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US4777111A Expired / Lapsed US ⏱️ 0.0 years remaining

Photographic element with diazo contrast enhancement layer and method of producing image in underlying photoresist layer of element

Assignee: Fairmount Chemical Co Inc
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Filing: 1987-03-23
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Granted: 1988-10-11
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Expires: 2007-03-23
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Abstract

Abstract This invention relates to a composition and method for enhancing the contrast of images of an underlying photolithographic layer. A photographic element, including a photoresist layer, is applied to a substrate. The photoresist layer contains a contrast-enhancing layer including at least one light-sensitive compound capable of producing acidic photoproducts upon exposure to actinic radiation, at least one indicator dye that changes color on exposure to acidic conditions and at least one polymeric binder soluble in water or weakly alkaline aqueous solutions. The photographic element is exposed to active radiation sufficient to cause photobleaching of the contrast enhancement layer and exposure of the photoresist layer. The photographic element is exposed to actinic radiation sufficient to cause photobleaching of the contrast enhancement layer and exposure of the photoresist layer. The photographic element is developed in an aqueous photoresist developer, whereby the contrast enhancement layer is stripped from the photoresist layer by the developer.

Inventors

  • 👤 David B. Blumel
  • 👤 Albert S. Deutsch

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-30 21:02
CPC Classifications
G; G03; G03F; G03F7/00; G03F7/004; G03F7/09; G03F7/091

Claims Analysis

Total Claims: 10
Claim 1
Independent Claim 253 words
A photographic element comprising: a positive photoresist layer applied to a substrate; and a contrast enhancement layer applied to said photoresist layer, said contrast enhancement layer including: at least one water-soluble light-sensitive compound producing acidic photoproducts upon exposure to actinic radiation and the absorbance of which to radiation in the range of about 300 to 400 nanometers substantially disappears, said sensitive compound being selected from the group consisting of naphthoquinone-1,2-(diazide-2)-5-sodium sulfonate, naphthoquinone-1,2-(diazide-2)-4-sodium sulfonate, 4-diazo-N-ethyl-N-hydroxyethylaniline; 4-diazo-2-chloro-N-N'-diethylaniline; 4-diazo-2-methyl-1-pyrrolidine benzene; 4-diazo-2,5-dibutoxy-N-benzoylaniline; 4-diazo-1-morpholinobenzene; 4-diazo-N-ethyl-2-toluidine; 4-diazodiethylaniline; 4-diazodimethylaniline; 4-diazodiphenylamine sulfate; and 4-diazo-2,5-diethoxyphenylmorpholine; at least one water soluble indicator dye which before exposure to acidic conditions is highly absorbent to radiation within the range of about 350 to about 450 nm, but upon exposure to acidic conditions, undergoes a substantial disappearance of its absorbance of radiation in said range, said dye being selected from the group consisting of 2,4-dinitrophenol, 3-nitrosalicylaldehyde, metaniline yellow, methyl orange, ethyl orange, propyl red, ethyl red, methyl red, p-nitrophenol, m-nitrophenol, sodium-p-nitrophenoxide and pyridine-2-azodimethylaniline; and at least one polymeric binder which is substantially transparent to radiation in the range of about 300 to about 450 nm and is soluble in a member of the group consisting of water and weakly alkaline aqueous solutions; wherein said compound is provided in an amount ranging between about 5 and about 90% by weight based on said polymeric binder and said indicator dye is provided in an amount not exceeding the amount at which said dye can be rendered transparent to said radiation range by said acidic photoproducing of said compound.
Claim 2
Dependent Claim 253 words
A photographic element comprising: a positive photoresist layer applied to a substrate; and a contrast enhancement layer applied to said photoresist layer, said contrast enhancement layer including: at least one water-soluble light-sensitive compound producing acidic photoproducts upon exposure to actinic radiation and the absorbance of which to radiation in the range of about 300 to 400 nanometers substantially disappears, said sensitive compound being selected from the group consisting of naphthoquinone-1,2-(diazide-2)-5-sodium sulfonate, naphthoquinone-1,2-(diazide-2)-4-sodium sulfonate, 4-diazo-N-ethyl-N-hydroxyethylaniline; 4-diazo-2-chloro-N-N'-diethylaniline; 4-diazo-2-methyl-1-pyrrolidine benzene; 4-diazo-2,5-dibutoxy-N-benzoylaniline; 4-diazo-1-morpholinobenzene; 4-diazo-N-ethyl-2-toluidine; 4-diazodiethylaniline; 4-diazodimethylaniline; 4-diazodiphenylamine sulfate; and 4-diazo-2,5-diethoxyphenylmorpholine; at least one water soluble indicator dye which before exposure to acidic conditions is highly absorbent to radiation within the range of about 350 to about 450 nm, but upon exposure to acidic conditions, undergoes a substantial disappearance of its absorbance of radiation in said range, said dye being selected from the group consisting of 2,4-dinitrophenol, 3-nitrosalicylaldehyde, metaniline yellow, methyl orange, ethyl orange, propyl red, ethyl red, methyl red, p-nitrophenol, m-nitrophenol, sodium-p-nitrophenoxide and pyridine-2-azodimethylaniline; and at least one polymeric binder which is substantially transparent to radiation in the range of about 300 to about 450 nm and is soluble in a member of the group consisting of water and weakly alkaline aqueous solutions; wherein said compound is provided in an amount ranging between about 5 and about 90% by weight based on said polymeric binder and said indicator dye is provided in an amount not exceeding the amount at which said dye can be rendered transparent to said radiation range by said acidic photoproducing of said compound.
Claim 3
Dependent Claim 22 words
The element of claim 1, wherein said binder is soluble in the developing solutions used for the development of said photoresist layer.
Claim 4
Dependent Claim 25 words
The element of claim 2, wherein said polymeric binder is selected from the group consisting of poly(vinyl alcohol), poly(vinyl pyrrolidone) and vinyl pyrrolidone/vinyl acetate copolymers.
Claim 5
Independent Claim 315 words
A method of producing an image in a photographic element by imagewise exposing said element to a source of actinic radiation, said method comprising the steps of: providing a photographic element including a positive photoresist layer applied to a substrate; applying to the photoresist layer a contrastenhancing layer including: at least one light-sensitive compound producing acidic photoproducts upon exposure to actinic radiation and the absorbance of which to radiation in the range of about 300 to about 400 nanometers substantially disappears, said sensitive compound being selected from the group consisting of naphthoquinone-1,2-(diazide-2)-5-sodium sulfonate, naphthoquinone-1,2-(diazide-2)-4-sodium sulfonate, 4-diazo-N-ethyl-N-hydroxyethylaniline; 4-diazo-2-chloro-N-N'-diethylaniline; 4-diazo-2-methyl-1-pyrrolidine benzene; 4-diazo-2,5-dibutoxy-N-benzoylaniline; 4-diazo-1-morpholinobenzene; 4-diazo-N-ethyl-2-toluidine; 4-diazodiethylaniline; 4-diazodimethylaniline; 4-diazodiphenylamine sulfate; and 4-diazo-2,5-diethoxyphenylmorpholine; at least one indicator dye which before exposure to acidic conditions is highly absorbent to radiation within the range of about 350 to about 450 nm, but upon exposure to acidic conditions, undergoes a substantial disappearance of its absorbance of radiation in said range, said dye being selected from the group consisting of 2,4-dinitrophenol, 3-nitrosalicylaldehyde, metaniline yellow, methyl orange, ethyl orange, propyl red, ethyl red, methyl red, p-nitrophenol, m-nitrophenol, sodium-p-nitrophenoxide and pyridine-2-azodimethylaniline that changes color on exposure to acidic conditions; and at least one polymeric binder which is substantially transparent to radiation in the range of about 300 to about 450 nm and is soluble in water or weakly alkaline aqueous solutions; wherein said compound is provided in an amount ranging between about 5 and about 90% by weight based on said polymeric binder and said indicator dye is provided in an amount not exceeding the amount at which said dye can be rendered transparent to said radiation range by said acidic photoproducing of said compound; exposing said photographic element having said contrast enhancing layer applied thereon to actinic radiation sufficient to cause photo-bleaching of said contrast enhancement layer and selective exposure of said photoresist layer; developing said exposed resist thereby causing removal of said exposed resist.
Claim 6
Independent Claim 315 words
A method of producing an image in a photographic element by imagewise exposing said element to a source of actinic radiation, said method comprising the steps of: providing a photographic element including a positive photoresist layer applied to a substrate; applying to the photoresist layer a contrastenhancing layer including: at least one light-sensitive compound producing acidic photoproducts upon exposure to actinic radiation and the absorbance of which to radiation in the range of about 300 to about 400 nanometers substantially disappears, said sensitive compound being selected from the group consisting of naphthoquinone-1,2-(diazide-2)-5-sodium sulfonate, naphthoquinone-1,2-(diazide-2)-4-sodium sulfonate, 4-diazo-N-ethyl-N-hydroxyethylaniline; 4-diazo-2-chloro-N-N'-diethylaniline; 4-diazo-2-methyl-1-pyrrolidine benzene; 4-diazo-2,5-dibutoxy-N-benzoylaniline; 4-diazo-1-morpholinobenzene; 4-diazo-N-ethyl-2-toluidine; 4-diazodiethylaniline; 4-diazodimethylaniline; 4-diazodiphenylamine sulfate; and 4-diazo-2,5-diethoxyphenylmorpholine; at least one indicator dye which before exposure to acidic conditions is highly absorbent to radiation within the range of about 350 to about 450 nm, but upon exposure to acidic conditions, undergoes a substantial disappearance of its absorbance of radiation in said range, said dye being selected from the group consisting of 2,4-dinitrophenol, 3-nitrosalicylaldehyde, metaniline yellow, methyl orange, ethyl orange, propyl red, ethyl red, methyl red, p-nitrophenol, m-nitrophenol, sodium-p-nitrophenoxide and pyridine-2-azodimethylaniline that changes color on exposure to acidic conditions; and at least one polymeric binder which is substantially transparent to radiation in the range of about 300 to about 450 nm and is soluble in water or weakly alkaline aqueous solutions; wherein said compound is provided in an amount ranging between about 5 and about 90% by weight based on said polymeric binder and said indicator dye is provided in an amount not exceeding the amount at which said dye can be rendered transparent to said radiation range by said acidic photoproducing of said compound; exposing said photographic element having said contrast enhancing layer applied thereon to actinic radiation sufficient to cause photo-bleaching of said contrast enhancement layer and selective exposure of said photoresist layer; developing said exposed resist thereby causing removal of said exposed resist.
Claim 7
Dependent Claim 23 words
The method of claim 4 wherein said actinic radiation to which said element is exposed ranges between about 300 and about 450 nm.
Claim 8
Dependent Claim 20 words
The method of claim 5, wherein said exposure lasts about twice the time of exposure of an uncoated photoresist material.
Claim 9
Dependent Claim 22 words
The method of claim 4, wherein said binder is soluble in the developing solutions used for the development of said photoresist layer.
Claim 10
Dependent Claim 25 words
The method of claim 7, wherein said polymeric binder is selected from the group consisting of poly(vinyl alcohol), poly(vinyl pyrrolidone) and vinyl pyrrolidone/vinyl acetate copolymers.

References Cited (Backward Citations)

US2702243A Cited
GB1041463A Cited
US4197128A Cited
GB1586573A Cited
US4125650A Cited
US4564581A Cited
EP0110165A2 Cited
EP0161660A2 Cited
US4672021A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1991-10-11 1992-04-11 1992-10-11 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1995-10-11 1996-04-11 1996-10-11 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1999-10-11 2000-04-11 2000-10-11 $7700.00 Window Closed / Lapsed

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