferrocene.

Claim 23

Article including a substrate to be pattern delineated provided with an intimately contacting coating of negative resist material, said material consisting essentially of a polymer consisting of a primarily carbonaceous chain with side branches containing radiation sensitive groupings which result in cross-linking, said sensitive groupings comprising epoxy groupings, characterized in that the polymer is of a composition represented by the formula: ##STR6## in which X is any grouping, X' is any grouping, Z, Y, and Y' are optional carbonaceous substituents containing from 0 to 4 carbon atoms, and X" is hydrogen or X" and Y" are optional substituents of the class represented by X' and Y', respectively, the said polymer being substantially ethylenically saturated, the said polymer having a molecular weight M of from about 10 3 to 10 6 in which said polymer the epoxy grouping ##STR7## are present in a number of at least one such substituent for every ten carbon atoms in the main polymer chain, in which the molecular weight distribution is defined as M w /M n , in which M w is the weight average molecular weight and M n is the number average molecular weight, is less than 5, in which the glass transition temperature T g is below any temperature attained prior to exposure, said polymer being produced by a single step addition polymerization process in which monomers contain the side chains shown in the formula, in which the order of the groupings one designated by the subscript n and one designated by the subscript n' is random and in which the groupings designated by the subscript n and/or groupings designated by the subscript n', while necessarily falling within the chamical classification set forth, are not necessarily identical.

Claim 24

Article including a substrate to be pattern delineated provided with an intimately contacting coating of negative resist material, said material consisting essentially of a polymer consisting of a primarily carbonaceous chain with side branches containing radiation sensitive groupings which result in cross-linking, said sensitive groupings comprising epoxy groupings, characterized in that the polymer is of a composition represented by the formula: ##STR6## in which X is any grouping, X' is any grouping, Z, Y, and Y' are optional carbonaceous substituents containing from 0 to 4 carbon atoms, and X" is hydrogen or X" and Y" are optional substituents of the class represented by X' and Y', respectively, the said polymer being substantially ethylenically saturated, the said polymer having a molecular weight M of from about 10 3 to 10 6 in which said polymer the epoxy grouping ##STR7## are present in a number of at least one such substituent for every ten carbon atoms in the main polymer chain, in which the molecular weight distribution is defined as M w /M n , in which M w is the weight average molecular weight and M n is the number average molecular weight, is less than 5, in which the glass transition temperature T g is below any temperature attained prior to exposure, said polymer being produced by a single step addition polymerization process in which monomers contain the side chains shown in the formula, in which the order of the groupings one designated by the subscript n and one designated by the subscript n' is random and in which the groupings designated by the subscript n and/or groupings designated by the subscript n', while necessarily falling within the chamical classification set forth, are not necessarily identical.

Claim 25

Article of claim 22 in which at least one of the substituents X', X", Y', and Y" is an aryl group selected from the group consisting of substituted and unsubstituted phenyl, naphthyl, and anthryl.

Claim 26

Article of claim 23 in which at least some of the said aryl groupings are halogenated.

Claim 27

Article of claim 24 in which halogenation is by at least one halogen selected from the group consisting of bromine and chlorine.

Claim 28

Article of claim 1 in which the said polymer contains aryl groupings in number at least equal to one such group for every twenty carbon atoms in the main polymer chain.

Claim 29

Article of claim 26 in which such aryl groupings are selected from the group consisting of substituted and unsubstituted phenyl, naphthyl, and anthryl groups.

Claim 30

Article of claim 27 in which at least some of such aryl groups contain at least one substituent halogen atom.

Claim 31

Article of claim 28 in which the said polymer contains epoxy-containing branches in number at least equal to one such branch for every ten carbon atoms in the main polymer chain and in which the said polymer contains aryl groupings in number at least equal to one such groupings for every twenty carbon atoms in the main polymer chain.

Claim 32

Article of claim 29 in which the said polymer is an addition polymer of monomers including substituted and unsubstituted styrene.

Claim 33

Article of claim 30 in which the said polymer is an addition polymer of monomers including substituted or unsubstituted glycidyl acrylate.

Claim 34

Article of claim 31 in which the said styrene is halogenated and in which the said acrylate includes glycidyl methacrylate.

Claim 35

Article of claim 32 in which the said styrene is selected from the group consisting of substituted or unsubstituted chlorostyrene and bromostyrene.

Claim 36

Article of claim 29 in which the temperature range defining the thermal glass transistion T g has a lower temperature limit which is above 22° C.

Claim 37

Article of claim 26 in which the said polymer contains substituent groupings which increase the absorption for X-ray radiation.

Claim 38

Process for pattern delineating a substrate surface on which there is a tightly adherent negative resist material comprising the steps of selectively exposing the said resist material to radiation with irradiated regions corresponding with a negative image of the pattern to be delineated on the substrate, so that the said radiation reduces the solubility of the said resist with respect to a developing reagent, in which the said resist material consists essentially of an uncured polymer having an epoxy grouping which is cured by impinging radiation, and subjecting irradiated resist material to the said developing reagent so as to selectively remove unirradiated portions thereof, following which a substrate together with a now pattern-delineated resist is subjected to a modifying influence for the said substrate thereby resulting in modification of substrate material in those areas bared during development, characterized in that the said uncured polymer is substantially ethylenically saturated; that the said polymer has a weight average molecular weight of about 10 3 to 10 6 ; that the said epoxy grouping ##STR8## is connected to the main polymer chain through at least one branch atom; in that the said epoxy grouping is unmodified by esterification with methacrylic acid; and that the molecular weight distribution of the said polymer defined as M w /M n , in which M w is the weight average molecular weight and M n is the number average molecular weight, is numerically equal to a value of less than 5, and in that the said radiation is selected from the group consisting of ultraviolet wave energy, X-ray wave energy and electron radiation.

Claim 39

Process for pattern delineating a substrate surface on which there is a tightly adherent negative resist material comprising the steps of selectively exposing the said resist material to radiation with irradiated regions corresponding with a negative image of the pattern to be delineated on the substrate, so that the said radiation reduces the solubility of the said resist with respect to a developing reagent, in which the said resist material consists essentially of an uncured polymer having an epoxy grouping which is cured by impinging radiation, and subjecting irradiated resist material to the said developing reagent so as to selectively remove unirradiated portions thereof, following which a substrate together with a now pattern-delineated resist is subjected to a modifying influence for the said substrate thereby resulting in modification of substrate material in those areas bared during development, characterized in that the said uncured polymer is substantially ethylenically saturated; that the said polymer has a weight average molecular weight of about 10 3 to 10 6 ; that the said epoxy grouping ##STR8## is connected to the main polymer chain through at least one branch atom; in that the said epoxy grouping is unmodified by esterification with methacrylic acid; and that the molecular weight distribution of the said polymer defined as M w /M n , in which M w is the weight average molecular weight and M n is the number average molecular weight, is numerically equal to a value of less than 5, and in that the said radiation is selected from the group consisting of ultraviolet wave energy, X-ray wave energy and electron radiation.

Claim 40

Process of claim 36 in which epoxy moieties are neither totally nor partially esterified with methacrylic acid.

Claim 41

Process of claim 36 in which the said modifying influence erodes the portions of the substrate bared during development.

Claim 42

Process of claim 38 in which erosion results from substrate attack by a chemical reagent.

Claim 43

Process of claim 38 in which the eroding influence is an ion beam.

Claim 44

Process of claim 36 in which the modifying influence results in deposition of material adherent at least to the portions of the substrate bared during development.

Claim 45

Process of claim 36 in which the radiation is electron radiation.

Claim 46

Process of claim 42 in which the radiation is a focused electron beam.

Claim 47

Process of claim 43 in which the beam diameter defined as the extremities of the beam within which the energy drop-off is a maximum of (1/e)th of the center energy is a maximum of 1 micrometer.

Claim 48

Process of claim 44 in which exposure results from a programmed scanning beam.

Claim 49

Process of claim 42 in which the radiation is a patterned array of electrons.

Claim 50

Process of claim 36 in which the said radiation is wave energy in the recited X-ray range.

Claim 51

Process of claim 47 in which exposure of selected areas results from passage of the said X-ray radiation through a mask.

Claim 52

Process in accordance with claim 36 comprising at least two sets of procedural steps as defined, said substrate comprising a semiconducting material.

Claim 53

Process of claim 49 in which at least a portion of the said substrate surface is oxidic.

Claim 54

Process of claim 36 in which at least a portion of the substrate surface at which the said resist makes intimate contact is an oxide of silicon and in which the said selected regions define the negative image of a diffraction grating.

Claim 55

Process of claim 36 in which the substrate comprises a semiconducting material in which at least a portion of the substrate surface with which the resist makes intimate contact is metallic and in which the said selected regions define a negative image of a circuit design.

Claim 56

Process of claim 36 in which the said polymer contains aryl groupings.

Claim 57

Process of claim 53 in which the said polymer contains at least one aryl grouping for every twenty chain carbon atoms.

Claim 58

Process of claim 53 in which the said aryl groupings are selected from the group consisting of halogenated and unhalogenated phenyl, napthyl, and anthryl.

Claim 59

Process of claim 53 in which the said modifying influence comprises ionizing radiation.

Claim 60

Process of claim 56 in which the said modifying influence defines sputter etching.

Claim 61

Process of claim 56 in which the said modifying influence defines ion milling.

Claim 62

Process of claim 56 in which the said modifying influence defines ion implantation.

Claim 63

Process of claim 53 in which the said impinging radiation defines an image of accelerated electrons delinated by passage through a mask.

Claim 64

Process of claim 53 in which the said impinging radiation defines an image of X-ray radiation delineated by passage through a mask.

Claim 65

The process of claim 53 in which the said polymer contains epoxy-containing branches in number at least equal to one such branch for every ten carbon atoms in the main polymer chain.