Patent US4587205A successfully refreshed from Google Patents.
← Back to Patent Explorer
US4587205A Expired / Lapsed US ⏱️ 0.0 years remaining

Method of using polysilane positive photoresist materials

Assignee: United States Department of Energy
•
Filing: 1984-11-29
•
Granted: 1986-05-06
•
Expires: 2004-11-29
📄 Original PDF 🌐 Google Patents 🔄 Sync Now

Abstract

Abstract New polysilane copolymers comprise recurring units of --Si(X)(Y)-- and Si(A)(B)--, Si(X)(Y) being different from Si(A)(B), wherein X and Y together have 1-13 carbon atoms, and X and Y each independently is hydrogen, alkyl, cycloalkyl, phenyl, alkylphenyl, or phenylalkyl, with the proviso that only one of X and Y contains a phenyl moiety, or together X and Y are an alkylene group forming a ring with the adjoining Si atom, and wherein A and B together have 3-13 carbon atoms, and A and B each independently is alkyl or cycloalkyl, with the proviso (a) that when one of A and B is ethyl, the other is not methyl or ethyl, and (b) that when one of A ad B is n-propyl and the other is methyl, X and Y are not both methyl. Corresponding homopolysilanes are also provided. Upon ultraviolet irradiation, they photodepolymerize to form volatile products. As a result, they represent a new class of photoresists which enable direct formation of a positive image eliminating the heretofore required development step.

Inventors

  • 👤 Larry A. Harrah
  • 👤 John M. Zeigler

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-29 12:35
CPC Classifications
G; G03; G03F; G03F7/00; G03F7/004; G03F7/075; G03F7/0754; C; C08; C08G; C08G77/00; C08G77/60

Claims Analysis

Total Claims: 17
Claim 1
Independent Claim 474 words
A method of photopatterning a positive image onto a substrate coated with a polysilane, comprising irradiating the coated substrate with actinic radiation forming a pattern of said positive image on the substrate, whereby the portions of the polysilane coating on which said radiation impinges are photodepolymerized to form products which volatilize and whereby said substrate becomes uncoated in the pattern of said positive image, wherein said polysilane is a homopolymer which is substantially free of low molecular weight oligomers or cyclic materials and which comprises recurring units of --Si(X)(Y)--, wherein X and Y together have 4 to 13 carbon atoms, and X and Y each independently is hydrogen, alkyl, cycloalkyl, substituted phenyl, 1- or 2-naphthyl, or phenylalkyl, or togehter X and Y are an alkylene group forming a ring with the adjoining Si atom, wherein X and Y groups which are not H can be substituted by one of C 1-6 -alkoxy, mono- or di(C 1-3 -alkyl)amino, C 2-6 -alkanoyl or the corresponding C 2-3 -ketal thereof, C 1-6 -alkyl, --NH 2 or --OH; with the proviso that only one of X and Y can be a substituted phenyl, and wherein, as a result of the selection of X and Y, said polysilane has sufficient photosensitivity to depolymerize upon exposure to actinic radiation, forming products which volatilize; or wherein said polysilane is a copolymer comprising recurring units of --Si(X)(Y)--, and Si(A)(B)--, Si(X)(Y)-- being different from Si(A)(B)--, wherein X and Y together have 1 to 13 carbon atoms, and X and Y each independently is hydrogen, alkyl, cycloalkyl, phenyl, alkylphenyl, or phenylalkyl, with the proviso that only one of X and Y contains a phenyl moiety, or together X and Y are an alkylene group forming a ring with the adjoining Si atom, and wherein A and B together have 3 to 13 carbon atoms, and A and B each independently is alkyl, 1- or 2-naphthyl, or cycloalkyl, wherein X, Y, A, or B groups which are not H can be substituted by one of C 1-6 -alkoxy, mono- or di-(C 1-3 -alkyl)amino, C 2-6 -alkanoyl or the corresponding C 2-3 -ketal thereof, C 1-6 -alkyl, --NH 2 , or --OH; with the proviso (a) that when one of A and B is ethyl, the other is not methyl or ethyl, and (b) that when one of A and B is n-propyl and the other is methyl, X and Y are not both methyl, wherein A and B are substituents imparting sufficient steric hindrance to the copolymer that it photodepolymerizes upon exposure to actinic radiation, and wherein X and Y are substituents of sufficiently low weight that the products of said photodepolymerization volatilize at the instantaneous temperature of the depolymerizing polymer during irradiation; and wherein said substituents in homo- or copolymers are such that the polymer undergoes substantially no self-crosslinking upon exposure to actinic radiation.
Claim 2
Independent Claim 474 words
A method of photopatterning a positive image onto a substrate coated with a polysilane, comprising irradiating the coated substrate with actinic radiation forming a pattern of said positive image on the substrate, whereby the portions of the polysilane coating on which said radiation impinges are photodepolymerized to form products which volatilize and whereby said substrate becomes uncoated in the pattern of said positive image, wherein said polysilane is a homopolymer which is substantially free of low molecular weight oligomers or cyclic materials and which comprises recurring units of --Si(X)(Y)--, wherein X and Y together have 4 to 13 carbon atoms, and X and Y each independently is hydrogen, alkyl, cycloalkyl, substituted phenyl, 1- or 2-naphthyl, or phenylalkyl, or togehter X and Y are an alkylene group forming a ring with the adjoining Si atom, wherein X and Y groups which are not H can be substituted by one of C 1-6 -alkoxy, mono- or di(C 1-3 -alkyl)amino, C 2-6 -alkanoyl or the corresponding C 2-3 -ketal thereof, C 1-6 -alkyl, --NH 2 or --OH; with the proviso that only one of X and Y can be a substituted phenyl, and wherein, as a result of the selection of X and Y, said polysilane has sufficient photosensitivity to depolymerize upon exposure to actinic radiation, forming products which volatilize; or wherein said polysilane is a copolymer comprising recurring units of --Si(X)(Y)--, and Si(A)(B)--, Si(X)(Y)-- being different from Si(A)(B)--, wherein X and Y together have 1 to 13 carbon atoms, and X and Y each independently is hydrogen, alkyl, cycloalkyl, phenyl, alkylphenyl, or phenylalkyl, with the proviso that only one of X and Y contains a phenyl moiety, or together X and Y are an alkylene group forming a ring with the adjoining Si atom, and wherein A and B together have 3 to 13 carbon atoms, and A and B each independently is alkyl, 1- or 2-naphthyl, or cycloalkyl, wherein X, Y, A, or B groups which are not H can be substituted by one of C 1-6 -alkoxy, mono- or di-(C 1-3 -alkyl)amino, C 2-6 -alkanoyl or the corresponding C 2-3 -ketal thereof, C 1-6 -alkyl, --NH 2 , or --OH; with the proviso (a) that when one of A and B is ethyl, the other is not methyl or ethyl, and (b) that when one of A and B is n-propyl and the other is methyl, X and Y are not both methyl, wherein A and B are substituents imparting sufficient steric hindrance to the copolymer that it photodepolymerizes upon exposure to actinic radiation, and wherein X and Y are substituents of sufficiently low weight that the products of said photodepolymerization volatilize at the instantaneous temperature of the depolymerizing polymer during irradiation; and wherein said substituents in homo- or copolymers are such that the polymer undergoes substantially no self-crosslinking upon exposure to actinic radiation.
Claim 3
Dependent Claim 19 words
A method of claim 1 wherein the temperature of the polysilane coating during the irradiation is about room temperature.
Claim 4
Dependent Claim 24 words
A method of claim 1 wherein the temperature of the polysilane coating during the irradiation is from about room temperature to about 230° C.
Claim 5
Dependent Claim 40 words
A method of claim 1 wherein the actinic radiation is U.V. radiation of a wavelength of about 250 nm or shorter and is of an intensity such that the average temperature of the polysilane coating remains substantially unchanged during irradiation.
Claim 6
Dependent Claim 65 words
A method of claim 3 wherein the actinic radiation is U.V. radiation of a wavelength of about 250 nm or shorter and is of an intensity sufficiently high to raise the instantaneous temperature of the depolymerizing polysilane during irradiation to a level sufficient to volatilize the products of the photodepolymerization but insufficient to cause irreversible thermal effects in the remaining polysilane which is not depolymerized.
Claim 7
Dependent Claim 17 words
A method of claim 1 wherein the resolution of the photopatterned positive image is about 1-4 μm.
Claim 8
Dependent Claim 15 words
The method of claim 1 wherein neither X nor Y in the copolymer is H.
Claim 9
Dependent Claim 26 words
A method of claim 1 wherein X and Y are both methyl and wherein one of A and B is methyl and the other is cyclohexyl.
Claim 10
Dependent Claim 31 words
A method of claim 1 wherein one of X and Y is methyl and the other is n-propyl, and one of A and B is methyl and the other is isopropyl.
Claim 11
Dependent Claim 44 words
A method of claim 1 wherein X and Y each is methyl, ethyl, or propyl, or X and Y together form pentamethylene; and wherein one of A and B is n-propyl, isopropyl, t-butyl, cyclohexyl, n-hexyl, or n-dodecyl and the other is methyl or ethyl.
Claim 12
Dependent Claim 50 words
A method of claim 1 wherein X and Y each is methyl, and one of A and B is cyclohexyl, n-hexyl or n-dodecyl; or wherein one of X and Y is methyl and the other is n-propyl, and one of A and B is methyl and the other is isopropyl.
Claim 13
Dependent Claim 17 words
A method of claim 1 wherein the substrate is one suitable for use in a microelectronic device.
Claim 14
Dependent Claim 18 words
A method of claim 1 further comprising, prior to said irradiation step, coating said substrate with said polysilane.
Claim 15
Dependent Claim 114 words
A radiative method of producing a positive image of a desired pattern in a surface of a substrate, comprising, (a) coating the surface with a polysilane, (b) photopatterning the polysilane coating with a positive image of said desired pattern according to the method of claim 1, the polysilane of step (a) above being that recited in claim 1, whereby the portions of the polysilane coating on which said radiation impinges are photodepolymerized to form products which volatilize and whereby said substrate becomes uncoated in the pattern of said positive image, (c) treating the thus-exposed surface areas to form the desired pattern in the substrate surface; and (d) removing the polysilane remaining on the surface.
Claim 16
Dependent Claim 28 words
A method of claim 14 wherein step (d) is carried out by exposing the surface to actinic radiation effective to photodepolymerize and volatilize the remaining polysilane or solvent.
Claim 17
Dependent Claim 19 words
A method of claim 14 wherein step (d) is carried out by dissolving the remaining polysilane in a solvent.

References Cited (Backward Citations)

US2554976A Cited
US2612511A Cited
US2606879A Cited
DE1236506B Cited
US3890149A Cited
US3907564A Cited
US4052430A Cited
US4276424A Cited
US4377677A Cited
US4324901A Cited
US4396702A Cited
US4464460A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1989-05-05 1989-11-04 1990-05-06 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1993-05-05 1993-11-04 1994-05-06 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1997-05-05 1997-11-04 1998-05-06 $7700.00 Window Closed / Lapsed

Assigned Categories & Tags

No categories assigned to this patent yet.

Assign Category Tag