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EP0251241A2
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Top imaged resists
Assignee: International Business Machines Corp
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Filing: 1987-06-26
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Granted: —
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Expires: 2007-06-26
Abstract
Abstract The present invention is concerned with a method of converting a single resist layer into a multilayered resist. The upper portion of the single resist layer can be patternwise converted into a chemically different composition or structure having altered absorptivity toward radiation. The difference in radiation absorptivity within the patterned upper portion of the resist enables subsequent use of blanket irradiation of the resist surface to create differences in chemical solubility between areas having the altered absorptivity toward radiation and non-altered areas. The difference in chemical solubility enables wet development of the patterned resist.
Inventors
- 👤 Robert David Allen
- 👤 Kaolin N. Chiong
- 👤 Ming-Fea Chow
- 👤 Scott Arthur Macdonald
- 👤 Jer-Ming Yang
- 👤 Carlton Grant Willson
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-04 19:39
CPC Classifications
G; G03; G03F; G03F7/00; G03F7/26; G03F7/265; G03F7/004; G03F7/038; G03F7/20; G03F7/2022; Y; Y10; Y10S; Y10S430/00; Y10S430/143; Y10S430/167; Y10S430/168
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
161 words
Method of converting the upper portion of a layer of polymeric material into a patterned, wet-developable multilayered resist, comprising: a) providing a layer of polymeric material comprised of at least one component which undergoes molecular rearrangement upon irradiation to produce reactive hydrogens; b) patternwise irradiating the surface of said layer of polymeric material to induce molecular rearrangement of said at least one component to form reaction products having reactive hydrogens in at least the upper portion of said patternwise irradiated layer; and c) treating said reaction products of said irradiated layer with a dye or reactive material capable of creating a dye upon reaction with said reaction products, so that a chemically different composition or structure having altered absorptivity toward radiation is created in the upper portion of said patternwise irradiated layer; and d) blanket irradiating said patternwise irradiated, dye-treated layer at a wavelength at which the dyed portions are strongly absorbing and the non-dyed, original polymeric material is significantly transparent.
Claim 2
Dependent Claim
161 words
Method of converting the upper portion of a layer of polymeric material into a patterned, wet-developable multilayered resist, comprising: a) providing a layer of polymeric material comprised of at least one component which undergoes molecular rearrangement upon irradiation to produce reactive hydrogens; b) patternwise irradiating the surface of said layer of polymeric material to induce molecular rearrangement of said at least one component to form reaction products having reactive hydrogens in at least the upper portion of said patternwise irradiated layer; and c) treating said reaction products of said irradiated layer with a dye or reactive material capable of creating a dye upon reaction with said reaction products, so that a chemically different composition or structure having altered absorptivity toward radiation is created in the upper portion of said patternwise irradiated layer; and d) blanket irradiating said patternwise irradiated, dye-treated layer at a wavelength at which the dyed portions are strongly absorbing and the non-dyed, original polymeric material is significantly transparent.
Claim 3
Dependent Claim
46 words
Method of claim 1 wherein said at least one component which undergoes molecular arrangement is selected from the group consisting of (1) o-nitrobenzyl derivates which rearrange on exposure to radiation to form alcohols, acids, and amines, (2) photo-fries reactive units, (3) diazoketones, and (4) mixtures thereof.
Claim 4
Dependent Claim
55 words
Method of claim 2 wherein said component of said polymeric material is selected from the group consisting of wherein R₁, R₂, R₃ and R₅ = H, alkyl, aryl, or part of a polymer backbone and R₄ = H, C n H 2n+1 wherein n ranges from about 1 to about 5, phenyl or substituted phenyls.
Claim 5
Dependent Claim
72 words
Method of claim 3 wherein R₁ = part of a polymer backbone, wherein said polymer is a styrene derivative or an acrylate based polymer; R₂, R₃ and R₅ = H, C n H 2n+1 wherein n ranges from 1 to about 15, phenyl, substituted phenyls, and other radicals which are benzene derivatives; and R₄ = H, C n H 2n+1 wherein n ranges from 1 to about 5, phenyl and substituted phenyls.
Claim 6
Dependent Claim
157 words
Method of converting the upper portion of a layer of sensitized polymeric resist material to a patterned, wet developable form, comprising: a) providing a layer of sensitized polymeric resist material comprised of a polymer having recurrent acid labile groups combined with an acid progenitor which generates acid on exposure to radiation; b) pattern-wise irradiating surface areas of said layer of polymeric resist material to induce said acid progenitor to generate an acid at least within the upper portion of said pattern-wise irradiated areas; c) heat treating said irradiated resist to generate functional groups in at least the upper portions of said polymeric resist material; and d) treating said functional groups with a dye or reactive material capable of creating a dye upon reaction with said functional groups; and e) blanket irradiating said patternwise irradiated, dye-treated layer at a wavelength at which the dyed portions are strongly absorbing and the non-dyed original sensitized polymeric material is significantly transparent.
Claim 7
Dependent Claim
157 words
Method of converting the upper portion of a layer of sensitized polymeric resist material to a patterned, wet developable form, comprising: a) providing a layer of sensitized polymeric resist material comprised of a polymer having recurrent acid labile groups combined with an acid progenitor which generates acid on exposure to radiation; b) pattern-wise irradiating surface areas of said layer of polymeric resist material to induce said acid progenitor to generate an acid at least within the upper portion of said pattern-wise irradiated areas; c) heat treating said irradiated resist to generate functional groups in at least the upper portions of said polymeric resist material; and d) treating said functional groups with a dye or reactive material capable of creating a dye upon reaction with said functional groups; and e) blanket irradiating said patternwise irradiated, dye-treated layer at a wavelength at which the dyed portions are strongly absorbing and the non-dyed original sensitized polymeric material is significantly transparent.
Claim 8
Dependent Claim
27 words
Method of claim 5 wherein said polymer comprising recurrent acid labile groups is selected from the group consisting of amides, urethanes, esters, ethers, non-basic amines, and ureas.
Claim 9
Dependent Claim
65 words
Method of claim 6 wherein said polymer comprising recurrent acid labile groups is selected from the group consisting of polycarbonates, polyethers, substituted polyvinylbenzoates; and substituted polyvinylphenols, substituted polystyrenes, substituted maleimide-comprising polymers, and substituted styrene-maleimide copolymers, wherein phenyl or nitrogen moieties within the polymeric structure are substituted with an acid labile functional group such as esters of a carboxylic acid and esters of a carbonic acid.
Claim 10
Dependent Claim
13 words
Method of claim 7 wherein said acid progenitor is a cationic photoactive compound.
Claim 11
Dependent Claim
15 words
Method of claim 8 wherein said cationic photoactive compound is an onium salt metal halide.
Claim 12
Dependent Claim
26 words
Method of claims 1 and 5 wherein said irradiation source is selected from the group consisting of photon emission sources, electron beam, ion beam, and X-ray.
Claim 13
Dependent Claim
30 words
Method of claim 10 wherein said irradiation source is a low acceleration voltage electron beam and wherein said electron beam voltage ranges from about 0.5 Kev to about 10 Kev.
Claim 14
Dependent Claim
27 words
Method of claim 1 and 5 including the additional step of: developing the patterned image in said irradiated and reacted areas by treatment with an oxygen plasma.
Claim 15
Dependent Claim
31 words
Method of claim 1 and 5 wherein said layer of polymeric resist material ranges from about 0.5 to about 20 micrometers, preferably from about 1.0 to about 3.0 micrometers in thickness.
Claim 16
Dependent Claim
40 words
Method of claims 1 and 5 wherein said upper portion of said layer of polymeric resist material or sensitized polymeric resist material ranges from about 0.1 to about 1.0 micrometers preferably from about 0.1 to about 0.5 micrometers in depth.
Claim 17
Dependent Claim
18 words
Method of claim 5 wherein said substrate comprises a radiation sensitive or a non radiation sensitive polymeric material
Claim 18
Dependent Claim
84 words
Method of claims 1 and 5 wherein said conversion of said upper portion of said patterned resist to a wet-developable form is limited to the upper portion of said layer of polymeric material or said layer of polymeric resist material by controlling the process conditions during treatment with said dye or reactive material capable of creating a dye, so that penetration of said organometallic reagent is limited to said upper portion of said layer of polymeric material or said layer of polymeric resist material.
Claim 19
Dependent Claim
38 words
Resist structure wherein patterned upper portions of a single resist layer are comprised of a dye which is strongly absorbing at some wavelength of radiation at which the non-dyed resist layer portions are both sensitive and significantly transparent.
Claim 20
Dependent Claim
38 words
Resist structure wherein patterned upper portions of a single resist layer are comprised of a dye which is strongly absorbing at some wavelength of radiation at which the non-dyed resist layer portions are both sensitive and significantly transparent.
Claim 21
Dependent Claim
120 words
Method of converting the upper portion of a layer comprising a sensitized polymeric resist material into a dry etch-resistant form, comprising, providing a layer of sensitized polymeric resist material comprising a polymer having recurrent acid labile groups combined with an acid progenitor hich generates acid on exposure to radiation; irradiating at least some areas of the surface of said sensitized polymeric resist material to induce said acid progenitor to generate an acid in at least the upper portions of said layer of sensitized polymeric resist material which have been irradiated; heat treating said irradiated resist material to generate functional groups capable of reacting with an organometallic reagent; and treating the reaction products of said functional groups with an organometallic reagent.
Claim 22
Dependent Claim
120 words
Method of converting the upper portion of a layer comprising a sensitized polymeric resist material into a dry etch-resistant form, comprising, providing a layer of sensitized polymeric resist material comprising a polymer having recurrent acid labile groups combined with an acid progenitor hich generates acid on exposure to radiation; irradiating at least some areas of the surface of said sensitized polymeric resist material to induce said acid progenitor to generate an acid in at least the upper portions of said layer of sensitized polymeric resist material which have been irradiated; heat treating said irradiated resist material to generate functional groups capable of reacting with an organometallic reagent; and treating the reaction products of said functional groups with an organometallic reagent.
Claim 23
Dependent Claim
14 words
Method of claim 18 wherein said reactive organometallic reagent is comprised of silicon-containing compound.
References Cited (Backward Citations)
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